CN110957093A - R-T-B series magnet material, raw material composition, preparation method and application - Google Patents

R-T-B series magnet material, raw material composition, preparation method and application Download PDF

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CN110957093A
CN110957093A CN201911316696.8A CN201911316696A CN110957093A CN 110957093 A CN110957093 A CN 110957093A CN 201911316696 A CN201911316696 A CN 201911316696A CN 110957093 A CN110957093 A CN 110957093A
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percentage
mass
magnet material
content
raw material
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CN110957093B (en
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付刚
陈大崑
黄佳莹
黄清芳
许德钦
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Fujian Jinlong Rare Earth Co ltd
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Xiamen Tungsten Co Ltd
Fujian Changting Jinlong Rare Earth Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets 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
    • H01F1/04Magnets 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
    • H01F1/047Alloys characterised by their composition
    • H01F1/053Alloys characterised by their composition containing rare earth metals
    • H01F1/055Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571Alloys 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
    • H01F1/0575Alloys 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
    • H01F1/0577Alloys 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/02Apparatus 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
    • H01F41/0253Apparatus 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/02Apparatus 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
    • H01F41/0253Apparatus 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
    • H01F41/0266Moulding; Pressing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/02Apparatus 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
    • H01F41/0253Apparatus 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
    • H01F41/0293Apparatus 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 an R-T-B series magnet material, a raw material composition, a preparation method and application. The raw material composition of the R-T-B series magnet material comprises the following components in percentage by mass: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3 percent; b: 0.9-1.2%; fe: 61-68% by mass of the total mass of the raw material composition of the R-T-B magnet material. The R-T-B series magnet material provided by the invention uses a formula of combining higher content of Pr with higher content of Cu, so that the coercive force of the R-T-B series magnet material can be obviously improved, and meanwhile, higher remanence can be maintained.

Description

R-T-B series magnet material, raw material composition, preparation method and application
Technical Field
The invention relates to an R-T-B series magnet material, a raw material composition, a preparation method and application.
Background
By Nd2Fe14The R-T-B system (NdFeB) magnet material with B as the main component has higher remanence, coercive force and maximum magnetic energy product, has excellent comprehensive magnetic performance, and is applied to the aspects of wind power generation, new energy automobiles, variable frequency household appliances and the like. At present, the rare earth component of the R-T-B magnet material in the prior art is mainly neodymium, only a small amount of Pr exists, and the performance of the magnet material can be improved by replacing a part of the Pr with the neodymium, but the improvement degree is limited. For example, the formula of the R-T-B magnet material disclosed in the currently reported Chinese patent document CN104979062A is as follows: 25-31 wt% of praseodymium, 0-5 wt% of neodymium, 0.12 wt% of gallium, 0.97-1 wt% of boron and other additive elements. The formula is added with a high content of praseodymium, but the coercive force can only reach 18kOe at most.
Disclosure of Invention
The invention aims to overcome the defect that the coercive force is improved to a limited extent after neodymium is replaced by partial Pr in an R-T-B series magnet material in the prior art, and provides the R-T-B series magnet material, a raw material composition, a preparation method and application. The R-T-B series magnet material provided by the invention uses higher content of Pr and higher content of Cu, so that the R-T-B series magnet material can maintain higher remanence while the coercive force is obviously improved.
The invention solves the technical problems through the following technical scheme.
The invention provides a raw material composition of an R-T-B series magnet material, which comprises the following components in percentage by mass:
r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent;
Cu:>1.3%;
B:0.9~1.2%;
fe: 61-68% by mass of the total mass of the raw material composition of the R-T-B magnet material.
In the present invention, the content of R' is preferably 29.65 to 31.65%, for example, 29.65%, 30.15%, 30.3%, 30.35%, 30.65%, 31.15%, 31.35%, or 31.65%, and the percentage means a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
In the present invention, the content of Pr is preferably 17.15 to 28.15%, for example, 17.15%, 18.15%, 19.15%, 20.15%, 20.85%, 21.15%, 22.15%, 22.85%, 23.15%, 24.15%, 25.15%, 25.85%, 26.15%, or 28.15%, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
In the present invention, the R' may further include Nd.
Wherein the mass ratio of Nd to R' is preferably less than 0.5, more preferably 0.08 to 0.45, for example, 9.5/31.65, 9.5/31.15, 9.5/30.65, 9.5/29.65, 8.5/31.35, 8.5/30.65, 7.5/30.65, 6.5/31.65, 6.5/30.65, 6.5/29.65, 5.5/31.65, 5.5/31.15, 5.5/30.65, 4.5/31.15, 4.5/30.65, 4.5/30.35, 4.5/29.65, 3.5/30.65, 3.5/30.15, 3.5/29.65, 2.5/30.65, 14/31.15, 13/31.15, 13.5/31.65, 13.5/30.65, 12/31.65, 12/31.15, 12/30.65, 12.5/30.65, 10.5/30.15/10.65, 10.5/30.10.10/30.15, 10.5/30.65, 10/10.10.10/10.5/30.15, 10.10.10/10.10.10.10.10.10/30.15, 10.10.10.10.10.10.10.15, 10.15, 10.10.5/30.15, 10.65.
The content of Nd is preferably 15% or less, more preferably 2.5 to 14.5%, for example, 2.5%, 3.5%, 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, 10%, 10.15%, 10.5%, 11.5%, 12%, 12.5%, 13%, 13.5%, or 14%, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
Wherein, said R' may also include Y.
In the present invention, the R' preferably further includes RH, which is a heavy rare earth element.
Wherein, the RH may be a heavy rare earth element conventional in the art, such as one or more of Dy, Tb and Ho, preferably Dy and/or Tb.
Wherein, the mass ratio of the RH to the R' can be the conventional mass ratio in the field, preferably less than 0.253, more preferably 0.1-1, such as 0, 1/31.65, 1.5/31.65, 2/31.65, 1.5/31.15, 1/30.65, 1/30.15, 2/31.35, 1/31.15, 0.5/30.15 or 1.5/30.15.
The RH content is preferably 2.5% or less, more preferably 0.5 to 2.5%, for example, 0.5%, 1%, 1.5% or 2%, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
When Tb is contained in the RH, the content of Tb is preferably 0.5 to 2%, for example, 0.5%, 1%, 1.5%, or 2%, and the percentage means the mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
When Dy is contained in the RH, the content of Dy is preferably 0.5 to 2%, for example, 0.5%, 1%, or 1.5%, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
In the present invention, the Cu content is preferably 1.3to 2.5%, for example, 1.31%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5%, and the percentage means a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
In the present invention, the content of B is preferably 0.92 to 1.2%, and for example, may be 0.905%, 0.955%, or 1.195%, and the percentage means a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
In the present invention, the content of Fe is preferably 61.8 to 68%, for example, 61.895%, 62.595%, 62.995%, 63.095%, 63.195%, 63.395%, 3.895%, 63.995%, 63.995%, 64.045%, 64.095%, 64.195%, 64.225%, 64.295%, 64.595%, 64.695%, 64.815%, 64.825%, 64.945%, 64.995%, 65.025%, 65.095%, 65.195%, 65.295%, 65.545%, 65.635%, 65.655%, 65.795%, 65.895%, 65.945%, 65.965%, 65.985%, 66.055%, 66.095%, 66.115%, 66.195%, 66.345%, 66.445%, 66.495%, 66.545%, 66.585%, 66.595%, 66.675%, 66.695%, 66.755%, 66.785%, 66.835%, 66.945%, 67.065%, 67.375%, 67.495%, 67.525% or 67.695%, and the percentage is a mass percentage of the total mass of the raw material composition of the R-T-B system magnet material.
In the present invention, the raw material composition of the R-T-B-based magnet material may further include one or more of Al, Ga, Co, Mn, Ni, Zn, Ag, In, Sn, Bi, V, Cr, Ta, and W.
Wherein, the content of Al can be the content conventional in the field, and is preferably 0-3% but not 0; for example, 0 to 0.03% but not 0, or 0.1 to 0.5%, or 0.5 to 3%; for another example, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.1%, 0.2%, 0.3%, 0.35%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.6%, or 2.9%, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
Wherein, the content of Ga may be a content conventionally used in the art, preferably less than 1%, more preferably 0.1 to 1%, for example, 0.1%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, and the percentage means a mass percentage based on the total mass of the raw material composition of the R-T-B based magnet material.
The content of Co may be a content conventionally used in the art, and is preferably 2% or less, more preferably 0.5 to 1.5%, for example, 0.5 or 1%, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
The content of Mn may be a content conventionally used in the art, and is preferably 0.05% or less, for example, 0.02% or 0.05%, and the percentage means a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
The content of Zn may be a content conventionally used in the art, and is preferably 0.05% or less, for example, 0.02% or 0.05%, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
In the present invention, the raw material composition of the R-T-B based magnet material may further include N, which generally refers to a high melting point metal in the art. The N species typically include Zr, Ti or Nb.
Wherein the content of N is a content which is conventional in the art, and is preferably 2.5% or less but not 0, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material.
When the kind of the N is Zr, the content of Zr is preferably 0.25 to 1%, for example, 0.25%, 0.3%, 0.5%, 0.8% or 1%, and the percentage means a mass percentage based on the total mass of the raw material composition of the R-T-B based magnet material.
When the N is Ti, the content of Ti is preferably 0.3 to 2.5%, for example, 0.3%, 0.6%, 1%, 1.5%, 2%, or 2.5%, and the percentage means the mass percentage based on the total mass of the raw material composition of the R-T-B based magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B based magnet material comprises the following components in parts by weight: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3-2.5%; al: 0 to 3% but not 0; b: 0.9-1.2%; fe: 61-68%, wherein the content of Al is preferably 0.5-3%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R' is a rare earth element and comprises Pr and Nd; wherein, the Pr: 17.15 to 28.15 percent; cu: 1.3-2.5%; al: 0.1-0.5%; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Nd is preferably 2.5-14.5%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R' is a rare earth element and comprises Pr and Nd; wherein, the Pr: 17.15 to 28.15 percent; cu: 1.3-2.5%; al: 0.5-3%; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Nd is preferably 2.5-14.5%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3-2.5%; al: 0 to 0.03% but not 0; ga: 0.25-1%; b: 0.9-1.2%; fe: 61-68%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R' is a rare earth element and comprises Pr and Nd; wherein, the Pr: 17.15 to 28.15 percent; cu: 1.3-2.5%; al: 0 to 0.03% but not 0; ga: 0.25-1%; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Nd is preferably 2.5-14.5%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3-2.5%; al: 0.1-0.5%; ti: 0.3-2.5%; b: 0.9-1.2%; fe: 61-68%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R' is a rare earth element and comprises Pr and Nd; wherein, the Pr: 17.15 to 28.15 percent; cu: 1.3-2.5%; al: 0.1-0.5%; ti: 0.3-2.5%; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Nd is preferably 2.5-14.5%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3-2.5%; al: 0.1-0.5%; ga: 0 to 0.25% but not 0; b: 0.9-1.2%; fe: 61-68%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material. Wherein, the content of Pr is preferably 17.15-28.15%; r' preferably further comprises Nd; the content of Nd is preferably 2.5-14.5%.
The invention provides a preparation method of an R-T-B series magnet material, wherein the raw material of the R-T-B series magnet material in the preparation method is the raw material composition adopting the R-T-B series magnet material.
In the present invention, the production method may be a method conventionally used in the art, for example, a melt of the raw material composition of the above-described R-T-B-based magnet material is subjected to casting, hydrogen fracturing, forming, sintering, and aging treatment.
In the present invention, the melt of the raw material composition of the R-T-B based magnet material can be prepared by a method conventional in the art, for example: smelting in a high-frequency vacuum induction smelting furnace. The vacuum degree of the smelting furnace can be 5 multiplied by 10-2Pa. The temperature of the smelting can be below 1500 ℃.
In the present invention, the operation and conditions for the casting may be those conventional in the art, for example, in an Ar atmosphere (e.g., 5.5X 10)4Pa in Ar atmosphere) at 10 deg.f2DEG C/sec-104Cooling at a rate of DEG C/sec.
In the present invention, the hydrogen decrepitation may be performed under conventional conditions. For example, the treatment of hydrogen absorption, dehydrogenation and cooling is carried out.
Wherein the hydrogen absorption can be carried out under the condition that the hydrogen pressure is 0.15 MPa.
Wherein the dehydrogenation is carried out under a condition of raising the temperature while evacuating.
In the present invention, the hydrogen may be broken and then pulverized by a conventional method in the art. The comminution process may be a comminution process conventional in the art, such as jet milling. The jet milling is preferably carried out under a nitrogen atmosphere having an oxidizing gas content of 150ppm or less. The oxidizing gas refers to oxygen or moisture content. The pressure of a crushing chamber for crushing by the jet mill is preferably 0.38 MPa; the jet mill pulverizing time is preferably 3 h.
After the pulverization, a lubricant such as zinc stearate may be added to the powder by a conventional method in the art. The amount of the lubricant added may be 0.10 to 0.15%, for example, 0.12% by weight of the mixed powder.
In the present invention, the operation and conditions of the forming may be those conventional in the art, such as a magnetic field forming method or a hot press hot deformation method.
In the present invention, the operation and conditions of the sintering may be those conventional in the art. For example, under vacuum conditions (e.g. at 5X 10)-3Pa, vacuum), preheating, sintering and cooling.
Wherein the preheating temperature is usually 300-600 ℃. The preheating time is usually 1-2 h. Preferably the preheating is for 1h at a temperature of 300 ℃ and 600 ℃ each.
Wherein, the sintering temperature is preferably 1030-1080 ℃, for example 1040 ℃.
The sintering time can be conventional in the art, and is usually 4 to 10 hours, for example 6 hours.
Wherein Ar gas can be introduced before cooling to ensure that the gas pressure reaches 0.1 MPa.
In the present invention, after the sintering and before the aging treatment, a grain boundary diffusion treatment is preferably further performed.
The operation and conditions for grain boundary diffusion can be those conventional in the art. For example, a Tb-containing substance and/or Dy-containing substance may be deposited on the surface of the R-T-B magnet material by vapor deposition, coating, or sputtering, and then subjected to diffusion heat treatment.
The Tb containing substance may be Tb metal, a Tb containing compound, such as a Tb containing fluoride or an alloy.
The Dy-containing substance may be Dy metal, a Dy-containing compound, such as a fluoride containing Dy, or an alloy.
The temperature of the diffusion heat treatment can be 800-900 ℃, for example 850 ℃.
The diffusion heat treatment time may be 12-48h, for example 24 h.
In the invention, in the aging treatment, the temperature of the secondary aging treatment is preferably 520-650 ℃, for example 550 ℃.
In the present invention, in the secondary aging treatment, the heating rate of heating to 520 to 650 ℃ is preferably 3to 5 ℃/min. The starting point of the warming may be room temperature.
The invention also provides an R-T-B series magnet material which is prepared by adopting the preparation method.
The invention also provides an R-T-B series magnet material, which comprises a grain boundary Fe-rich phase; the grain boundary Fe-rich phase comprises the following components in percentage by mass: r': 49-60%, wherein R 'is a rare earth element, and R' comprises Pr; t: 39-50%, wherein T comprises Fe; m: 1.5-4%, wherein M comprises Cu; the percentage is the mass percentage of each component in the total mass of the grain boundary Fe-rich phase.
In the invention, the grain boundary Fe-rich phase refers to R in atomic percentage6T13M1And (4) phase(s).
Wherein, R is6T13M1Preferably, the amount of the metal oxide is 2 to 25%, for example, 15% by volume based on the total volume of the R-T-B based magnet material.
In the grain boundary Fe-rich phase, the content of R' is preferably 49%, 51%, 52.3%, 53.4%, 54%, 54.5%, 55.5%, 56% or 57.1%, and the percentage is the mass percentage of each component in the total mass of the grain boundary Fe-rich phase.
In the grain boundary Fe-rich, R' can also comprise Nd.
In the grain boundary Fe-rich phase, the T can also comprise one or more of Co, Al and Ti.
In the grain boundary Fe-rich phase, the T content is preferably 39.5-46%, such as 39.55%, 40.65%, 40.74%, 41.45%, 41.68%, 42.22%, 42.31%, 42.32%, 42.85%, 43.3%, 43.89%, 44.22%, 45.45% or 47.67%, by mass, based on the total mass of the grain boundary Fe-rich phase.
In the grain boundary Fe-rich phase, the Cu content is preferably 1.5 to 3.8%, for example, 1.52%, 1.68%, 1.72%, 1.76%, 1.85%, 3.55%, 3.68%, 3.75%, 3.78%, 3.81%, 3.82%, or 3.85%, in percentage by mass based on the total mass of the grain boundary Fe-rich phase.
In the grain boundary Fe-rich phase, M may further include Ga.
When the M contains Ga, the content of the Ga is preferably 1.51%, 1.53%, 1.58%, 1.59%, 1.61% or 1.63% by mass based on the total mass of the grain boundary Fe-rich phase.
In the present invention, the R-T-B magnet material generally contains a main phase.
Wherein, the main phase preferably comprises the following components in percentage by mass: r': 26-28%, wherein R 'is a rare earth element, and R' comprises Pr; b: 0.9-1.2%; t: 70-72%, wherein the T comprises Fe, and the percentage is the mass percentage of each component in the total mass of the main phase.
In the main phase, the content of R' is preferably 26.5 to 28%, for example 26.2%, 26.9%, 27.2%, 27.3%, 27.4%, 27.5% or 27.8%, by mass, based on the total mass of the main phase.
In the main phase, the R' may further include Nd.
In the main phase, the content of B is preferably 0.95 to 1.2%, for example, 0.98%, 1.01%, 1.06%, or 1.17%, in mass% based on the total mass of the main phase.
In the main phase, the content of T is preferably 71 to 72%, for example, 71.14%, 71.33%, 71.53%, 1.62%, 71.64%, 71.69%, 71.72%, 71.74%, 71.82%, 71.93%, 72.09% or 72.79%, by mass, based on the total mass of the main phase.
In the main phase, the kind of T may further include one or more of Co, Al, and N. Wherein said N comprises Ti or Zr.
In the present invention, the R-T-B-based magnet material usually further includes a grain boundary R 'rich phase, and R' is a rare earth element.
The grain boundary R' -rich phase preferably comprises the following components in percentage by mass: r': 84-87%, O: 13-16%, wherein R 'comprises Pr, and the percentage is the mass percentage of each component in the total mass of the crystal boundary R' rich phase.
The grain boundary is rich in R 'phase, and the R' also comprises Nd.
In the grain boundary R ' rich phase, the content of R ' is preferably 84.5 to 86.5%, for example, 84.7%, 85.2%, or 86.3%, and the percentage is the mass percentage of each component in the total mass of the grain boundary R ' rich phase.
In the grain boundary R 'rich phase, the content of O is preferably 13.5 to 16%, for example, 13.7%, 14.8% or 15.7%, and the percentages are mass percentages of the components in the total mass of the grain boundary R' rich phase.
The invention also provides an R-T-B series magnet material which comprises the following components in percentage by mass:
r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: not less than 17.14%;
Cu:>1.3%;
B:0.9~1.2%;
fe: 61-68% by mass of the total mass of the R-T-B magnet material.
In the present invention, the content of R' is preferably 29.6 to 31.7%, for example, 29.638%, 29.639%, 29.652%, 30.118%, 30.139%, 30.158%, 30.171%, 30.188%, 30.289%, 30.356%, 30.628%, 30.629%, 30.639%, 30.65%, 30.652%, 30.654%, 30.658%, 30.659%, 30.661%, 30.669%, 30.671%, 30.673%, 30.689%, 31.131%, 31.14%, 31.167%, 31.168%, 31.172%, 31.199%, 31.332%, 31.378%, 31.628%, 31.629%, 31.641%, 31.651%, 31.652%, 31.658%, 31.661%, 31.672%, 31.68%, 31.682% or 31.697%, where the percentage is a mass percentage of the total mass of the R-T-B magnet material.
In the present invention, the content of Pr is preferably 17.14 to 28.15%, for example, 17.148%, 17.149%, 17.151%, 17.152%, 18.148%, 18.149%, 18.151%, 19.148%, 19.151%, 20.147%, 20.148%, 20.149%, 20.151%, 20.847%, 21.149%, 21.151%, 22.148%, 22.149%, 22.152%, 22.852%, 23.149%, 23.151%, 24.148%, 24.151%, 25.147%, 25.148%, 25.149%, 25.15%, 25.151%, 25.851%, 26.148%, 26.149%, 26.151%, 28.148% or 28.149%, where the percentage is a mass percentage of the total mass of the R-T-B magnet material.
In the present invention, the R' may further include Nd.
Wherein the mass ratio of Nd to R' is preferably less than 0.5, more preferably 0.08 to 0.45, such as 0.081, 0.082, 0.114, 0.115, 0.116, 0.118, 0.144, 0.147, 0.148, 0.151, 0.174, 0.176, 0.180, 0.205, 0.206, 0.213, 0.219, 0.245, 0.271, 0.277, 0.278, 0.300, 0.304, 0.310, 0.320, 0.332, 0.335, 0.343, 0.348, 0.363, 0.364, 0.375, 0.380, 0.385, 0.395, 0.398, 0.408, 0.417, 0.426, 0.440, 0.441 or 0.450.
The Nd content is preferably 15% or less, more preferably 2.4 to 14.5%, for example, 2.48%, 2.51%, 3.48%, 3.49%, 3.501%, 3.502%, 3.51%, 4.49%, 4.505%, 4.52%, 5.49%, 5.501%, 5.51%, 6.47%, 6.501%, 6.51%, 6.52%, 7.52%, 8.48%, 8.49%, 8.501%, 8.502%, 8.51%, 9.49%, 9.501%, 9.51%, 9.52%, 10.02%, 10.14%, 10.48%, 10.501%, 10.52%, 11.48%, 11.51%, 12.02%, 12.51%, 12.98%, 13.47%, 13.48%, 13.49%, 13.501%, 13.502%, 13.51%, 13.52% or 14.02%, by mass percentage, based on the total mass of the R-T-B magnet material.
Wherein, said R' may also include Y.
In the present invention, it is known to those skilled in the art that the R' preferably further includes RH, which is a heavy rare earth element.
Wherein, the RH may be a heavy rare earth element conventional in the art, such as one or more of Dy, Tb and Ho, preferably Dy and/or Tb.
In the present invention, the mass ratio of RH to R' may be a conventional mass ratio in the art, and is preferably less than 0.253, and more preferably 0.1 to 1, such as 0.017, 0.032, 0.033, 0.047, 0.048, 0.050, 0.063, or 0.064.
The RH content is preferably 2.5% or less, preferably 0.4 to 2.5%, for example, 0.49%, 0.99%, 1.02%, 1.03%, 1.501%, 1.502%, 1.51%, 1.53%, 2.01%, or 2.03%, and the percentage is a mass percentage based on the total mass of the R-T-B-based magnet material.
When Tb is contained in the RH, the content of Tb is preferably 0.45 to 2%, for example, 0.49%, 0.51%, 1.02%, 1.03%, 1.502%, 1.51%, 2.01%, or 2.03%, and the percentage means a mass percentage based on the total mass of the R-T-B-based magnet material.
When Dy is contained in the RH, the content of Dy is preferably 0.45 to 2%, for example, 0.45%, 0.51%, 0.52%, 0.99%, 1.02%, 1.03%, or 1.501%, and the percentage means a mass percentage based on the total mass of the R-T-B-based magnet material.
In the present invention, the Cu content is preferably 1.3to 2.52%, for example, 1.3%, 1.309%, 1.31%, 1.311%, 1.32%, 1.39%, 1.403%, 1.41%, 1.42%, 1.49%, 1.501%, 1.51%, 1.601%, 1.602%, 1.68%, 1.701%, 1.71%, 1.79%, 1.802%, 1.81%, 1.88%, 1.901%, 1.91%, 2.02%, 2.08%, 2.101%, 2.11%, 2.19%, 2.201%, 2.21%, 2.22%, 2.29%, 2.301%, 2.31%, 2.32%, 2.403%, 2.41%, 2.49%, 2.498%, 2.503%, 2.51%, or 2.52%, and the percentage is a mass percentage of the total mass of the R-T-B magnet material.
In the present invention, the content of B is preferably 0.92 to 1.2%, and may be, for example, 0.904%, 0.952%, 0.953%, 0.954%, 0.955%, or 1.194%, and the percentage means a mass percentage based on the total mass of the R-T-B-based magnet material.
In the present invention, the content of Fe is preferably 61.8 to 68%, for example, 61.878%, 62.595%, 62.963%, 63.089%, 63.107%, 63.166%, 63.359%, 63.838%, 63.948%, 63.966%, 63.969%, 64.024%, 64.183%, 64.239%, 64.244%, 64.595%, 64.686%, 64.717%, 64.7842%, 64.797%, 64.905%, 64.971%, 64.985%, 65.063%, 65.161%, 65.193%, 65.277%, 65.522%, 65.646%, 65.65%, 65.815%, 65.865%, 65.884%, 65.907%, 65.955%, 65.967%, 66.044%, 66.055% or 66.055% by mass of the total magnet material in the T-T system.
In the present invention, the R-T-B-based magnet material may further include one or more of Al, Ga, Co, Mn, Ni, Zn, Ag, In, Sn, Bi, V, Cr, Ta, and W.
Wherein, the content of Al can be the content conventional in the field, and is preferably 0-3% but not 0. For example, 0 to 0.03% but not 0, or 0.1 to 0.5%, or 0.5 to 3%; specifically, for example, 0.01%, 0.019%, 0.031%, 0.039%, 0.049%, 0.059%, 0.06%, 0.071%, 0.102%, 0.11%, 0.111%, 0.19%, 0.29%, 0.349%, 0.482%, 0.5%, 0.51%, 0.791%, 0.8%, 1.02%, 1.03%, 1.2%, 1.21%, 1.51%, 1.52%, 1.8%, 1.81%, 2.02%, 2.3%, 2.6%, or 2.9% is defined as a mass percentage based on the total mass of the R-T-B magnet material.
Wherein, the content of Ga may be a content conventionally used in the art, preferably less than 1%, more preferably 0.1 to 1%, such as 0.101%, 0.102%, 0.21%, 0.251%, 0.31%, 0.402%, 0.41%, 0.49%, 0.501%, 0.503%, 0.59%, 0.602%, 0.71%, 0.801%, 0.88%, 1.02%, or 1.03%, by mass, based on the total mass of the R-T-B based magnet material.
The content of Co is a conventional content in the art, and is preferably 2% or less, more preferably 0.5 to 1.5%, for example, 0.51% or 1.02%, and the percentage is a mass percentage based on the total mass of the R-T-B-based magnet material.
Wherein the content of Mn may be a content conventional in the art, preferably 0.052% or less, for example, 0.018% or 0.051%, the percentage referring to the mass percentage based on the total mass of the R-T-B based magnet material.
Wherein the Zn content may be a content conventional in the art, preferably 0.05% or less, for example, 0.019% or 0.0548%, and the percentage means a mass percentage based on the total mass of the R-T-B based magnet material.
In the present invention, the R-T-B based magnet material may further include N, which generally refers to a refractory metal in the art. The N species typically include Zr, Ti or Nb.
Wherein, the content of N can be the content conventional in the field, preferably below 2.5%, and the percentage refers to the mass percentage of the total mass of the R-T-B series magnet material.
When the kind of the N is Zr, the Zr content is preferably 0.25 to 1.05%, for example, 0.251%, 0.302%, 0.501%, 0.503%, 0.51%, 0.802%, or 1.03%, and the percentage means a mass percentage based on the total mass of the R-T-B based magnet material.
When the kind of the N is Ti, the content of the Ti is preferably 0.3 to 2.5%, for example, 0.32%, 0.61%, 1.02%, 1.49%, 2.02%, or 2.48%, and the percentage means a mass percentage based on the total mass of the R-T-B based magnet material.
In a preferred embodiment of the present invention, the R-T-B based magnet material comprises the following components in parts by weight: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: not less than 17.14%; cu: 1.3-2.52%; al: 0 to 3% but not 0; b: 0.9-1.2%; fe: 61-68%, wherein the content of Al is preferably 0.5-3%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material.
In a preferred embodiment of the present invention, the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R' is a rare earth element and comprises Pr and Nd; wherein, the Pr: 17.14 to 28.15 percent; cu: 1.3-2.52%; al: 0.1-0.5%; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Nd is preferably 2.4-14.5%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material.
In a preferred embodiment of the present invention, the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R' is a rare earth element and comprises Pr and Nd; wherein, the Pr: 17.14 to 28.15 percent; cu: 1.3-2.52%; al: 0.5-3%; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Nd is preferably 2.4-14.5%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material.
In a preferred embodiment of the present invention, the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: not less than 17.14%; cu: 1.3-2.52%; al: 0 to 0.03% but not 0; ga: 0.25 to 1% but not 0; b: 0.9-1.2%; fe: 61-68%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material.
In a preferred embodiment of the present invention, the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R' is a rare earth element and comprises Pr and Nd; wherein, the Pr: 17.14 to 28.15 percent; cu: 1.3-2.52%; al: 0 to 0.03% but not 0; ga: 0.25-1%; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Nd is preferably 2.4-14.5%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material.
In a preferred embodiment of the present invention, the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: not less than 17.14%; cu: 1.3-2.52%; al: 0.1-0.5%; ti: 0.3-2.5%; b: 0.9-1.2%; fe: 61-68%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material.
In a preferred embodiment of the present invention, the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R' is a rare earth element and comprises Pr and Nd; wherein, the Pr: 17.14 to 28.15 percent; cu: 1.3-2.52%; al: 0.1-0.5%; ti: 0.3-2.5%; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Nd is preferably 2.4-14.5%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material.
In a preferred embodiment of the present invention, the R-T-B based magnet material includes the following components in amounts: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: not less than 17.14%; cu: 1.3-2.52%; al: 0.1-0.5%; ga: 0 to 0.25% but not 0; b: 0.9-1.2%; fe: 61-68%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material. Wherein, the content of Pr is preferably 17.14 to 28.15 percent; r' preferably further comprises Nd; the content of Nd is preferably 2.5-14.5%.
In the present invention, the R-T-B system magnet material preferably contains a grain boundary Fe-rich phase having the composition and content described above.
In the present invention, the R-T-B magnet material generally further contains a main phase. Wherein the components and contents of the main phase are preferably as described above.
In the present invention, the R-T-B magnet material generally contains a grain boundary rare earth-rich phase. Wherein the composition and content of the grain boundary rare earth-rich phase are preferably as described above.
The invention also provides an application of the R-T-B series magnet material as an electronic element.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
In the invention, Pr is praseodymium, Nd is neodymium, Cu is copper, B is boron, Fe is iron, Al is aluminum, Ga is gallium, Co is cobalt, Zr is zirconium, Ti is titanium, Zn is zinc, Dy is dysprosium, Tb is terbium, Ni is nickel, Ag is silver, In is indium, Sn is tin, Bi is bismuth, V is vanadium, Cr is chromium, Ta is tungsten, and O is oxygen.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the R-T-B series magnet material provided by the invention uses higher content of Pr and higher content of Cu, so that the R-T-B series magnet material can maintain higher remanence while the coercive force is obviously improved; in a further preferred embodiment of the present invention, R-T-B magnet material may be R6T13M1The coercive force of the magnet material can be further improved.
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.
The raw material compositions of the R-T-B system magnet materials in the respective examples and comparative examples are shown in Table 1 below.
TABLE 1
Figure BDA0002326012780000161
Figure BDA0002326012780000171
Figure BDA0002326012780000181
Note: the numbers 1 to 60 in Table 1 refer to examples 1 to 60, and the numbers 61 to 64 refer to comparative examples 61 to 64.
The preparation process of the R-T-B series magnet material of example 1 is as follows:
(1) and (3) casting: according to the formulation shown in Table 1, the raw materials prepared in example 1 were placed in a crucible made of alumina, and placed in a high-frequency vacuum induction melting furnace at 5X 10-2Vacuum melting is carried out at a temperature of 1500 ℃ or lower in a vacuum of Pa. Ar gas is introduced into a melting furnace after vacuum melting to make the gas pressure reach 5.5 ten thousand Pa, and then casting is carried out at 10 degrees2DEG C/sec-104The cooling rate of DEG C/second obtains the quenched alloy.
(2) Hydrogen crushing and crushing: vacuumizing the smelting furnace in which the quenching alloy is placed at room temperature, introducing hydrogen with the purity of 99.9% into the hydrogen cracking furnace, maintaining the hydrogen pressure at 0.15MPa, fully absorbing hydrogen, vacuumizing while heating, fully dehydrogenating, cooling, and taking out the powder after hydrogen cracking and crushing.
(3) A micro-grinding process: the powder after hydrogen crushing was pulverized by jet milling for 3 hours under a nitrogen atmosphere having an oxidizing gas content of 150ppm or less at a pressure in the pulverization chamber of 0.38MPa to obtain a fine powder. The oxidizing gas refers to oxygen or moisture.
(4) Adding zinc stearate into the powder crushed by the jet mill, wherein the adding amount of the zinc stearate is 0.12 percent of the weight of the mixed powder, and then fully mixing the zinc stearate and the mixed powder by using a V-shaped mixer.
(5) Magnetic field forming process:using a magnetic field forming machine of a perpendicular orientation type, in an orientation magnetic field of 1.6T, at 0.35ton/cm2The powder added with zinc stearate was once formed into a cube with a side length of 25mm under the molding pressure of (1), and demagnetized in a magnetic field of 0.2T after the primary molding. The molded article after the primary molding was sealed so as not to contact air, and then subjected to secondary molding (isostatic pressing) at 1.3ton/cm2Secondary forming is performed under pressure of (1).
(6) And (3) sintering: the molded bodies were transferred to a sintering furnace and sintered at 5X 10-3Pa at 300 deg.C and 600 deg.C for 1 hr, sintering at 1040 deg.C for 6 hr, introducing Ar gas to make the pressure reach 0.1MPa, and cooling to room temperature.
(7) And (3) aging treatment process: the sintered body was heat-treated in high-purity Ar gas at 550 ℃ for 3 hours, cooled to room temperature, and taken out.
The R-T-B magnet materials of examples 2 to 60 and comparative examples 61 to 64 were prepared according to the formulation of the raw material composition shown in Table 1 by the same preparation process as in example 1.
Example 1.1 Dy grain boundary diffusion method
The raw material composition formulation of example 1 in table 1 was prepared by the preparation method of example 1, first, obtaining a sintered body, followed by grain boundary diffusion and then aging treatment. The aging treatment process is the same as that of the example 1, and the treatment process of grain boundary diffusion is as follows:
processing the sintered body into a magnet with the diameter of 20mm and the sheet thickness of less than 3mm, wherein the thickness direction is the magnetic field orientation direction, cleaning the surface, using a raw material prepared by Dy fluoride, spraying and coating the whole surface on the magnet, drying the coated magnet, sputtering metal attached with Dy element on the surface of the magnet in a high-purity Ar gas atmosphere, performing diffusion heat treatment at the temperature of 850 ℃ for 24 hours, and then cooling to the room temperature.
EXAMPLE 1.2 Tb grain boundary diffusion method was used
Example 1 in table 1 a sintered body was first prepared according to the preparation of the sintered body of example 1, and grain boundary diffusion was first performed, followed by aging treatment. The aging treatment process is the same as that of the example 1, and the treatment process of grain boundary diffusion is as follows:
processing the sintered body into a magnet with the diameter of 20mm and the sheet thickness of less than 7mm, wherein the thickness direction is the magnetic field orientation direction, cleaning the surface, using a raw material prepared from Tb fluoride, spraying and coating the whole surface of the raw material on the magnet, drying the coated magnet, sputtering metal attached with Tb on the surface of the magnet in a high-purity Ar gas atmosphere, and performing diffusion heat treatment at the temperature of 850 ℃ for 24 hours. And cooling to room temperature.
Effect example 1
The magnetic properties and components of the R-T-B magnet materials prepared in the examples and comparative examples were measured.
(1) Evaluation of magnetic Properties: the sintered magnet is subjected to magnetic property detection by using an NIM-10000H type BH bulk rare earth permanent magnet nondestructive measurement system of China measurement institute. The following table 2 shows the results of magnetic property measurements.
TABLE 2
Figure BDA0002326012780000191
Figure BDA0002326012780000201
Figure BDA0002326012780000211
Figure BDA0002326012780000221
(2) Component determination: the R-T-B magnet materials of the numbers 1 to 64 were measured by using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES). The following table 3 shows the results of component detection.
TABLE 3
Figure BDA0002326012780000222
Figure BDA0002326012780000231
Note: 6:13:1 phases mean R 'in R-T-B based magnet material'6T13M1And phase R ' is a rare earth element, T is one or more of Fe, Co, Al and N, M is Cu and/or Ga, and O in the table represents R ' formed in the R-T-B magnet material '6T13M1X in the table represents R 'not formed in the R-T-B magnet material'6T13M1And (4) phase(s).
(3) FE-EPMA detection: R-T-B magnet materials 1, 2, 3, 11, 12, 23, 25, 28, 29, 31, 33, 35, 36, 41, 45, 61, 62, 63, 64, which were prepared in Table 3, were used. The vertical orientation surface of the sintered magnet was polished and examined by a field emission electron probe microanalyzer (FE-EPMA) (JEOL 8530F). The test results are shown in table 4 below. In table 4, the grain boundary Fe-rich phase is converted to atomic percent, wherein R': t: the atomic ratio of M is close to 6:13:1, wherein R 'is a rare earth element and R' comprises Pr; the kind of T includes one or more of Fe, Co, Al and N, but at least includes Fe; m comprises Cu and/or Ga.
TABLE 4
Figure BDA0002326012780000241

Claims (10)

1. A raw material composition of an R-T-B series magnet material is characterized by comprising the following components in percentage by mass: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr;
wherein, the Pr: more than or equal to 17.15 percent;
Cu:>1.3%;
B:0.9~1.2%;
fe: 61-68% by mass of the total mass of the raw material composition of the R-T-B magnet material.
2. The raw material composition according to claim 1, wherein the content of R' is 29.65 to 31.65%, preferably 29.65%, 30.15%, 30.3%, 30.35%, 30.65%, 31.15%, 31.35%, or 31.65%, and the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B-based magnet material;
and/or the content of Pr is 17.15-28.15%, preferably 17.15%, 18.15%, 19.15%, 20.15%, 20.85%, 21.15%, 22.15%, 22.85%, 23.15%, 24.15%, 25.15%, 25.85%, 26.15% or 28.15%, the percentage being mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
and/or, said R' further comprises Nd; preferably, the mass ratio of Nd to R' is less than 0.5, preferably 0.08-0.45; more preferably, the content of Nd is 15% or less, preferably 2.5 to 14.5%, more preferably 2.5%, 3.5%, 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, 10%, 10.15%, 10.5%, 11.5%, 12%, 12.5%, 13%, 13.5%, or 14%, and the percentage is a mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material;
and/or, the R' also comprises RH which is a heavy rare earth element; preferably, the RH species includes one or more of Dy, Tb and Ho, more preferably Dy and/or Tb; preferably, the mass ratio of the RH to the R' is less than 0.253, and preferably 0.1-1; preferably, the content of the RH is less than 2.5%, preferably 0.5-2.5%; preferably, when the RH contains Tb, the content of Tb is 0.5-2%; preferably, when Dy is contained in the RH, the content of Dy is 0.5-2%;
and/or the Cu content is 1.3-2.5%, preferably 1.31%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4% or 2.5%, and the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
and/or the content of B is 0.92-1.2%;
and/or the content of Fe is 61.8-68%;
and/or, the raw material composition of the R-T-B series magnet material can also comprise one or more of Al, Ga, Co, Mn, Ni, Zn, Ag, In, Sn, Bi, V, Cr, Ta and W;
and/or the raw material composition of the R-T-B magnet material also comprises N, and the type of the N comprises Zr, Ti or Nb.
3. The raw material composition according to claim 2, wherein the content of Al is 0 to 3% but not 0; preferably 0 to 0.03% but not 0, or 0.1 to 0.5%, or 0.5 to 3%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
and/or the Ga content is less than 1%, preferably 0.1-1%, and the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
and/or the content of Co is less than 2%, preferably 0.5-1.5%, and the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
and/or the Mn content is 0.05% or less, preferably 0.02% or 0.05%, the percentage being the mass percentage based on the total mass of the raw material composition of the R-T-B-based magnet material;
and/or the Zn content is less than 0.05%, preferably 0.02% or 0.05%, the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
and/or the content of N is less than 2.5 percent, and the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material; preferably, when the kind of the N is Zr, the content of the Zr is 0.25 to 1 percent, and the percentage refers to the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material; preferably, when the type of N is Ti, the content of Ti is 0.3 to 2.5% by mass of the total mass of the raw material composition of the R-T-B-based magnet material.
4. A raw material composition according to any one of claims 1 to 3, wherein the raw material composition of the R-T-B based magnet material comprises the following components in amounts: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3-2.5%; al: 0 to 3% but not 0; b: 0.9-1.2%; fe: 61-68%, wherein the content of Al is preferably 0.5-3%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
or the raw material composition of the R-T-B series magnet material comprises the following components in percentage by weight: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3-2.5%; al: 0 to 0.03% but not 0; ga: 0.25-1%; b: 0.9-1.2%; fe: 61-68%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
or the raw material composition of the R-T-B series magnet material comprises the following components in percentage by weight: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3-2.5%; al: 0.1-0.5%; ti: 0.3-2.5%; b: 0.9-1.2%; fe: 61-68%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series magnet material;
or the raw material composition of the R-T-B series magnet material comprises the following components in percentage by weight: r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr; wherein, the Pr: more than or equal to 17.15 percent; cu: 1.3-2.5%; al: 0.1-0.5%; ga: 0 to 0.25% but not 0; b: 0.9-1.2%; fe: 61-68%; wherein, the content of Pr is preferably 17.15-28.15%; r' preferably further comprises Nd; the content of Nd is preferably 2.5-14.5%; the percentages are mass percentages based on the total mass of the raw material composition of the R-T-B magnet material.
5. A method for producing an R-T-B-based magnet material, characterized in that a raw material composition for the R-T-B-based magnet material according to any one of claims 1 to 4 is used as a raw material for the R-T-B-based magnet material in the production method;
preferably, the preparation method comprises the following steps: subjecting a melt of a raw material composition for an R-T-B system magnet material according to any one of claims 1 to 4 to fusion casting, hydrogen decrepitation, shaping, sintering and aging treatment; wherein, the smelting temperature in the fusion casting is preferably below 1500 ℃; preferably, the sintering temperature is 1030-1080 ℃; preferably, the sintering time is 4-10 h; preferably, after the sintering and before the aging treatment, grain boundary diffusion treatment is also carried out; preferably, the temperature of the diffusion heat treatment in the grain boundary diffusion treatment is 800-900 ℃; preferably, the time of the diffusion heat treatment in the grain boundary diffusion treatment is 12-48 h; preferably, in the aging treatment, the temperature of the secondary aging treatment is 520-650 ℃, preferably 550 ℃.
6. An R-T-B system magnet material, characterized in that it is produced by the production method according to claim 5.
7. An R-T-B system magnet material, characterized in that it comprises a grain boundary Fe-rich phase; the grain boundary Fe-rich phase comprises the following components in percentage by mass: r': 49-60%, wherein R 'is a rare earth element, and R' comprises Pr; t: 39-50%, wherein T comprises Fe; m: 1.5-4%, wherein M comprises Cu; the percentage is the mass percentage of each component in the total mass of the grain boundary Fe-rich phase;
preferably, the grain boundary Fe-rich phase accounts for 2-25% of the total volume of the R-T-B series magnet material;
preferably, the R-T-B series magnet material also comprises a main phase; more preferably, the main phase preferably comprises the following components in percentage by mass: r': 26-28%, wherein R 'is a rare earth element, and R' comprises Pr; b: 0.9-1.2%; t: 70-72%, wherein the T comprises Fe, and the percentage is the mass percentage of each component in the total mass of the main phase;
preferably, the R-T-B series magnet material further comprises a grain boundary R 'rich phase, wherein R' is a rare earth element; the grain boundary R' -rich phase preferably comprises the following components in percentage by mass: r': 84-87%, O: 13-16%, wherein R 'comprises Pr, and the percentage is the mass percentage of each component in the total mass of the crystal boundary R' rich phase.
8. An R-T-B series magnet material is characterized by comprising the following components in percentage by mass:
r': 29.5-32%, wherein R 'is a rare earth element, and R' comprises Pr;
wherein, the Pr: not less than 17.14%;
Cu:>1.3%;
B:0.9~1.2%;
fe: 61-68% by mass of the total mass of the R-T-B magnet material.
9. The R-T-B magnet material according to claim 8, wherein the content of R' is 29.6 to 31.7% by mass based on the total mass of the R-T-B magnet material;
and/or the content of Pr is 17.14-28.15%, and the percentage is the mass percentage of the total mass of the R-T-B series magnet material;
and/or, said R' further comprises Nd; preferably, the mass ratio of Nd to R' is less than 0.5, more preferably 0.08-0.45; more preferably, the content of Nd is less than 15%, preferably 2.4-14.5%;
and/or, said R' further comprises Y;
and/or, the R' also comprises RH which is a heavy rare earth element; preferably, the RH species comprises one or more of Dy, Tb and Ho, preferably Dy and/or Tb; preferably, the mass ratio of the RH to the R' is less than 0.253, and preferably 0.1-1; preferably, the content of the RH is less than 2.5%, preferably 0.4-2.5%; more preferably, when the RH contains Tb, the content of Tb is 0.45-2%; more preferably, when Dy is contained in the RH, the content of Dy is 0.45-2%; the percentage is the mass percentage of the total mass of the R-T-B series magnet material;
and/or the content of Cu is 1.3-2.52%, and the percentage is the mass percentage of the total mass of the R-T-B series magnet material;
and/or the content of B is 0.92-1.2%, and the percentage is the mass percentage of the total mass of the R-T-B series magnet material;
and/or the content of Fe is 61.8-68%, and the percentage is the mass percentage of the total mass of the R-T-B series magnet material;
and/or, the R-T-B series magnet material further comprises one or more of Al, Ga, Co, Mn, Ni, Zn, Ag, In, Sn, Bi, V, Cr, Ta and W; wherein, the content of Al is preferably 0-3% but not 0, more preferably 0-0.03% but not 0, or 0.1-0.5%, or 0.5-3%; wherein, the content of Ga is preferably less than 1%, and more preferably 0.1-1%; wherein, the content of Co is preferably below 2%, preferably 0.5-1.5%; wherein, the content of Mn is preferably below 0.052%; wherein, the Zn content is preferably less than 0.05%, and the percentage is the mass percentage of the total mass of the R-T-B series magnet material;
and/or the R-T-B series magnet material also comprises N, and the type of the N comprises Zr, Ti or Nb; wherein, the content of N is preferably below 2.5%; preferably, when the N is Zr, the Zr content is 0.25-1.05%; preferably, when the type of N is Ti, the content of Ti is 0.3-2.5%;
and/or the R-T-B series magnet material contains a grain boundary Fe-rich phase; preferably, the Fe-rich phase comprises the following components in percentage by mass: r': 49-60%, wherein R 'is a rare earth element, and R' comprises Pr; t: 39-50%, wherein T comprises Fe; m: 1.5-4%, wherein M comprises Cu; the percentage is the mass percentage of each component in the total mass of the grain boundary Fe-rich phase;
and/or, the R-T-B series magnet material also contains a main phase; preferably, the main phase comprises the following components in percentage by mass: r': 26-28%, wherein R 'is a rare earth element, and R' comprises Pr; b: 0.9-1.2%; t: 70-72%, wherein the T comprises Fe, and the percentage is the mass percentage of each component in the total mass of the main phase;
and/or the R-T-B series magnet material also comprises a grain boundary R 'rich phase, wherein R' is a rare earth element; preferably, the grain boundary R' rich phase comprises the following components in percentage by mass: r': 84-87%, O: 13-16%, wherein R 'comprises Pr, and the percentage is the mass percentage of each component in the total mass of the crystal boundary R' rich phase.
10. Use of the R-T-B based magnet material according to any one of claims 6 to 9 as an electronic component.
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