CN111326306A - R-T-B series permanent magnetic material and preparation method and application thereof - Google Patents

R-T-B series permanent magnetic material and preparation method and application thereof Download PDF

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CN111326306A
CN111326306A CN202010132226.2A CN202010132226A CN111326306A CN 111326306 A CN111326306 A CN 111326306A CN 202010132226 A CN202010132226 A CN 202010132226A CN 111326306 A CN111326306 A CN 111326306A
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percentage
mass
content
raw material
material composition
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CN111326306B (en
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付刚
黄佳莹
黄清芳
房明海
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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Priority to PCT/CN2021/077183 priority patent/WO2021169897A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • C—CHEMISTRY; METALLURGY
    • 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%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

The invention discloses an R-T-B series permanent magnetic material and 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 weight: r: 28.5-34%; r is a rare earth element, and the R comprises Nd; ga is more than 0.5%; cu is more than or equal to 0.4 percent; b: 0.84-0.94%; co is less than or equal to 2.5 percent; fe: 59-69%; n: one or more of Ti, Zr and Nb; when N contains Ti, Ti is 0.15-0.25%; when N contains Zr, Zr is 0.2-0.35%; when N contains Nb, Nb is 0.2-0.5%; the percentage is the mass percentage of the total mass of the raw material composition. When heavy rare earth is not added, the rare earth permanent magnet material adopts a low-boron aluminum-free system with better magnetic properties such as remanence, coercive force, temperature stability and squareness, and the magnetic properties of the permanent magnet materials in the same batch are uniform.

Description

R-T-B series permanent magnetic material and preparation method and application thereof
Technical Field
The invention particularly relates to an R-T-B series permanent magnetic material and a preparation method and application thereof.
Background
R-T-B series permanent magnetic materials (R means rare earth element, T means transition metal element and third main group metal element, and B means boron element) are widely used in the fields of electronic products, automobiles, wind power, household electrical appliances, elevators, industrial robots, etc., for example, as energy sources in permanent magnetic motors such as hard disks, mobile phones, earphones, elevator traction machines, generators, etc., due to their excellent magnetic properties, and the demands of various manufacturers on magnet properties such as remanence, coercive force property, temperature stability, magnet squareness, etc. are gradually increasing.
The R-T-B series permanent magnetic material mainly comprises R2T14The main phase of the B compound and a grain boundary phase located in a grain boundary portion of the main phase. The R is2T14The B compound is a ferromagnetic material having a high saturation magnetization and an anisotropic magnetic field. The coercive force of the R-T-B series permanent magnetic material is reduced at high temperature, so irreversible thermal demagnetization occurs. It is currently known that: replacement of R as the main phase by the heavy rare earth element RH2T14In the compound B, part of the light rare earth RL in R is increased in coercive force, and the coercive force is increased with the increase in substitution amount. On the other hand, however, the residual magnetic flux Br decreases. In addition, RH is a scarce resource and expensive resource. In order to improve the remanence of the R-T-B permanent magnetic material, the content of B is generally required to be reduced. However, when the content of B is at a low level, R is formed2T17And (4) phase(s). And R is2T17Not having room temperatureThe uniaxial anisotropy, in turn, deteriorates the performance of the magnet.
The squareness of the magnet material is a ratio of a magnetic field value Hk (knee point coercive force) corresponding to a magnetic polarization strength J of 0.9Jr (Jr is remanent polarization, and is equal to a remanent induction strength Br, and both are collectively referred to as remanence) on the J-H demagnetization curve to a magnetic field value Hcj (intrinsic coercive force) corresponding to a magnetic polarization strength J of 0 on the J-H demagnetization curve, that is, Hk/Hcj. Having a higher squareness is a necessary condition for a high-quality magnet. So as to reduce the loss of magnetism during the use process, especially under the environment with higher relative use temperature, and ensure that the magnet still has high magnetic performance when used in the environment for a long time. Even though the coercive force and the remanence of the permanent magnet material in the prior art are high, the squareness of the permanent magnet material cannot be improved to a better level at the same time.
Therefore, under the condition of not adding or adding a small amount of heavy rare earth, how to prepare the R-T-B permanent magnetic material with high coercivity, high remanence, squareness and good consistency by adopting a method of a low-B Al-free system is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to overcome the defects that a large amount of heavy rare earth elements are usually required to be added when the rare earth permanent magnetic material adopts a low B system to improve the magnetic property in the prior art, and the magnetic property (remanence, coercive force, temperature stability and squareness) can not be obviously improved even if the heavy rare earth elements are added, and provides an R-T-B system permanent magnetic material and a preparation method and application thereof. On the premise of not adding heavy rare earth elements, the R-T-B series permanent magnet material can still be prepared to have better magnetic performance (remanence, coercive force, temperature stability and squareness degree) by adopting a low-boron aluminum-free system, and meanwhile, the permanent magnet materials in the same batch have uniform magnetic performance.
It should be noted that, in the prior art, a certain amount of Al is usually added to the R-T-B series permanent magnetic material to obtain a magnet material with better performance, but the inventor finds out through multiple experiments that: although the addition of Al improves the magnetic properties of the magnet material, the magnetic properties are not uniform in the production of the same batch of products, i.e., the difference between the maximum value and the minimum value of the coercive force in the same batch of products is greater than 1.5 kOe. And the R-T-B series permanent magnetic material finally obtained by the invention has better uniformity through a specific formula.
The invention adopts the following technical scheme to solve the technical problems.
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:
r: 28.5-34%; r is a rare earth element and at least comprises Nd;
Ga：>0.5％；
Cu：≥0.4％；
B：0.84～0.94％；
co: less than or equal to 2.5 percent but not 0 percent;
Fe：59～69％；
n: one or more of Ti, Zr and Nb;
when the N comprises Ti, the content of the Ti is 0.15-0.25%;
when the N comprises Zr, the content of Zr is 0.2-0.35%;
when the N comprises Nb, the content of Nb is 0.2-0.5%;
the percentage is the mass percentage of each component in the total mass of the raw material composition.
It should be noted that each component and the corresponding content in the raw material composition are actively added, and the components and/or the content introduced in the preparation process and/or impurities are not included.
In the present invention, the content of R is preferably 29 to 34%, for example, 29.4%, 30%, 30.3%, 30.4%, 30.5%, 31%, 31.2%, 31.5%, 31.8%, 32%, 33.8% or 34%, more preferably 30 to 31.6%, in mass% based on the total mass of the raw material composition.
In the present invention, the content of Nd is preferably 8 to 13%, or 25 to 31.5%, for example, 9.5%, 10.5%, 25%, 29%, 30%, 31%, 31.4% or 31.5%; more preferably 9.5-10.5% or 29-31.5%, the percentage is the mass percentage of the total mass of the raw material composition.
In the present invention, the raw material composition preferably does not contain Al; it means that Al is not actively added, but a trace amount of Al (below 0.08%) may be introduced during the addition of other elements (e.g., Fe) or during the manufacturing process (e.g., alumina crucible preparation melt).
In the present invention, in the raw material composition, the R may generally further include Pr.
When the raw material composition contains Pr, the content of Pr is preferably less than 8% and is not 0, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5% or 6.5%, and more preferably 0.1-0.5%; or the content of Pr is preferably 18.5 to 30%, more preferably 20.5 to 21.5%, for example 20.5% or 21.5%, by mass, based on the total mass of the raw material composition.
In the invention, the raw material composition does not contain heavy rare earth elements, and can also reach the level equivalent to the residual magnetism and the coercive force of the magnet material in the prior art. Alternatively, the raw material composition may further include RH, which is a heavy rare earth element.
When the raw material composition contains RH, the content of RH is preferably 1 to 2.5% by mass of the total mass of the raw material composition.
Wherein, the RH preferably includes one or more of Dy, Tb and Ho.
When the RH includes Dy, the content of Dy is preferably 1 to 2.5%, for example, 2%, in mass percentage based on the total mass of the raw material composition.
When the RH includes Tb, the content of Tb is preferably 1 to 2.5%, for example 2%, and the percentage is the mass percentage of the total mass of the raw material composition.
In the present invention, the content of B is preferably 0.86 to 0.94%, for example, 0.86%, 0.88%, 0.9%, 0.92% or 0.94%, more preferably 0.86 to 0.92%, in percentage by mass based on the total mass of the raw material composition.
In the present invention, the atomic percentages of R and B in the raw material composition preferably satisfy the following relationship: B/R is more than or equal to 0.38, wherein in the formula, the atom percentage of B in the raw material composition is shown, and the atom percentage of R in the raw material composition is shown.
In the present invention, when Pr is included in the raw material composition, it is preferable that B and Nd satisfy the following relationship: B/(Pr + Nd) ≥ 0.405, wherein B refers to the atomic percentage of B in the raw material composition, Pr refers to the atomic percentage of Pr in the raw material composition, and Nd refers to the atomic percentage of Nd in the raw material composition.
In the present invention, the Ga content is preferably 0.52 to 1.8%, for example, 0.52%, 0.55%, 0.65%, 0.85%, 1.05%, 1.25%, 1.75%, or 1.8%, more preferably 0.6 to 1.8%, in percentage by mass based on the total mass of the raw material composition.
In the present invention, the content of Cu is preferably 0.4 to 2%, for example, 0.4%, 0.45%, 0.55%, 0.6%, 0.65%, 0.85%, 1%, 1.25%, 1.5%, 1.85%, or 2%, more preferably 0.55 to 1.05%, or 1.25 to 2%, in mass% based on the total mass of the raw material composition.
In the present invention, the content of Co is preferably 0.5 to 2.5%, for example, 0.5%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, or 2.5%, more preferably 0.5 to 2%, by mass, based on the total mass of the raw material composition.
In the present invention, the content of Fe is preferably 59.5 to 67.3%, such as 59.68%, 60.01%, 62.28%, 62.38%, 62.84%, 63.84%, 64.09%, 64.35%, 64.38%, 64.74%, 64.92%, 65.46%, 65.5%, 65.75%, 67.06%, or 67.24%, more preferably 60 to 66%, by mass based on the total mass of the raw material composition.
In the present invention, when the N includes Ti, the content of Ti is preferably 0.2 to 0.25%, for example, 0.15%, 0.2%, 0.22%, or 0.25%, in percentage by mass based on the total mass of the raw material composition.
In the present invention, when the N contains Zr, the content of Zr is preferably 0.22 to 0.35%, for example, 0.22%, 0.25%, 0.26%, 0.32% or 0.35%, more preferably 0.26 to 0.32%, in percentage by mass based on the total mass of the raw material composition.
In the present invention, when Zr is contained in the N, the content of Zr is preferably: zr is more than or equal to 0.26 percent and less than 3.48B-2.67, and B is the mass percent of the raw material composition. For example, when the content of B is 0.86%, B in the formula is 0.86.
In the present invention, when the N includes Nb, the content of Nb is preferably 0.2 to 0.32%, for example, 0.2%, 0.22%, 0.25%, or 0.32%, in percentage by mass based on the total mass of the raw material composition.
In the present invention, when the raw material composition contains Ti and Nb, it is preferable that the Ti/Nb is greater than or equal to 1.5, where Ti is a mass percentage in the raw material composition, and Nb is a mass percentage in the raw material composition.
In the invention, the raw material composition of the R-T-B series permanent magnetic material preferably comprises the following components in percentage by mass: r: 29-32%; r is a rare earth element and at least comprises Nd;
B：0.86～0.94％；
Ga：0.52～1.8％；
Cu：0.45～2％；
Co：0.45～2.5％；
Fe：59.5～67.3％；
n: one or more of Ti, Zr and Nb;
when the N contains Ti, the content of the Ti is 0.2-0.25%;
when the N contains Zr, the content of Zr is 0.25-0.35%;
when the N contains Nb, the content of Nb is 0.25-0.5%; the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition.
In the invention, the raw material composition of the R-T-B series permanent magnetic material preferably comprises the following components in percentage by mass: r: 29-32%; the R is a rare earth element and comprises Nd and Pr; pr: 0.1-0.5% or 18.5-25%;
B：0.86～0.94％；
Ga：0.52～1.8％；
Cu：0.45～2％；
Co：0.45～2.5％；
Fe：62.8～67.25％；
ti: 0.2-0.25%; the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition.
In the invention, the raw material composition of the R-T-B series permanent magnetic material preferably comprises the following components in percentage by mass: r: 29-32%; the R is a rare earth element and comprises Nd and Pr; pr: 0.1-0.5% or 18.5-25%;
B：0.86～0.94％；
Ga：0.52～0.55％；
Cu：0.45～2％；
Co：0.45～2.5％；
Fe：62.8～67.25％；
ti: 0.2-0.25%; the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition.
In the invention, the raw material composition of the R-T-B series permanent magnetic material preferably comprises the following components in percentage by mass: r: 29-32%; r is a rare earth element and at least comprises Nd;
B：0.86～0.94％；
Ga：0.52～1.8％；
Cu：0.45～2％；
Co：0.45～2.5％；
Fe：60～67.1％；
Zr：0.25～0.35％；
the raw material composition does not contain Al;
the percentage is the mass percentage of each component in the total mass of the raw material composition.
In the invention, the raw material composition of the R-T-B permanent magnetic material preferably comprises the following components in percentage by mass: r: 29-32%; r is a rare earth element and at least comprises Nd;
B：0.86～0.94％；
Ga：0.52～0.55％；
Cu：0.45～2％；
Co：0.45～0.55％；
Fe：60～67.1％；
Zr：0.25～0.35％；
the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 30% of Nd, 0.3% of Pr, 0.52% of Ga, 0.45% of Cu, 0.5% of Co, 0.15% of Ti, 0.84% of B and 67.24% of Fe67, wherein the percentages are mass percentages of the components in the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: nd 31%, Pr 0.2%, Ga 0.52%, Cu 1%, Co 0.5%, Ti 0.2%, Nb 0.2%, B0.88% and Fe65.5%, wherein the percentages are mass percentages of the components in the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components by mass: 10.5% of Nd, 21.5% of Pr, 0.55% of Ga, 1.5% of Cu, 0.5% of Co, 0.22% of Ti, 0.22% of Nb, 0.92% of B and 64.09% of Fe, wherein the percentage is that the mass of each component accounts for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 9.5% of Nd, 21.5% of Pr, 0.55% of Ga, 2% of Cu, 1.2% of Co, 0.25% of Ti, 0.22% of Nb, 0.94% of B and 63.84% of Fe, wherein the percentages are mass percentages of the components in the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 9.5% of Nd, 21.5% of Pr, 1.05% of Ga, 0.55% of Cu, 1.5% of Co, 0.22% of Ti, 0.94% of B and 64.74% of FeC, wherein the percentages are mass percentages of the components accounting for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 9.5% of Nd, 21.5% of Pr, 1.75% of Ga, 1.25% of Cu, 2% of Co, 0.22% of Ti, 0.94% of B and 62.84% of FeS, wherein the percentages are mass percentages of the components accounting for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: nd 29%, Pr 0.4%, Ga 0.52%, Cu 0.45%, Co 1.2%, Zr 0.26%, Nb 0.25%, B0.86% and Fe 67.06%, wherein the percentages are mass percentages of the components in the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 30% of Nd, 0.4% of Pr, 0.55% of Ga, 0.6% of Cu, 1.2% of Co, 0.32% of Zr, 0.32% of Nb, 0.86% of B and 65.75% of Fe, wherein the percentages are mass percentages of the components in the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 30.3% of Nd, 0.2% of Pr, 0.85% of Ga, 0.65% of Cu, 1.6% of Co, 0.2% of Ti, 0.2% of Zr, 0.2% of Nb0.2%, 0.88% of B and 64.92% of Fe, wherein the percentage is that the mass of each component accounts for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 31.5 percent of Nd 31.4 percent, Pr 0.1 percent, Ga 0.55 percent, Cu 0.85 percent, Co 1.6 percent, Zr 0.22 percent, B0.9 percent and Fe64.38 percent, wherein the percentage is the mass percentage of each component in the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 25% of Nd, 6.5% of Pr, 0.55% of Ga, 0.85% of Cu, 1.6% of Co, 0.22% of Zr, 0.9% of B and 64.38% of FeC, wherein the percentages are mass percentages of the components accounting for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 9.5 percent of Nd, 21.5 percent of Pr21, 0.65 percent of Ga, 1.25 percent of Cu, 1.6 percent of Co, 0.25 percent of Zr, 0.9 percent of B and 64.35 percent of FeC, wherein the percentages are mass percentages of all the components accounting for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 10.5% of Nd, 21.5% of Pr, 0.85% of Ga, 1.85% of Cu, 1.8% of Co, 0.32% of Zr, 0.9% of B and 62.28% of FeC, wherein the percentages are mass percentages of the components accounting for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 10.5% of Nd, 21.5% of Pr, 0.85% of Ga, 1.85% of Cu, 1.8% of Co, 0.22% of Zr, 0.9% of B and 62.38% of FeC, wherein the percentages are mass percentages of the components accounting for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 9.5% of Nd, 20.5% of Pr, 0.85% of Ga, 0.65% of Cu, 1.8% of Co, 0.32% of Zr, 0.92% of B and 65.46% of FeC, wherein the percentages are mass percentages of the components accounting for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the rare earth permanent magnetic material comprises the following components: 31.5% of Nd, 0.3% of Pr, 2%, 1.25% of Ga, 2% of Cu, 2% of Co, 0.35% of Zr, 0.92% of B and 59.68% of Fes, wherein the percentages are mass percentages of the components accounting for the total mass of the raw material composition.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: 31.5% of Nd, 0.5% of Pr, 2%, 1.8% of Ga, 0.4% of Cu, 2.5% of Co, 0.35% of Zr, 0.94% of B and 60.01% of FeC, wherein the percentages are mass percentages of the components in the total mass of the raw material composition.
The invention also provides a preparation method of the R-T-B series permanent magnetic material, which comprises the following steps: which comprises the following steps: the raw material composition of the R-T-B series permanent magnet material is subjected to casting, powder making, molding, sintering and aging treatment.
In the present invention, the person skilled in the art knows that the casting usually also comprises smelting.
Wherein the smelting operations and conditions may be conventional in the art. The vacuum degree of the smelting can be 0.05 Pa. The temperature of the smelting can be below 1500 ℃. The smelting equipment can be a high-frequency vacuum induction smelting furnace.
In the present invention, the casting operation and conditions may be those conventional in the art. The casting is typically at 10 deg.f2DEG C/sec-104Cooling at a rate of C/sec to produce an alloy sheet, the atmosphere of the casting may typically be argon, the pressure of the casting may typically be 5.5 × 104Pa。
The cooling can be realized by introducing cooling water into the roller. Preferably, the water inlet temperature of the roller is less than or equal to 25 ℃, such as 22.5 ℃, 22.8 ℃, 23.1 ℃, 23.4 ℃, 23.5 ℃, 23.6 ℃ or 23.8 ℃, and more preferably 22.5-24 ℃. The roller may be a copper roller.
In the present invention, the operation and conditions for milling can be those conventional in the art. The milling typically includes a hydrogen milling process and a jet milling process.
The hydrogen breaking process can be a hydrogen breaking process conventional in the art, and for example, the hydrogen breaking process can be performed through hydrogen absorption, dehydrogenation and cooling treatment. The hydrogen absorption can be carried out under the condition that the hydrogen pressure is 0.15 MPa. The dehydrogenation can be carried out under the condition of vacuum pumping and temperature rise.
Wherein, the jet milling process can be a jet milling process which is conventional in the field, and the jet milling process can be carried out under a nitrogen atmosphere with the content of the oxidizing gas of below 120 ppm. The oxidizing gas refers to oxygen or moisture content.
The pressure of the crushing chamber in the jet milling process can be 0.3-0.4 MPa, such as 0.38 MPa.
The duration of the jet milling process may be 2 to 4 hours, for example 3 hours.
After the jet milling process, a lubricant, such as zinc stearate, may be added to the powder as is conventional 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 molding operation and conditions may be those conventional in the art. Including, for example, magnetic field forming or hot-press hot-deformation.
In the present invention, the sintering operation and conditions may be sintering operation conditions conventional in the art.
Wherein the sintering environment may be a vacuum, and the pressure of the vacuum may be 5 × 10-3Pa。
Wherein, the sintering also comprises preheating before. The preheating temperature can be 300-600 ℃. The preheating time can be 1-2 h. The preheating is preferably at a temperature of 300 ℃ and 600 ℃ for 1 hour each.
Wherein the sintering temperature is preferably 1060 to 1090 ℃, for example 1065 ℃, 1068 ℃, 1070 ℃, 1073 ℃, 1075 ℃ or 1085 ℃, more preferably 1065 to 1085 ℃.
The sintering time is preferably 5-10 h, such as 8 h.
In the present invention, the aging treatment preferably includes a primary aging treatment and a secondary aging treatment.
Wherein, the temperature of the primary aging treatment is preferably 850-950 ℃, and more preferably 900 ℃.
The time of the primary aging treatment is preferably 2 to 4 hours, for example 3 hours, and the time refers to the time at the temperature of the primary aging treatment.
The temperature of the secondary aging treatment is preferably 440 to 475 ℃, such as 440 ℃, 450 ℃, 455 ℃, 460 ℃, 465 ℃ or 472 ℃, more preferably 440 to 460 ℃.
The time of the secondary aging treatment is preferably 2 to 4 hours, for example 3 hours, and the time refers to the time at the temperature of the secondary aging treatment.
Wherein the rate of raising the temperature to the temperature of the primary aging treatment or the secondary aging treatment can be conventional in the art, and is usually 3-5 ℃/min.
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:
r: 28.5-34%; r is a rare earth element and at least comprises Nd;
Ga：>0.5％；
Cu：≥0.4％；
B：0.835～0.943％；
Al：<0.08％；
co: 2.502% or less but not 0;
Fe：59～69％；
n: one or more of Ti, Zr and Nb;
when N contains Ti, the content of Ti is 0.15-0.251%;
when N contains Zr, the content of Zr is 0.2-0.352%;
when the N contains Nb, the content of Nb is 0.2-0.5%;
the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material.
In the present invention, the grain boundary phase of the R-T-B permanent magnetic material preferably further includes R6T13M phase, wherein T refers to Fe and/or Co, and M refers to Cu and/or Ga.
Wherein, R is6T13The volume of the M phase compared to the total volume of the "grain boundary phase, main phase and rare earth-rich phase" is preferably 4 to 10%, for example 4.2%, 4.6%, 5.2%, 5.4%, 5.7%, 6.3%, 6.5%, 7.5%, 7.6%, 7.7% or 9.8%, more preferably 5to 9.8%. In the present invention, theGrain boundary phases mean two or more Nd2Tl4B is a general term for grain boundary phases between grains.
In the present invention, the grain boundary phase of the R-T-B permanent magnetic material preferably does not contain R6T13An Al phase. Wherein R is rare earth element, and T is Fe and/or Co.
In the present invention, the content of R is preferably 29 to 34%, for example, 29.414%, 30%, 30.19%, 30.381%, 30.502%, 30.997%, 31.003%, 31.004%, 31.007%, 31.215%, 31.502%, 31.505%, 32.005%, 32.006%, 32.007%, 33.77% or 33.983%, more preferably 30 to 31.6%, by mass, based on the total mass of the R-T-B permanent magnetic material.
In the present invention, the content of Nd is preferably 8 to 13% or 25 to 31.502%, for example, 9.5%, 9.501%, 9.505%, 10.503%, 10.504%, 25%, 29.012%, 29.895%, 29.979%, 30.302%, 31.012%, 31.402%, 31.497% or 31.502%, more preferably 9.5 to 10.503% or 29 to 31.502%, by mass, based on the total mass of the R-T-B permanent magnetic material.
In the R-T-B series permanent magnetic material, the R can also comprise Pr generally.
Wherein, when the R-T-B permanent magnetic material contains Pr, the content of Pr is preferably less than 8% and not 0, such as 0.103%, 0.2%, 0.203%, 0.295%, 0.303%, 0.402%, 0.502% or 6.502%, more preferably 0.1-0.502%; or the content of Pr is preferably 18.5 to 30%, more preferably 20.5 to 21.504%, for example 20.5%, 21.497%, 21.501%, 21.502%, 21.503% or 21.504, the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material.
In the invention, the R-T-B series permanent magnetic material does not contain heavy rare earth elements, and can also reach the level equivalent to the remanence and coercive force of the magnet material in the prior art. Or, the R-T-B series permanent magnetic material can also comprise RH which is a heavy rare earth element.
Wherein, when the R-T-B series permanent magnet material contains RH, the content of the RH is preferably 1-2.5% by mass of the total mass of the R-T-B series permanent magnet material.
Wherein, the RH preferably includes one or more of Dy, Tb and Ho.
When the RH includes Dy, the content of Dy is preferably 1 to 2.5%, for example, 1.965%, in mass% based on the total mass of the R-T-B based permanent magnetic material.
When the RH includes Tb, the content of Tb is preferably 1 to 2.5%, for example 1.984%, in mass percent based on the total mass of the R-T-B series permanent magnetic material.
In the present invention, the content of B is preferably 0.86 to 0.943%, for example, 0.861%, 0.862%, 0.879%, 0.88%, 0.902%, 0.903%, 0.905%, 0.906%, 0.92%, 0.921%, 0.922%, 0.942%, or 0.943%, more preferably 0.861 to 0.922%, in mass% based on the total mass of the R-T-B based permanent magnetic material.
In the invention, the atomic percentage of R and the atomic percentage of B in the R-T-B series permanent magnetic material preferably satisfy the following relational expression: B/R is more than or equal to 0.38, wherein in the formula, the atomic percent of B in the raw material composition is as follows, and the atomic percent of R in the R-T-B series permanent magnet material is as follows.
In the present invention, when Pr is included in the R-T-B based permanent magnetic material, it is preferable that B and Nd satisfy the following relationship: B/(Pr + Nd) is not less than 0.405, wherein B refers to the atomic percent of B in the R-T-B series permanent magnetic material, Pr refers to the atomic percent of Pr in the R-T-B series permanent magnetic material, and Nd refers to the atomic percent of Nd in the raw material composition.
In the present invention, the Ga content is preferably 0.52 to 1.8%, for example, 0.522%, 0.552%, 0.553%, 0.654%, 0.85%, 0.851%, 0.852%, 1.052%, 1.252%, 1.75%, or 1.792%, more preferably 0.6 to 1.8%, in mass% based on the total mass of the R-T-B-based permanent magnet material.
In the present invention, the content of Cu is preferably 0.405 to 2.001%, for example, 0.405%, 0.452%, 0.454%, 0.551%, 0.601%, 0.65%, 0.852%, 0.854%, 0.994%, 1.25%, 1.254%, 1.502%, 1.854%, 1.857%, 1.985%, or 2.001%, more preferably 0.55 to 1.05%, or 1.25 to 2.001%, in percentage by mass based on the total mass of the R-T-B-based permanent magnetic material.
In the present invention, the content of Co is preferably 0.49 to 2.5%, for example, 0.49%, 0.492%, 0.497%, 1.202%, 1.503%, 1.594%, 1.6%, 1.602%, 1.8%, 1.804%, 1.991%, 2%, or 2.502%, more preferably 0.49 to 2%, by mass, based on the total mass of the R-T-B-based permanent magnetic material.
In the invention, a person skilled in the art knows that although Al is not actively added in the raw material formula, the addition of other elements, such as Fe, Co and the like, can not reach 100% in purity according to the means of the current process, and other impurities can be inevitably introduced, wherein Al can be contained; in addition, in the preparation process, a person skilled in the art generally uses an aluminum crucible for melting, and a trace amount of Al is also inevitably introduced, so that the formulation of the final product of the present invention contains a trace amount (0.08% or less) of Al.
In the present invention, the content of Al is preferably 0.01 to 0.05%, for example, 0.014%, 0.015%, 0.025%, 0.032%, or 0.041%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material.
In the present invention, the content of Fe is preferably 59.5 to 67.32%, for example, 59.681%, 60.009%, 62.244%, 62.331%, 62.799%, 63.811%, 64.042%, 64.312%, 64.324%, 64.331%, 64.71%, 64.903%, 65.419%, 65.469%, 65.744%, 67.008% or 67.32%, more preferably 60 to 66%, in percentage by mass based on the total mass of the R-T-B permanent magnetic material.
In the present invention, when the N includes Ti, the content of Ti is preferably 0.2 to 0.251%, for example, 0.2%, 0.202%, 0.22%, 0.222%, 0.224%, or 0.251%, in terms of mass% based on the total mass of the R-T-B-based permanent magnetic material.
In the present invention, when the N includes Zr, the content of Zr is preferably 0.22 to 0.352%, for example, 0.222%, 0.224%, 0.252%, 0.263%, 0.32%, 0.322%, 0.324%, or 0.352%, and more preferably 0.26 to 0.32%, in percentage by mass based on the total mass of the R-T-B-based permanent magnetic material.
In the present invention, when the N contains Zr, the content of Zr is preferably: zr is more than or equal to 0.26 percent and less than 3.48B-2.67, and B is the mass percent of the R-T-B series permanent magnetic material. For example, when the content of B is 0.86%, B in the formula is 0.86.
In the present invention, when the N includes Nb, the content of Nb is preferably 0.2 to 0.321%, for example, 0.2%, 0.202%, 0.221%, 0.222%, 0.251%, or 0.321%, in mass% based on the total mass of the R-T-B based permanent magnetic material.
In the invention, when the R-T-B series permanent magnet material contains Ti and Nb, the Ti/Nb ratio is preferably more than or equal to 1.5, wherein Ti is the mass percentage of the R-T-B series permanent magnet material, and Nb is the mass percentage of the R-T-B series permanent magnet material.
In the invention, the R-T-B series permanent magnetic material preferably comprises the following components in percentage by mass: r: 29-32%; r is a rare earth element and at least comprises Nd;
B：0.86～0.943％；
Ga：0.52～1.8％；
Cu：0.405～2.001％；
Co：0.49～2.502％；
Al：0.01～0.05％；
Fe：59.5～67.32％；
n: one or more of Ti, Zr and Nb;
when the N contains Ti, the content of the Ti is 0.2-0.251%;
when the N contains Zr, the content of Zr is 0.22-0.352%;
when the N contains Nb, the content of Nb is 0.22-0.321%;
percent (wt.)The ratio is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material; the grain boundary phase of the R-T-B series permanent magnet material also comprises R6T13An M phase; the R is6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 4-10%.
In the invention, the R-T-B series permanent magnetic material preferably comprises the following components in percentage by mass: r: 30-31.6%; the R is a rare earth element and comprises Nd and Pr; pr: 0.1-0.502% or 20.5-21.504%;
B：0.861～0.922％；
Ga：0.52～1.8％；
Cu：0.994～2.001％；
Co：0.49～2％；
Al：0.01～0.05％；
Fe：60～66％；
n: one or more of Ti, Zr and Nb;
when the N contains Ti, the content of the Ti is 0.2-0.251%;
when the N contains Zr, the content of Zr is 0.22-0.352%;
when the N contains Nb, the content of Nb is 0.22-0.321%;
the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material; the grain boundary phase of the R-T-B series permanent magnet material also comprises R6T13An M phase; the R is6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 5-9.8%.
In the invention, the R-T-B series permanent magnetic material preferably comprises the following components in percentage by mass: r: 30-31.6%; the R is a rare earth element and comprises Nd and Pr; pr: 0.1-0.502% or 20.5-21.504%;
B：0.861～0.922％；
Ga：0.6～1.8％；
Cu：0.405～2.001％；
Co：0.49～2％；
Al：0.01～0.05％；
Fe：60～66％；
ti: 0.2-0.251%; the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material; the grain boundary phase of the R-T-B series permanent magnet material also comprises R6T13An M phase; the R is6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 5-9.8%.
In the invention, the R-T-B series permanent magnetic material preferably comprises the following components in percentage by mass: r: 29-32%; r is a rare earth element and at least comprises Nd;
B：0.86～0.943％；
Ga：0.52～1.8％；
Cu：0.405～2％；
Co：0.45～2.5％；
Al：0.01～0.05％；
Fe：60～67.1％；
Zr：0.22～0.352％；
the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material; the grain boundary phase of the R-T-B series permanent magnet material also comprises R6T13An M phase; the R is6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 5-9.8%.
The invention also provides application of the R-T-B series permanent magnetic material as an electronic component.
The application field can be the automobile driving field, the wind power field, the servo motor field and the household appliance field (such as an air conditioner).
In the present invention, the room temperature means 25 ℃. + -. 5 ℃.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: on the premise of not adding heavy rare earth elements, the R-T-B series permanent magnet material can still be prepared to have better magnetic performance (remanence, coercive force, temperature stability and squareness degree) by adopting a low-boron aluminum-free system, and meanwhile, the permanent magnet materials in the same batch have uniform magnetic performance.
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. Example 1
The raw materials used for preparing the R-T-B series permanent magnetic material in this example are shown in table 1, and the preparation process is as follows:
(1) smelting process according to the formula shown in example 1 in Table 1, the prepared raw materials are put into a crucible made of alumina, and are put into a high-frequency vacuum induction smelting furnace at 5 × 10-2Vacuum melting is carried out at a temperature of 1500 ℃ or lower in a vacuum of Pa.
(2) The casting process comprises the following steps: introducing Ar gas into a smelting furnace after vacuum smelting to enable the air pressure to reach 5.5 ten thousand Pa, then casting, and enabling the molten liquid to pass through a copper roller with the rotation speed of 29 revolutions per minute to prepare a rapid hardening alloy sheet with the thickness of 0.12-0.35mm, wherein in the casting process, chilled water needs to be introduced into the copper roller, and the water inlet temperature is 23.5 ℃; at 102DEG C/sec-104The cooling rate of DEG C/second obtains the quenched alloy.
(3) Hydrogen crushing and crushing: 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 hydrogen pressure at 0.15MPa, fully absorbing hydrogen, vacuumizing while heating, fully dehydrogenating, cooling, and taking out the powder after hydrogen breaking and crushing.
(4) 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 120ppm or less and a pressure in the pulverization chamber of 0.38MPa to obtain a fine powder. The oxidizing gas refers to oxygen or moisture.
(5) 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.
(6) 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).
(7) Sintering process, each formed body is moved to a sintering furnace for sintering, and sintering is carried out at 5 × 10-3Pa at 300 deg.C and 600 deg.C for 1 hr, sintering at 1070 deg.C for 8 hr, introducing Ar gas to make pressure reach 0.1MPa, and cooling to room temperature.
(8) And (3) aging treatment process: and (3) heating the sintered body from 20 ℃ to 900 ℃ at the heating rate of 3-5 ℃/min in high-purity Ar gas, carrying out first-stage aging treatment at the temperature of 900 ℃ for 3 hours, cooling to room temperature, and taking out. Then, the temperature is raised from 20 ℃ to 465 ℃ at the heating rate of 3-5 ℃/min, and the secondary aging temperature is carried out at the temperature of 465 ℃.
TABLE 1 formulation (wt%) of raw material composition of R-T-B series permanent magnet material of examples 1 to 15 and comparative examples 1 to 10, and water inlet temperature, sintering temperature, secondary aging temperature in preparation method
Figure BDA0002396104660000191
Figure BDA0002396104660000201
Note: "/" means that the element is not included. The wt% is mass percent.
It should be noted that: the magnetic performance of the R-T-B series permanent magnet materials in the comparative examples 1-10 is the best performance obtained by the formula of the comparative examples 1-10 after process optimization (aging temperature, sintering temperature or water inlet temperature).
2. The raw material formulations of the R-T-B series permanent magnet materials in examples 2 to 15 and comparative examples 1 to 10 are shown in Table 1, and the parameters of the preparation methods are the same as those of example 1 except that the sintering temperature, the secondary aging temperature and the water inlet temperature in step 2 are shown in Table 1.
3. Component determination: the R-T-B permanent magnet materials of examples 1 to 15 and comparative examples 1 to 10 were measured by using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES). The test results are shown in table 2 below.
TABLE 2 composition and content (wt%) of rare earth permanent magnet material
Figure BDA0002396104660000202
Figure BDA0002396104660000211
Note: "/" means that the element is not included. The wt% is mass percent.
Effect example 1
Magnetic Properties of R-T-B permanent magnet materials in examples 1 to 15 and comparative examples 1 to 10
1. Microstructure: the perpendicular orientation plane of the R-T-B system permanent magnetic material was polished by FE-EPMA detection, and detected by field emission electron probe microanalyzer (FE-EPMA) (JEOL 8530F, Japan Electron Ltd.). Detection of R in grain boundaries6T13M phase and R6T13Al phase, T refers to Fe and/or Co, and M refers to Ga and/or Cu. The test results are shown in table 3 below.
Wherein R is6T13M phase or R6T13The Al phase ratio means: r6T13M phase or R6T13The ratio of the volume of the Al phase to the total volume of the "main phase, grain boundary phase and rare earth-rich phase".
2. Remanence and coercive force: the sintered magnet is detected by using an NIM-10000H type BH large rare earth permanent magnet nondestructive measurement system of China measurement institute. And the temperature coefficient of remanence and the temperature coefficient of coercive force are obtained by calculation. The test results are shown in table 3 below.
Wherein, Br or Hcj both mean values: and (3) calculating an average value by testing the residual magnetism or the coercive force of 5 rare earth permanent magnetic materials in the same batch.
3. Consistency detection of magnetic performance of R-T-B series permanent magnetic material
Squareness ═ Hk/Hcj; where Hk is the value of the external magnetic field H when Br is 90% Br, and Hcj is the coercive force.
The relative magnetic permeability is Br/Hcb; wherein Br is remanence, Hcb is magnetic induction coercive force, and when an inflection point exists in the J-H curve, the magnetic conductivity is taken before the inflection point.
Max (Max hcj) -Min (hcj): in the same example or the same comparative example, the coercivity minimum value is subtracted from the coercivity maximum value, and if it is more than 1.5kOe, the magnetic uniformity is poor.
Several ndfeb materials were prepared in each example and comparative example of the present invention, and the same lot refers to several ndfeb materials obtained in each example and comparative example. For each test in table 3, each ndfeb material refers to a 10mm by 10mm cylinder cut according to the unit of performance test.
TABLE 3
Figure BDA0002396104660000221
Figure BDA0002396104660000231
Note that "×" means that R is not present6T13M phase or R6T13An Al phase.
The remaining parameters in Table 3 are the average values of 5R-T-B series permanent magnetic materials in the same batch, except for Max (Hcj) -Min (Hcj).
In Table 3, data of a Br temperature coefficient α (Br)%/DEG C at 20 to 80 ℃, a Hcj temperature coefficient β (Hcj)%/DEG C at 20 to 80 ℃, a Br temperature coefficient β (Hcj)%/DEG C at 20 to 150 ℃, and a Hcj temperature coefficient β (Hcj)%/DEG C at 20 to 150 ℃ are absolute values.

Claims (10)

1. A raw material composition of an R-T-B series permanent magnetic material is characterized by comprising the following components in percentage by mass:
r: 28.5-34%; r is a rare earth element and at least comprises Nd;
Ga：>0.5％；
Cu：≥0.4％；
B：0.84～0.94％；
co: less than or equal to 2.5 percent but not 0 percent;
Fe：59～69％；
n: one or more of Ti, Zr and Nb;
when the N comprises Ti, the content of the Ti is 0.15-0.25%;
when the N comprises Zr, the content of Zr is 0.2-0.35%;
when the N comprises Nb, the content of Nb is 0.2-0.5%;
the percentage is the mass percentage of each component in the total mass of the raw material composition.
2. The raw material composition according to claim 1, wherein the content of R is 29 to 34%, preferably 30 to 31.6%, in mass percent based on the total mass of the raw material composition;
and/or the content of Nd is 8-13% or 25-31.5%, preferably 9.5-10.5% or 29-31.5%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or, the raw material composition does not contain Al;
and/or, in the raw material composition, the R also comprises Pr;
when the raw material composition contains Pr, the content of Pr is preferably less than 8% and not 0% or 18.5-30%; more preferably 0.1-0.5 or 20.5-21.5%, the percentage is the mass percentage of the total mass of the raw material composition;
and/or in the raw material composition, the R also comprises RH which is a heavy rare earth element;
when the raw material composition further comprises RH, the content of the RH is preferably 1-2.5%, and the percentage is the mass percentage of the total mass of the raw material composition;
wherein the RH preferably includes one or more of Dy, Tb and Ho;
when the RH comprises Dy, the content of Dy is preferably 1-2.5% by mass of the total mass of the raw material composition;
when the RH comprises Tb, the content of Tb is preferably 1-2.5%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or the content of B is 0.86-0.94%, preferably 0.86-0.92%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or, in the raw material composition, the atomic percent of R and the atomic percent of B satisfy the following relational expression: B/R is more than or equal to 0.38, wherein B is the atomic percentage in the raw material composition, and R is the atomic percentage in the raw material composition;
and/or the content of Ga is 0.52-1.8%, preferably 0.6-1.8%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or the Cu content is 0.4-2%, preferably 0.55-1.05% or 1.25-2%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or the content of Co is 0.5-2.5%, preferably 0.5-2%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or the content of Fe is 59.5-67.3%, preferably 60-66%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or when the N contains Ti, the content of the Ti is 0.2-0.25 percent, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or, when the N contains Zr, the Zr content is 0.22-0.35%, preferably 0.26-0.32%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or when the N contains Zr, the Zr content is as follows: zr is more than or equal to 0.26 percent and less than 3.48B-2.67, wherein B is the mass percent of the raw material composition;
and/or when the N contains Nb, the content of Nb is 0.2-0.32%, and the percentage is the mass percentage of the total mass of the raw material composition.
3. The raw material composition according to claim 1 or 2, wherein the raw material composition of the R-T-B series permanent magnetic material comprises the following components in percentage by weight: r: 29-32%; r is a rare earth element and at least comprises Nd; b: 0.86-0.94%; ga: 0.52-1.8%; cu: 0.45-2%; co: 0.45-2.5%; fe: 59.5-67.3%; n: one or more of Ti, Zr and Nb; when the N contains Ti, the content of the Ti is 0.2-0.25%; when the N contains Zr, the content of Zr is 0.25-0.35%; when the N contains Nb, the content of Nb is 0.25-0.35%; the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition;
or the raw material composition of the R-T-B series permanent magnet material comprises the following components in percentage by weight: r: 29-32%; the R is a rare earth element and comprises Nd and Pr; pr: 0.1-0.5% or 18.5-25%; b: 0.86-0.94%; ga: 0.52-1.8%; cu: 0.45-2%; co: 0.45-2.5%; fe: 62.8-67.25%; ti: 0.2-0.25%; the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition;
or the raw material composition of the R-T-B series permanent magnet material comprises the following components in percentage by weight: r: 29-32%; the R is a rare earth element and comprises Nd and Pr; pr: 0.1-0.5% or 18.5-25%; b: 0.86-0.94%; ga: 0.52-0.55%; cu: 0.45-2%; co: 0.45-2.5%; fe: 62.8-67.25%; ti: 0.2-0.25%; the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition;
or the raw material composition of the R-T-B series permanent magnetic material comprises the following components in percentage by mass: r: 29-32%; r is a rare earth element and at least comprises Nd; b: 0.86-0.94%; ga: 0.52-1.8%; cu: 0.45-2%; co: 0.45-2.5%; fe: 60-67.1%; zr: 0.25 to 0.35 percent; the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition;
or the raw material composition of the R-T-B permanent magnet material comprises the following components in percentage by weight: r: 29-32%; r is a rare earth element and at least comprises Nd; b: 0.86-0.94%; ga: 0.52-0.55%; cu: 0.45-2%; co: 0.45-0.55%; fe: 60-67.1%; zr: 0.25 to 0.35 percent; the raw material composition does not contain Al; the percentage is the mass percentage of each component in the total mass of the raw material composition.
4. A preparation method of an R-T-B series permanent magnetic material is characterized by comprising the following steps: the raw material composition of the R-T-B series permanent magnet material according to any one of claims 1 to 3 is subjected to casting, milling, forming, sintering and aging treatment.
5. The method of claim 4, wherein the casting further comprises melting;
wherein the smelting temperature is preferably below 1500 ℃;
and/or said casting is at 102DEG C/sec-104Cooling at a speed of DEG C/second;
wherein the cooling is preferably realized by introducing cooling water into the rollers;
the water inlet temperature of the roller is preferably less than or equal to 25 ℃, and more preferably 22.5-24 ℃;
and/or, the milling comprises a hydrogen crushing process and an airflow milling process;
wherein, the hydrogen breaking process preferably comprises hydrogen absorption, dehydrogenation and cooling treatment;
wherein the jet milling process is preferably carried out under a nitrogen atmosphere having an oxidizing gas content of 120ppm or less;
wherein, the pressure of the crushing chamber of the jet milling process is preferably 0.3-0.4 MPa;
wherein the time of the air flow milling process is preferably 2-4 hours;
after the jet milling process, a lubricant is preferably added into the powder; the addition amount of the lubricant is preferably 0.10-0.15% of the weight of the mixed powder;
and/or, the forming comprises a magnetic field forming method or a hot-pressing hot-deformation method;
and/or, the sintering also comprises preheating; the preheating temperature is preferably 300-600 ℃; the preheating time is preferably 1-2 h;
and/or the sintering temperature is 1060-1090 ℃, preferably 1065-1085 ℃;
and/or the sintering time is 5-10 h;
and/or the aging treatment comprises primary aging treatment and secondary aging treatment;
wherein, the temperature of the first-stage aging treatment is preferably 850-950 ℃, and more preferably 900 ℃;
wherein the time of the primary aging treatment is preferably 2-4 h;
wherein, the temperature of the secondary aging treatment is preferably 440 to 475 ℃, and more preferably 440 to 460 ℃;
wherein the time of the secondary aging treatment is preferably 2-4 h;
wherein the rate of raising the temperature to the temperature of the primary or secondary aging treatment is preferably 3to 5 ℃/min.
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:
r: 28.5-34%; r is a rare earth element and at least comprises Nd;
Ga：>0.5％；
Cu：≥0.4％；
B：0.835～0.943％；
Al：<0.08％；
co: 2.502% or less but not 0;
Fe：59～69％；
n: one or more of Ti, Zr and Nb;
when N contains Ti, the content of Ti is 0.15-0.251%;
when N contains Zr, the content of Zr is 0.2-0.352%;
when the N contains Nb, the content of Nb is 0.2-0.5%;
the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material.
8. The R-T-B permanent magnetic material according to claim 7, further comprising R in a grain boundary phase of the R-T-B permanent magnetic material6T13An M phase, wherein T refers to Fe and/or Co, M refers to Cu and/or Ga;
wherein, said R6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 4-10%, preferably 5-9.8%;
and/or the content of R is 29-34%, preferably 30-31.6%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or, the content of Nd is 8-13% or 25-31.502%, preferably 9.5-10.503% or 29-31.502%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material;
and/or in the R-T-B series permanent magnetic material, the R also comprises Pr;
wherein, when the R-T-B series permanent magnetic material contains Pr, the content of Pr is preferably below 8% and not 0, and more preferably 0.1-0.502%; or, the content of Pr is preferably 18.5 to 30%, more preferably 20.5 to 21.504%, the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or the R-T-B series permanent magnetic material also comprises RH which is a heavy rare earth element;
when the R-T-B series permanent magnet material contains RH, the content of the RH is preferably 1-2.5%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
wherein the RH preferably includes one or more of Dy, Tb and Ho;
when the RH contains Dy, the content of Dy is preferably 1-2.5% by mass of the total mass of the R-T-B series permanent magnet material;
when the RH comprises Tb, the content of Tb is preferably 1-2.5%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or the content of B is 0.86-0.943%, preferably 0.861-0.922%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or the atomic percent of R and the atomic percent of B in the R-T-B series permanent magnetic material satisfy the following relational expression: B/R is more than or equal to 0.38, wherein in the formula, the atomic percent of B in the raw material composition and the atomic percent of R in the R-T-B series permanent magnet material are shown in the specification;
and/or the content of Ga is 0.52-1.8%, preferably 0.6-1.8%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material;
and/or the Cu content is 0.405-2.001%, preferably 0.55-1.05% or 1.25-2.001%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or the content of Co is 0.49-2.5%, preferably 0.49-2%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or the Al content is 0.01-0.05%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or the content of Fe is 59.5-67.32%, preferably 60-66%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or when the N contains Ti, the content of the Ti is 0.2-0.251%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material;
and/or, when the N contains Zr, the content of the Zr is 0.22-0.352%, preferably 0.26-0.32%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material;
and/or, when the N comprises Zr, the Zr content is as follows: zr is more than or equal to 0.26 percent and less than 3.48B-2.67, and B is the mass percent of the R-T-B series permanent magnetic material;
and/or when the N comprises Nb, the content of Nb is 0.2-0.321%, and the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
9. The R-T-B system permanent magnetic material according to claim 7 or 8, wherein the R-T-B system permanent magnetic material comprises the following components in percentage by weight: r: 29-32%; r is a rare earth element and at least comprises Nd; b: 0.86-0.943%; ga: 0.52-1.8%; cu: 0.405-2.001%; co: 0.49-2.502%; al: 0.01-0.05%; fe: 59.5-67.32%; n: one or more of Ti, Zr and Nb; when the N contains Ti, the content of the Ti is 0.2-0.251%; when the N contains Zr, the content of Zr is 0.22-0.352%; when the N contains Nb, the content of Nb is 0.22-0.321%; the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material; the grain boundary phase of the R-T-B series permanent magnet material also comprises R6T13An M phase; the R is6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 4-10%;
or the R-T-B series permanent magnetic material comprises the following components in percentage by weight: r: 30-31.6%; r is rareThe R comprises Nd and Pr; pr: 0.1-0.502% or 20.5-21.504%; b: 0.861-0.922%; ga: 0.52-1.8%; cu: 0.994-2.001%; co: 0.49-2%; al: 0.01-0.05%; fe: 60-66%; n: one or more of Ti, Zr and Nb; when the N contains Ti, the content of the Ti is 0.2-0.251%; when the N contains Zr, the content of Zr is 0.22-0.352%; when the N contains Nb, the content of Nb is 0.22-0.321%; the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material; the grain boundary phase of the R-T-B series permanent magnet material also comprises R6T13An M phase; the R is6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 5-9.8%;
or the R-T-B series permanent magnetic material comprises the following components in percentage by weight: r: 30-31.6%; the R is a rare earth element and comprises Nd and Pr; pr: 0.1-0.502% or 20.5-21.504%; b: 0.861-0.922%; ga: 0.6-1.8%; cu: 0.405-2.001%; co: 0.49-2%; al: 0.01-0.05%; fe: 60-66%; ti: 0.2-0.251%; the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material; the grain boundary phase of the R-T-B series permanent magnet material also comprises R6T13An M phase; the R is6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 5-9.8%;
or the R-T-B series permanent magnetic material comprises the following components in percentage by weight: r: 29-32%; r is a rare earth element and at least comprises Nd; b: 0.86-0.943%; ga: 0.52-1.8%; cu: 0.405-2%; co: 0.45-2.5%; al: 0.01-0.05%; fe: 60-67.1%; zr: 0.22-0.352%; the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnetic material; the grain boundary phase of the R-T-B series permanent magnet material also comprises R6T13An M phase; the R is6T13The ratio of the volume of the M phase to the total volume of the grain boundary phase, the main phase and the rare earth-rich phase is 5-9.8%.
10. An application of the R-T-B series permanent magnetic material as claimed in any one of claims 6 to 9 as an electronic component.
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