WO2019242581A1 - 一种低B含量的R-Fe-B系烧结磁铁及其制备方法 - Google Patents

一种低B含量的R-Fe-B系烧结磁铁及其制备方法 Download PDF

Info

Publication number
WO2019242581A1
WO2019242581A1 PCT/CN2019/091536 CN2019091536W WO2019242581A1 WO 2019242581 A1 WO2019242581 A1 WO 2019242581A1 CN 2019091536 W CN2019091536 W CN 2019091536W WO 2019242581 A1 WO2019242581 A1 WO 2019242581A1
Authority
WO
WIPO (PCT)
Prior art keywords
content
sintered magnet
low
phase
sintered
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/091536
Other languages
English (en)
French (fr)
Inventor
蓝琴
周燕
永田浩
施尧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen Tungsten Co Ltd
Original Assignee
Xiamen Tungsten Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen Tungsten Co Ltd filed Critical Xiamen Tungsten Co Ltd
Priority to DK19822708.4T priority Critical patent/DK3745430T3/da
Priority to JP2020551894A priority patent/JP7379362B2/ja
Priority to EP19822708.4A priority patent/EP3745430B1/en
Priority to ES19822708T priority patent/ES2905485T3/es
Priority to US16/964,645 priority patent/US11993836B2/en
Publication of WO2019242581A1 publication Critical patent/WO2019242581A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • C—CHEMISTRY; METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • 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
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • 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
    • H01F41/0266—Moulding; Pressing
    • 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
    • H01F41/0273—Imparting anisotropy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2202/00—Treatment under specific physical conditions
    • B22F2202/05—Use of magnetic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/35—Iron
    • B22F2301/355—Rare Earth - Fe intermetallic alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic
    • 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
    • H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working

Definitions

  • the present invention relates to the technical field of manufacturing magnets, and in particular, to a low B content R-Fe-B series sintered magnet.
  • RTB series sintered magnets (R refers to rare earth elements, T refers to transition metal elements, and B refers to boron elements) are widely used in the field of wind power generation, electric vehicles and inverter air conditioners due to their excellent magnetic properties. And the requirements of various manufacturers for the performance of magnets have gradually increased.
  • RTB-based sintered magnets In order to improve Hcj, RTB-based sintered magnets usually add more heavy rare-earth elements such as Dy and Tb with larger anisotropic fields. However, this method has the problem of reducing the residual magnetic flux density Br. Equal weight rare earth resources are limited and expensive, and they also have problems such as unstable supply and large price fluctuations. Therefore, it is required to develop a technology that reduces the use of heavy rare earths such as Dy and Tb and increases the R-T-B based sintered magnets Hcj and Br.
  • the content of B is limited to a relatively small specific range compared with the conventionally used RTB-based alloys, and it contains one or more metals selected from Al, Ga, and Cu Element M, thereby generating the R 2 T 17 phase, and by sufficiently ensuring the volume ratio of the transition metal-rich phase R 6 T 13 M generated using the R 2 T 17 phase as a raw material, thereby suppressing the content of heavy rare earth and improving the Hcj RTB series sintered magnet.
  • the RT-Ga phase is formed by reducing the B content compared to ordinary RTB alloys.
  • the RT-Ga phase also has some magnetic properties.
  • RTB When a large number of RT-Ga phases are present in the crystal grains of the sintered magnets, the increase in Hcj is hindered.
  • the amount of Ga are in an optimum range corresponding to the amount of R 2 T 17 phase produced.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a low B content R-Fe-B series sintered magnet.
  • the optimal range of R, B, Co, Cu, Ga and Ti is selected to ensure the main phase. Under the premise of optimal volume fraction, it has a higher Br value than conventional B content magnets.
  • R 6 -T 13- ⁇ M 1 + ⁇ system phase by forming a special composition of R 6 -T 13- ⁇ M 1 + ⁇ system phase and increasing its volume ratio in the grain boundary phase To get higher Hcj and SQ values.
  • a low-B content R-Fe-B-based sintered magnet which contains a R 2 Fe 14 B-type main phase.
  • the R is at least one rare earth element including Nd.
  • the sintered magnet includes the following: ingredient:
  • the sintered magnet has an R 6 -T 13- ⁇ -M 1 + ⁇ phase, which accounts for more than 75% of the total volume of the grain boundary.
  • T is selected from at least one of Fe or Co.
  • M includes 80% by weight of Ga and 20% by weight. % Cu, ⁇ is (-0.14-0.04).
  • the wt% in the present invention is a weight percentage.
  • the R mentioned in the present invention is at least one selected from the group consisting of Nd, Pr, Dy, Tb, Ho, La, Ce, Pm, Sm, Eu, Gd, Er, Tm, Yb, Lu, or yttrium.
  • the magnet Br increases due to the reduction of the heterogeneous phase and the high volume fraction of the main phase; meanwhile, a specific content range of Co, Cu, Ga, Ti is added to form the above-mentioned special composition R 6 -T 13 - ⁇ M 1 + ⁇ phase, and increase its volume fraction in the sintered magnet grain boundary phase, so that the grain boundary distribution is more uniform and continuous, forming a thin grain boundary layer Nd-rich phase, and further optimize the crystal
  • the boundary plays a role of demagnetization, which increases the nucleation field of the demagnetized domain nucleus. Therefore, Hcj is significantly improved, and the squareness is improved.
  • the R 6 -T 13- ⁇ -M 1 + ⁇ phase with the above specific composition, M may be selected from at least one of Cu, Ga, or Ti and must contain Ga.
  • R 6 -T 13 Ga 1-ys Ti y Cu s ).
  • the sintered magnet is a sintered magnet after heat treatment.
  • the heat treatment stage helps to form more R 6 -T 13- ⁇ -M 1 + ⁇ series phases (referred to as R 6 -T 13 -M phase) with the above-mentioned special composition, and improves Hcj.
  • the sintered magnet is prepared by the following steps: a step of preparing a quenched alloy at a cooling rate of 10 2 °C / sec to 10 4 °C / sec in a raw material component of the sintered magnet;
  • the sintered magnet alloy is hydrogen-absorbed and crushed, and then finely pulverized to make a fine powder;
  • a formed body is obtained by a magnetic field forming method or hot pressing and hot deformation, and the temperature is 900 ° C-1100 ° C in a vacuum or inert gas.
  • the formed body is obtained by sintering, followed by heat treatment.
  • the cooling rate is 10 2 °C / sec-10 4 °C / s
  • the sintering temperature is 900 °C -1100 °C, which is a conventional choice in the industry. Therefore, in the embodiment, the above-mentioned cooling rate and sintering are not used. The temperature range is tested and verified.
  • a method for preparing a low B content R-Fe-B series sintered magnet which contains a R 2 Fe 14 B type main phase, wherein R is at least one rare earth element including Nd, and the sintering is characterized in that
  • the magnet includes the following components:
  • the method is as follows: the step of preparing the molten material of the sintered magnet raw material component into a sintered magnet alloy at a cooling rate of 10 2 °C / sec to 10 4 °C / sec; Then, a step of finely pulverizing to obtain a fine powder; obtaining a formed body by a magnetic field forming method, and sintering the formed body at a temperature of 900 ° C. to 1100 ° C. in a vacuum or an inert gas, followed by heat treatment.
  • the volume fraction of the above-specified R 6 -T 13- ⁇ M 1 + ⁇ phase in the sintered magnet can be increased, so that the grain boundary distribution is more Uniform and more continuous, forming a thin layer of Nd-rich phase at the grain boundary, further optimizing the grain boundary, and acting as a demagnetization coupling.
  • the temperature range of the heat treatment is a conventional choice in the industry, therefore, the above temperature range is not tested and verified in the examples.
  • the content of Fe is 61 wt% to 69.5 wt%, ⁇ is (-0.14-0.04), a cooling rate of 10 2 ° C / sec to 10 4 ° C / sec, and a temperature of 900 ° C to 1100 ° C.
  • the content range of the sintering temperature and the like is a conventional choice in the industry. Therefore, in the examples, the ranges of Fe, ⁇ , etc. have not been tested and verified.
  • Example 1 is a distribution diagram of Nd, Cu, Ga, and Co formed by scanning an EPMA surface of a sintered magnet in Example 1.7;
  • the sintered magnet uses the NIM-10000H type BH bulk rare earth permanent magnet non-destructive measurement system of China Metrology Institute for magnetic performance testing.
  • composition measurement Each composition was measured using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES).
  • ICP-OES high-frequency inductively coupled plasma emission spectrometer
  • O amount of oxygen
  • N amount of nitrogen
  • C carbon amount
  • FE-EPMA inspection Polish the vertical orientation surface of the sintered magnet, and use a field emission electron probe microanalyzer (FE-EPMA) [JEOL, 8530F] inspection.
  • FE-EPMA field emission electron probe microanalyzer
  • the selected heat treatment temperature range and heat treatment method are conventional choices in the industry.
  • a two-stage heat treatment is used.
  • the heat treatment temperature of the first stage heat treatment is 800 ° C-950 ° C
  • the heat treatment temperature of the second stage heat treatment is 400 ° C. -650 ° C.
  • the composition includes X and 5.0% by weight and unavoidable impurities, and X is selected from Zn, Al, In, Si, Ti, V, Cr, Mn, Ni, Ge, Zr, Total content of Nb, Zr, and Cr when at least one element of Nb, Mo, Pd, Ag, Cd, Sn, Sb, Hf, Ta, or W is included in X when it includes at least one of Nb, Zr, or Cr Below 0.20wt%.
  • X is selected from Zn, Al, In, Si, Ti, V, Cr, Mn, Ni, Ge, Zr, Total content of Nb, Zr, and Cr when at least one element of Nb, Mo, Pd, Ag, Cd, Sn, Sb, Hf, Ta, or W is included in X when it includes at least one of Nb, Zr, or Cr Below 0.20wt%.
  • Fe is the balance.
  • the unavoidable impurities include O
  • the O content of the sintered magnet is 0.5 wt% or less.
  • low oxygen content magnets below 5000ppm
  • R 6 -T 13 -M phase can be more fully utilized to improve Hcj
  • RO compounds have less heterogeneous phases, square shape. Degree increased.
  • the unavoidable impurities mentioned in the present invention also include a small amount of C, N, S, P, and other impurities that are unavoidably mixed in the raw materials or in the manufacturing process. Therefore, the sintered magnets mentioned in the present invention In the manufacturing process, it is best to control the C content to less than 0.25% by weight, more preferably 0.1% by weight, the N content to be controlled to 0.15% by weight, the S content to be controlled to 0.05% by weight, and the P content to be controlled to 0.05 wt% or less.
  • the fine pulverization is a process of jet pulverization.
  • the degree of dispersion of the R 6 -T 13 -M phase in the sintered magnet is further improved.
  • the content of Dy, Tb, Gd or Ho in the R is 1% or less.
  • the presence of R 6 -T 13- ⁇ M 1 + ⁇ series phases has a more significant effect of increasing the magnet Hcj.
  • Raw material preparation process Nd, Dy with a purity of 99.5%, Fe-B for industrial use, Fe for industrial use, Co, Cu, Ti, Ga, and Al with a purity of 99.9%.
  • Melting process Put the prepared raw materials into a crucible made of alumina, and perform vacuum melting in a high-frequency vacuum induction melting furnace in a vacuum of 10 -2 Pa at a temperature below 1500 ° C.
  • Casting process Ar gas is introduced into the smelting furnace after vacuum melting so that the air pressure reaches 50,000 Pa, and the casting is performed by a single roll quenching method to obtain a quenched alloy at a cooling rate of 10 2 °C / sec to 10 4 °C / sec.
  • the quenched alloy was heat-treated at 600 ° C for 60 minutes, and then cooled to room temperature.
  • Hydrogen breaking and pulverizing process Vacuum the hydrogen breaking furnace in which the quenched alloy is placed at room temperature, and then pass hydrogen with a purity of 99.5% into the hydrogen breaking furnace to maintain a hydrogen pressure of 0.1 MPa. After fully absorbing hydrogen, evacuate While raising the temperature, a vacuum was evacuated at a temperature of 500 ° C, followed by cooling, and the hydrogen-pulverized powder was taken out.
  • Fine pulverization step In a nitrogen atmosphere with an oxidizing gas content of 100 ppm or less, the powder after hydrogen pulverization is pulverized for 2 hours under a pressure of a pulverization chamber pressure of 0.4 MPa to obtain a fine powder.
  • Oxidizing gas refers to oxygen or moisture.
  • Methyl octoate was added to the powder after jet milling, and the amount of methyl octoate was 0.15% of the weight of the powder after mixing, and then mixed thoroughly with a V-type mixer.
  • Magnetic field forming process Using a right-angle orientation type magnetic field forming machine, in a 1.8T orientation magnetic field, under the forming pressure of 0.4ton / cm 2 , the above powder added with methyl octoate was formed into a cube with a side length of 25mm. After one-time forming, it is demagnetized in a magnetic field of 0.2T.
  • the secondary forming was performed using a secondary forming machine (isostatic press) at a pressure of 1.4 ton / cm 2 .
  • Sintering process Each formed body is moved to a sintering furnace for sintering. After sintering under a vacuum of 10 -3 Pa, the temperature is maintained at 200 ° C and 800 ° C for 2 hours each, and then sintered at 1060 ° C for 2 hours. Ar gas was introduced to make the pressure reach 0.1 MPa, and then cooled to room temperature.
  • Heat treatment process The sintered body is subjected to a first-stage heat treatment at 900 ° C for 2 hours in a high-purity Ar gas, and then a second-stage heat treatment at 520 ° C for 2 hours, and then taken out after cooling to room temperature.
  • the sintered body is processed into a magnet with a diameter of 10mm and a thickness of 5mm, and the direction of the magnetic field is 5mm to obtain a sintered magnet.
  • the magnets made of the sintered bodies of Examples and Comparative Examples were directly subjected to ICP-OES inspection and magnetic performance inspection to evaluate their magnetic characteristics.
  • the components and evaluation results of the magnets of the examples and comparative examples are shown in Tables 1 and 2:
  • the B content exceeds 0.94 wt%
  • the B content increases, resulting in the formation of B-rich phases, such as R 1.1 Fe 4 B 4
  • the M phase also does not significantly increase the Hcj of the sintered magnet.
  • the coordinated addition of Co, Cu, Ga, and Ti ensures that a sufficient volume fraction of R is generated in the grain boundaries.
  • the 6 -T 13 -M phase improves the performance of sintered magnets more significantly.
  • the FE-EPMA test was performed on the sintered magnet of Example 1.7. The results are shown in Figure 1 and Table 3, where Figure 1 is the concentration distribution of Nd, Cu, Ga, and Co and the corresponding position BSE chart. Table 3 is a single Quantitative point analysis results show that there are at least three phases in the BSE image.
  • the off-white area 1 is the R 6 -T 13 -M phase, R is Nd, T is mainly Fe and Co, and M includes 80% by weight of Ga and 20% by weight.
  • the black region 2 is the R 2 Fe 14 B main phase, and the bright white region 3 is another R-rich phase.
  • Example R 6 -T 13 -M phase comprises More than 80% of the total grain boundary volume.
  • the volume of the R 6 -T 13 -M phase accounted for more than 75% of the total volume of the grain boundary, and the R 6- In the T 13 -M phase, R is Nd, or Nd and Dy, T is mainly Fe and Co, and M includes 80% by weight of Ga and 20% by weight of Cu.
  • the FE-EPMA test was performed on Comparative Example 1.4.
  • the results are shown in Figure 2, which respectively represent the concentration distributions of Nd, Cu, Ga, and Co and the corresponding BSE diagrams.
  • the gray-white area 1a in the BSE diagram is R 6 -T 13 -M Phase
  • the black region 2a is an R 2 Fe 14 B phase
  • the bright white region 3a is another R-rich phase. It can be seen that the proportion of the off-white R 6 -T 13 M phase in the grain boundary phase of the comparative example is small, and most of them are bright white Nd-rich phases of other compositions.
  • Raw material preparation process prepare Nd, Dy with purity of 99.8%, industrial Fe-B, pure Fe for industry, Co, Cu, Ti, Ga, Zr, Si with purity of 99.9%.
  • Melting process Put the prepared raw materials into a crucible made of alumina, and perform vacuum melting in a high-frequency vacuum induction melting furnace in a vacuum of 5 ⁇ 10 -2 Pa at a temperature below 1500 ° C.
  • Hydrogen breaking and pulverizing process Vacuum the hydrogen breaking furnace where the quenched alloy is placed at room temperature, and then pass hydrogen with a purity of 99.9% into the hydrogen breaking furnace to maintain the hydrogen pressure of 0.15 MPa. After fully absorbing hydrogen, vacuum While raising the temperature, dehydrogenation was sufficiently performed, and then cooling was performed, and the powder after hydrogen pulverization was taken out.
  • Fine pulverization step In a nitrogen atmosphere with an oxidizing gas content of 150 ppm or less, the powder after hydrogen pulverization is pulverized for 3 hours under a pressure of a pulverization chamber pressure of 0.38 MPa to obtain a fine powder.
  • Oxidizing gas refers to oxygen or moisture.
  • Zinc stearate was added to the powder after jet milling, and the amount of zinc stearate was 0.12% of the weight of the powder after mixing, and then mixed thoroughly with a V-type mixer.
  • Magnetic field forming process Using a right-angle orientation type magnetic field forming machine, in a 1.6T orientation magnetic field, under the forming pressure of 0.35ton / cm 2 , the above powder with zinc stearate was formed into a 25mm side length. The cube is demagnetized in a magnetic field of 0.2T after one forming.
  • the secondary forming was performed using a secondary forming machine (isostatic press forming machine) under a pressure of 1.3 ton / cm 2 .
  • Sintering process Each formed body is moved to a sintering furnace for sintering.
  • the sintering is carried out under a vacuum of 5 ⁇ 10 -3 Pa, at a temperature of 300 ° C and 600 ° C for 1 hour, and then at a temperature of 1040 ° C for 2 hours.
  • Ar gas was passed in to adjust the pressure to 0.1 MPa, and then cooled to room temperature.
  • Heat treatment process The sintered body is subjected to primary heat treatment at 880 ° C for 3 hours in high-purity Ar gas, and then subjected to secondary heat treatment at 500 ° C for 3 hours, and then taken out after cooling to room temperature.
  • the sintered body is processed into a magnet with a diameter of 20 mm and a thickness of 5 mm, and the thickness direction is the magnetic field orientation direction to obtain a sintered magnet.
  • the magnets made of the sintered bodies of the examples and comparative examples were directly subjected to ICP-OES testing and magnetic performance testing to evaluate their magnetic characteristics.
  • the composition and evaluation results of the magnets of the respective examples and comparative examples are shown in Tables 4 and 5:
  • the performance of sintered magnets is not significantly improved, and for Co in the range of 0.2 wt% to 1.0 wt%
  • the synergistic addition of Cu, Ga, and Ti ensures that more than 75% of the R 6 -T 13 -M phase is formed in the grain boundaries, and the Ga content in M is greater than 80% and the Cu content is less than 20%.
  • the performance improvement is even more obvious.
  • FE-EPMA was performed on the sintered magnets of Comparative Examples 2.1 and 2.3, and R 6 -T 13 -M phases were observed in the grain boundaries of the sintered magnets.
  • the R 6 -T 13 -M phases were smaller than the total volume of the grain boundaries. 75%.
  • Raw material preparation process prepare Nd, Dy with purity of 99.8%, industrial Fe-B, pure Fe for industry, Co, Cu, Ti, Ga, Ni, Nb, Mn with purity 99.9%.
  • Melting process Put the prepared raw materials into a crucible made of alumina, and perform vacuum melting in a high-frequency vacuum induction melting furnace in a vacuum of 5 ⁇ 10 -2 Pa.
  • Hydrogen breaking and pulverizing process Vacuum the hydrogen breaking furnace where the quenched alloy is placed at room temperature, and then pass hydrogen with a purity of 99.9% into the hydrogen breaking furnace to maintain the hydrogen pressure of 0.12 MPa. After fully absorbing hydrogen, evacuate While raising the temperature, dehydrogenation was sufficiently performed, and then cooling was performed, and the powder after hydrogen pulverization was taken out.
  • Fine pulverization step In a nitrogen atmosphere with an oxidizing gas content of 200 ppm or less, the powder after hydrogen pulverization is pulverized for 2 hours under a pressure of a pulverization chamber pressure of 0.42 MPa to obtain a fine powder.
  • Oxidizing gas refers to oxygen or moisture.
  • Zinc stearate was added to the powder after jet milling, and the amount of zinc stearate was 0.1% of the weight of the powder after mixing, and then mixed thoroughly with a V-type mixer.
  • Magnetic field forming process Using a right-angle orientation type magnetic field forming machine, in a 1.5T orientation magnetic field, under the forming pressure of 0.45ton / cm 2 , the above powder with zinc stearate was formed into a side length of 25mm. Cube, once demagnetized.
  • the secondary forming was performed using a secondary forming machine (isostatic pressing forming machine) under a pressure of 1.2 ton / cm 2 .
  • Sintering process Each formed body is moved to a sintering furnace for sintering.
  • the sintering is performed under a vacuum of 5 ⁇ 10 -4 Pa, at a temperature of 300 ° C and 700 ° C for 1.5 hours each, and then sintered at a temperature of 1050 ° C.
  • Ar gas was introduced to make the atmospheric pressure reach atmospheric pressure, it was circulated and cooled to room temperature.
  • Heat treatment process The sintered body is subjected to a primary heat treatment at 890 ° C for 3.5 hours in a high-purity Ar gas, and then subjected to a secondary heat treatment at a temperature of 550 ° C for 3.5 hours, and then taken out after cooling to room temperature.
  • the sintered body is processed into a magnet with a diameter of 20 mm and a thickness of 5 mm, and the thickness direction is the magnetic field orientation direction to obtain a sintered magnet.
  • the magnets made of the sintered bodies of the examples and comparative examples were directly subjected to ICP-OES testing and magnetic performance testing to evaluate their magnetic characteristics.
  • the composition and evaluation results of the magnets in the examples and comparative examples are shown in Tables 6 and 7:
  • the performance of sintered magnets is also not significantly improved, and for Ga in 0.3wt% -0.5wt%, the cooperative addition of Co, Cu, and Ti ensures that more than 75% of R 6 -T 13 is generated in the grain boundary -M phase, and the Ga content in M is greater than 80%, and the Cu content is less than 20%, which improves the performance of sintered magnets more significantly.
  • the insufficient B content leads to an increase in the R 2 -T 17 phase.
  • the synergistic addition of Cu, Ga, and Co is not present in the grain boundaries.
  • the formation of sufficient R 6 -T 13 M phase also does not significantly improve the performance of sintered magnets.
  • the magnet can be fully sintered.
  • Subsequent heat treatment can ensure that more than 75% of the R 6 -T 13 -M phase is formed in the grain boundaries, and the Ga content in M is greater than 80% and the Cu content is less than 20%, which significantly improves the performance of the sintered magnet.
  • R 6 -T 13 -M phase with a composition of more than 75% of the total volume of the grain boundary R is Nd and Dy
  • T is mainly For Fe and Co
  • M includes 80% by weight of Ga and 20% by weight of Cu.
  • Comparative Examples 3.2, 3.3, 3.4, and 3.5 were tested by FE-EPMA.
  • R 6 -T 13 -M phase was observed in the grain boundary of the sintered magnet, and R 6 -T 13 -M phase was less than 75% of the total volume of the grain boundary. .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Hard Magnetic Materials (AREA)
  • Manufacturing Cores, Coils, And Magnets (AREA)
  • Continuous Casting (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

本发明公开了一种低B含量的R-Fe-B系烧结磁铁及其制备方法，包括如下成分：28.5wt％-31.5wt％的R，0.86wt％-0.94wt％的B，0.2wt％-1wt％的Co，0.2wt％-0.45wt％的Cu，0.3wt％-0.5wt％的Ga，0.02wt％-0.2wt％的Ti，以及61wt％-69.5wt％的Fe，所述烧结磁铁具有占晶界总体积75％以上的R6-T13-δM1+δ系相。其选择最优范围含量的R、B、Co、Cu、Ga和Ti，通过形成特殊组成的R6-T13-δM1+δ系相并提高其在晶界相中的体积率，获得更高Hcj和SQ值。

Description

一种低B含量的R-Fe-B系烧结磁铁及其制备方法 技术领域
本发明涉及磁铁的制造技术领域，特别是涉及一种低B含量的R-Fe-B系烧结磁铁。
背景技术
R-T-B系烧结磁铁(R指稀土元素，T指过渡金属元素，B指硼元素)由于其优异的磁特性而被广泛应用于风力发电领域、电动汽车领域和变频空调领域等，其需求日益扩大，且各产商对于磁铁性能的要求也逐步提升。
为了提高Hcj，通常在R-T-B系烧结磁铁中添加较多的各向异性场更大的Dy、Tb等重稀土元素，但该种方式存在残留磁通密度Br降低的问题，同时，由于Dy、Tb等重稀土资源有限，价格昂贵，还具有供给不稳定、价格波动大等问题。因此，要求开发减少使用Dy、Tb等重稀土的使用量并提高R-T-B系烧结磁铁Hcj和Br的技术。
国际公开第2013/008756号记载了以下内容：通过与以往通常使用的R-T-B系合金相比，B含量限定到相对少的特定范围，并且含有选自Al、Ga、Cu中的1种以上的金属元素M，从而生成R 2T 17相，通过充分确保以该R 2T 17相为原料生成的过渡金属富集相R 6T 13M的体积率，从而获得抑制重稀土的含量并且提高Hcj的R-T-B系烧结磁铁。
CN105453195A记载了以下内容：通过与通常的R-T-B合金相比，降低B含量，由此形成了R-T-Ga相，但是，根据发明人等研究的结果，R-T-Ga相也具有若干的磁性，当R-T-B系烧结磁铁的晶粒中存在较多的R-T-Ga相时，变得妨碍Hcj的提高。为了在R-T-B系烧结磁铁中将R-T-Ga相的生成量抑制为较低，有必要通过将R量和B量设为合适的范围，从而降低R 2T 17相的生成量，且使R量和Ga量在与R 2T 17相的生成量相应的最适范围。其认为，抑制R 6-T 13-Ga相的生成量，使晶界形成较多的R-Ga和R-Ga-Cu相，从而获得高Br和高Hcj的磁铁。并且认为，在合金粉末阶段抑制R-T-Ga相的生成量，能够最终抑制最终获得的R-T-B系烧结磁铁的R-T-Ga相的生成量。
综上，现有技术侧重将烧结磁铁的R-T-Ga相作为一个整体进行研究，而忽略不同组成的R-T-Ga相的不同表现，从而在不同的文献中，得出了R-T-Ga相具有相反技术效果的结 论。
发明内容
本发明的目的在于克服现有技术之不足，提供一种低B含量的R-Fe-B系烧结磁铁，选择最优范围含量的R、B、Co、Cu、Ga和Ti，在确保主相体积分数最优的前提下，具有比常规B含量磁铁更高的Br值，同时通过形成特殊组成的R 6-T 13-δM 1+δ系相并提高其在晶界相中的体积率，获得更高Hcj和SQ值。
本发明提供的技术方案如下：
一种低B含量的R-Fe-B系烧结磁铁，其含有R 2Fe 14B型主相，所述的R为包括Nd的至少一种稀土元素，其特征在于，所述烧结磁铁包括如下成分：
28.5wt％-31.5wt％的R，
0.86wt％-0.94wt％的B，
0.2wt％-1wt％的Co，
0.2wt％-0.45wt％的Cu，
0.3wt％-0.5wt％的Ga，
0.02wt％-0.2wt％的Ti，以及
61wt％-69.5wt％的Fe，
所述烧结磁铁具有占晶界总体积75％以上的R 6-T 13-δ-M 1+δ系相，T选自Fe或Co的至少一种，M中包括80wt％以上的Ga和20wt％以下的Cu，δ为(-0.14-0.04)。
本发明中所述的wt％为重量百分比。
本发明所提及的R选自Nd、Pr、Dy、Tb、Ho、La、Ce、Pm、Sm、Eu、Gd、Er、Tm、Yb、Lu或钇元素中的至少一种。
在低TRE(稀土总含量)和低B含量的磁铁中，由于杂相减少，主相体积分数高，所以磁铁Br提高；同时添加特定含量范围的Co、Cu、Ga、Ti，形成上述特殊组成的R 6-T 13- δM 1+δ系相，并提高其在烧结磁铁晶界相中的体积分数，使晶界分布更均匀更连续，形成晶界薄层富Nd相，进一步优化晶界，起到去磁耦合作用，使反磁化畴核的形核场提高，因此Hcj显著提升，且方形度提高。
上述特定组成的R 6-T 13-δ-M 1+δ系相，M可以选自Cu、Ga或Ti等中的至少一种且必须含有Ga，举例来说，有成为R 6-T 13(Ga 1-y-sTi yCu s)的情形。
在推荐的实施方式中，所述烧结磁铁为经过热处理之后的烧结磁铁。热处理阶段有助于形成更多上述特殊组成的R 6-T 13-δ-M 1+δ系相(简称为R 6-T 13-M相)，提高Hcj。
在推荐的实施方式中，所述烧结磁铁由如下的步骤制得：将烧结磁铁的原料成分熔融液以10 2℃/秒-10 4℃/秒的冷却速度制备成急冷合金的工序；将所述烧结磁铁用合金吸氢破碎，之后再通过微粉碎制成细粉的工序；用磁场成形法或热压热变形获得成形体，并在真空或惰性气体中以900℃-1100℃的温度对所述成形体进行烧结，之后进行热处理获得。
本发明中，冷却速度采用10 2℃/秒-10 4℃/秒，烧结温度采用900℃-1100℃的温度为本行业的常规选择，因此，在实施例中，没有对上述冷却速度和烧结温度的范围加以试验和验证。
本发明提供的另一种技术方案如下：
一种低B含量的R-Fe-B系烧结磁铁的制备方法，其含有R 2Fe 14B型主相，所述的R为包括Nd的至少一种稀土元素，其特征在于，所述烧结磁铁包括如下成分：
28.5wt％-31.5wt％的R，
0.86wt％-0.94wt％的B，
0.2wt％-1wt％的Co，
0.2wt％-0.45wt％的Cu，
0.3wt％-0.5wt％的Ga，
0.02wt％-0.2wt％的Ti，以及
61wt％-69.5wt％的Fe，
并采用如下的方式制得：将烧结磁铁原料成分熔融液以10 2℃/秒-10 4℃/秒的冷却速度制备成烧结磁铁用合金的工序；将所述烧结磁铁用合金吸氢破碎，之后再通过微粉碎制成细粉的工序；用磁场成形法获得成形体，并在真空或惰性气体中以900℃-1100℃的温度对所述成形体进行烧结，之后进行热处理获得。
这样，就可以在低TRE(稀土总含量)和低B含量的磁铁中，提高上述特殊组成的 R 6-T 13-δM 1+δ系相在烧结磁铁的体积分数，使晶界分布更均匀更连续，形成晶界薄层富Nd相，进一步优化晶界，起到去磁耦合作用。
本发明中，热处理的温度范围为本行业的常规选择，因此，没有在实施例中对上述温度范围加以试验和验证。
需要说明的是，本发明中，Fe的含量为61wt％-69.5wt％、δ为(-0.14-0.04)、10 2℃/秒-10 4℃/秒的冷却速度、900℃-1100℃的烧结温度等的含量范围为本行业的常规选择，因此，在实施例中，没有对Fe、δ等的范围加以试验和验证。
本发明中公布的数字范围包括这个范围的所有点值。
附图说明
图1为实施例1.7烧结磁铁由EPMA面扫描形成的Nd、Cu、Ga、Co的分布图；
图2为对比例1.4烧结磁铁由EPMA面扫描形成的Nd、Cu、Ga、Co的分布图。
具体实施方式
以下结合实施例对本发明作进一步详细说明。
各实施例中提及的磁性能评价过程、成分测定、FE-EPMA检测的方法如下：
磁性能评价过程：烧结磁铁使用中国计量院的NIM-10000H型BH大块稀土永磁无损测量系统进行磁性能检测。
成分测定：各成分使用高频电感耦合等离子体发射光谱仪(ICP-OES)进行测定。另外，O(氧量)使用基于气体熔解-红外线吸收法的气体分析装置进行测定，N(氮量)使用基于气体熔解-导热法的气体分析装置进行测定，C(碳量)使用基于燃烧-红外线吸收法的气体分析装置进行测定。
FE-EPMA检测：对烧结磁铁的垂直取向面进行抛光，采用场发射电子探针显微分析仪(FE-EPMA)【日本电子株式会社(JEOL)，8530F】检测。首先通过定量分析Quantative和面扫描Mapping确定磁铁中的R 6-T 13-M相及M中Ga、Cu的含量，测试条件为加速电压15kV，探针束流50nA。然后通过背散射图像BSE统计R 6-T 13-M相的体积率，具体方法为随机拍摄10张放大倍率为2000倍的BSE图像，采用图像解析软件进行占比统计。
本发明中，所选用的热处理温度范围和热处理方式为本行业的常规选择，通常选用二 级热处理，第一级热处理的热处理温度为800℃-950℃，第二级热处理的热处理温度为400℃-650℃。
在推荐的实施方式中，所述成分中包括5.0wt％以下的X和不可避免的杂质，X为选自Zn、Al、In、Si、Ti、V、Cr、Mn、Ni、Ge、Zr、Nb、Mo、Pd、Ag、Cd、Sn、Sb、Hf、Ta或W中的至少1种元素，在X包括Nb、Zr或Cr中的至少一种之时，Nb、Zr和Cr的总含量在0.20wt％以下。
在推荐的实施方式中，Fe为余量。
在推荐的实施方式中，所述不可避免的杂质包括O，且所述烧结磁铁的O含量为0.5wt％以下。对于低氧含量磁铁(5000ppm以下)来说，虽然具有很好的磁性能，但在较高温度下烧结时容易发生晶粒的聚集长大，因此，其对于急冷合金、粉末、烧结磁铁极微量的微观结构改善等产生效果的响应更为灵敏，同时，由于氧含量低，R-O化合物少，能更充分利用R形成R 6-T 13-M相，提高Hcj，且R-O化合物杂相少，方形度提高。
另外，本发明中提及的不可避免的杂质还包括在原料中或者在制造过程中不可避免混入的少量C、N、S、P及其他杂质，因此，本发明中提及的所述烧结磁铁在制作过程中，最好将C含量控制在0.25wt％以下，更优选在0.1wt％以下，N含量则控制在0.15wt％以下，S含量则控制在0.05wt％以下，P含量则控制在0.05wt％以下。
需要说明的是，由于磁铁的低氧制造工序已是现有技术，且本发明的所有实施例全部采用低氧制造方式，在此不再予以详细描述。
在推荐的实施方式中，所述微粉碎为气流粉碎的工序。通过上述的方式，进一步提高烧结磁铁中R 6-T 13-M相的分散度。
在推荐的实施方式中，所述R中，Dy、Tb、Gd或Ho的含量为1％以下。对于Dy、Tb、Gd或Ho的含量为1％以下的烧结磁铁来说，R 6-T 13-δM 1+δ系相的存在，升高磁铁Hcj的效果更为显著。
实施例一
原料配制过程：准备纯度99.5％的Nd、Dy，工业用Fe-B，工业用纯Fe，纯度99.9％的Co、Cu、Ti、Ga、Al。
熔炼过程：取配制好的原料放入氧化铝制的坩埚中，在高频真空感应熔炼炉中在10 -2Pa的真空中以1500℃以下的温度进行真空熔炼。
铸造过程：在真空熔炼后的熔炼炉中通入Ar气体使气压达到5万Pa后，使用单辊急冷法进行铸造，以10 2℃/秒～10 4℃/秒的冷却速度获得急冷合金，将急冷合金在600℃进行60分钟的保温热处理，然后冷却到室温。
氢破粉碎过程：在室温下将放置急冷合金的氢破用炉抽真空，而后向氢破用炉内通入纯度为99.5％的氢气，维持氢气压力0.1MPa，充分吸氢后，边抽真空边升温，在500℃的温度下抽真空，之后进行冷却，取出氢破粉碎后的粉末。
微粉碎工序：在氧化气体含量100ppm以下的氮气气氛下，在粉碎室压力为0.4MPa的压力下对氢破粉碎后的粉末进行2小时的气流磨粉碎，得到细粉。氧化气体指的是氧或水分。
在气流磨粉碎后的粉末中添加辛酸甲酯，辛酸甲酯的添加量为混合后粉末重量的0.15％，再用V型混料机充分混合。
磁场成形过程：使用直角取向型的磁场成型机，在1.8T的取向磁场中，在0.4ton/cm 2的成型压力下，将上述添加了辛酸甲酯的粉末一次成形成边长为25mm的立方体，一次成形后在0.2T的磁场中退磁。
为使一次成形后的成形体不接触到空气，将其进行密封，再使用二次成形机(等静压成形机)在1.4ton/cm 2的压力下进行二次成形。
烧结过程：将各成形体搬至烧结炉进行烧结，烧结在10 -3Pa的真空下，在200℃和800℃的温度下各保持2小时后，以1060℃的温度烧结2小时，之后通入Ar气体使气压达到0.1MPa后，冷却至室温。
热处理过程：烧结体在高纯度Ar气中，以900℃进行2小时一级热处理后，再以520℃进行2小时二级热处理后，冷却至室温后取出。
加工过程：将烧结体加工成直径10mm、厚度5mm的磁铁，5mm方向为磁场取向方向，获得烧结磁铁。
各实施例和各对比例的烧结体制成的磁铁直接进行ICP-OES检测和磁性能检测，评定 其磁特性。各实施例和各对比例磁铁的成分和评价结果如表1、表2中所示：
表1 各元素的配比(wt％)
Figure PCTCN2019091536-appb-000001
表2 实施例的磁性能评价情况
Figure PCTCN2019091536-appb-000002
表3 实施例1.7烧结磁铁FE-EPMA单点定量分析结果
Figure PCTCN2019091536-appb-000003
作为结论我们可以得出：
对于低TRE(总稀土含量)烧结磁铁而言，在B含量小于0.86wt％之时，由于B含量过少，生成了过多的2-17相，Co、Cu、Ga、Ti协同添加，只在晶界中形成了少量的R 6-T 13M相，对烧结磁铁的Hcj提升不明显，且方形度下降，相对地，在B含量超过0.94wt％之时，由于B含量增加，生成了富B相，如R 1.1Fe 4B 4，导致主相体积分数下降，烧结磁铁的Br下降，Co、Cu、Ga、Ti的协同添加，没有或只形成很少量的R 6-T 13-M相，同样对烧结磁铁的Hcj提升不明显，而对于B在0.86wt％-0.94wt％来说，Co、Cu、Ga、Ti的协同添加，确保在晶界中生成了足够体积分数的R 6-T 13-M相，对烧结磁铁性能的提升更为明显。
另外，对于低B含量的烧结磁铁而言，在TRE(总稀土含量)含量小于28.5wt％之时，由于TRE含量过少，α-Fe析出，导致烧结磁铁的性能下降，相对地，在TRE含量超过31.5wt％之时，由于TRE含量增加，主相的体积分数下降，所以烧结磁铁的Br下降，同时Co、Cu、Ga、Ti的协同添加，由于R较多在晶界中生成了其他R-Ga-Cu相，导致R 6-T 13-M相的比例减少，因此对烧结磁铁的Hcj提升不明显，而对于TRE在28.5wt％-31.5wt％来说，Co、Cu、Ga、Ti的协同添加，确保在低B磁铁晶界中生成了足够体积分数的R 6-T 13M相，对烧结磁铁性能的提升更为明显。
对实施例1.7的烧结磁铁进行FE-EPMA检测，结果如图1中和表3所示，其中图1分别为Nd、Cu、Ga、Co的浓度分布和对应位置的BSE图，表3为单点定量分析结果，可知BSE图像中至少3个相，其中灰白色区域1为R 6-T 13-M相，R为Nd，T主要为Fe和Co，M中包括80wt％以上的Ga和20wt％以下的Cu，黑色区域2为R 2Fe 14B主相，亮白色区域3为其他富R相。随机拍摄10张放大倍率为2000倍的BSE图像，通过图像解析软件进行计算，统计出R 6-T 13-M相的体积率，可以得到该实施例样品中R 6-T 13-M相占晶界总体积的 80％以上。同样地，对实施例1.1-1.6，实施例1.8的烧结磁铁进行FE-EPMA检测，均可以观察到R 6-T 13-M相的体积占晶界总体积的75％以上，在R 6-T 13-M相中，R为Nd、或Nd和Dy，T主要为Fe和Co，M中包括80wt％以上的Ga和20wt％以下的Cu。
对对比例1.4进行FE-EPMA检测，结果如图2所示，分别代表Nd、Cu、Ga、Co的浓度分布和对应位置的BSE图，BSE图中灰白色区域1a为R 6-T 13-M相，黑色区域2a为R 2Fe 14B相，亮白色区域3a为其他富R相。可知，对比例的晶界相中灰白色R 6-T 13M相占比很小，大部分为其他组成的亮白色富Nd相。
对对比例1.1-1.3进行检测，在烧结磁铁的晶界中基本没有观测到R 6-T 13M相，或者R 6-T 13M相的体积小于晶界总体积的75％。
实施例二
原料配制过程：准备纯度99.8％的Nd、Dy，工业用Fe-B，工业用纯Fe，纯度99.9％的Co、Cu、Ti、Ga、Zr、Si。
熔炼过程：取配制好的原料放入氧化铝制的坩埚中，在高频真空感应熔炼炉中在5×10 -2Pa的真空中以1500℃以下的温度进行真空熔炼。
铸造过程：在真空熔炼后的熔炼炉中通入Ar气体使气压达到5.5万Pa后，进行铸造，以10 2℃/秒～10 4℃/秒的冷却速度获得急冷合金。
氢破粉碎过程：在室温下将放置急冷合金的氢破用炉抽真空，而后向氢破用炉内通入纯度为99.9％的氢气，维持氢气压力0.15MPa，充分吸氢后，边抽真空边升温，充分脱氢，之后进行冷却，取出氢破粉碎后的粉末。
微粉碎工序：在氧化气体含量150ppm以下的氮气气氛下，在粉碎室压力为0.38MPa的压力下对氢破粉碎后的粉末进行3小时的气流磨粉碎，得到细粉。氧化气体指的是氧或水分。
在气流磨粉碎后的粉末中添加硬脂酸锌，硬脂酸锌的添加量为混合后粉末重量的0.12％，再用V型混料机充分混合。
磁场成形过程：使用直角取向型的磁场成型机，在1.6T的取向磁场中，在0.35ton/cm 2的成型压力下，将上述添加了硬脂酸锌的粉末一次成形成边长为25mm的立方体，一次成 形后在0.2T的磁场中退磁。
为使一次成形后的成形体不接触到空气，将其进行密封，再使用二次成形机(等静压成形机)在1.3ton/cm 2的压力下进行二次成形。
烧结过程：将各成形体搬至烧结炉进行烧结，烧结在5×10 -3Pa的真空下，在300℃和600℃的温度下各保持1小时后，以1040℃的温度烧结2小时，之后通入Ar气体使气压达到0.1MPa后，冷却至室温。
热处理过程：烧结体在高纯度Ar气中，880℃进行3小时一级热处理后，再以500℃温度进行3小时二级热处理后，冷却至室温后取出。
加工过程：将烧结体加工成直径20mm、厚度5mm的磁铁，厚度方向为磁场取向方向，获得烧结磁铁。
各实施例和各对比例的烧结体制成的磁铁直接进行ICP-OES检测和磁性能检测，评定其磁特性。各实施例和各对比例磁铁的成分和评价结果如表4、表5中所示：
表4 各元素的配比(wt％)
Figure PCTCN2019091536-appb-000004
表5 实施例的磁性能评价情况
Figure PCTCN2019091536-appb-000005
Figure PCTCN2019091536-appb-000006
作为结论我们可以得出：
对于低TRE(总稀土含量)低B系烧结磁铁而言，在Cu含量小于0.2wt％之时，由于Cu含量过少，没有足够的量进入晶界中，Co、Ga、Ti的协同添加，在晶界中未形成足够的R 6-T 13M相，对烧结磁铁的Hcj提升不明显，相对地，在Cu含量超过0.45wt％之时，由于Cu含量过多，Co、Ga、Ti的协同添加，形成的R 6-T 13M相中M含有的Cu含量高于20％，同样对烧结磁铁性能的提升不明显，而对于Cu在0.2wt％-0.45wt％来说，Co、Ga、Ti的协同添加，确保在晶界中生成75％以上的R 6-T 13-M相，且M中Ga含量大于80％，Cu含量低于20％，对烧结磁铁性能的提升更为明显。
对于低TRE(总稀土含量)低B系烧结磁铁而言，在Co含量小于0.2wt％之时，由于Co含量过少，优先形成了其他R-Co相，Cu、Ga、Ti的协同添加，在晶界中未形成足够的R 6-T 13-M相，对烧结磁铁性能的提升不明显，相对地，在Co含量超过1.0wt％之时，由于Co含量过多，部分进入晶界，Cu、Ga、Ti的协同添加，形成的R 6-T 13-M相中M含有Ga含量低于80％，同样对烧结磁铁性能的提升不明显，而对于Co在0.2wt％-1.0wt％来说，Cu、Ga、Ti的协同添加，确保在晶界中生成75％以上的R 6-T 13-M相，且M中Ga含量大于80％，Cu含量低于20％，对烧结磁铁性能的提升更为明显。
同样地，对实施例2.1-2.7的烧结磁铁进行FE-EPMA检测，可以观察到占晶界总体积的75％以上组成的R 6-T 13-M相，R为Nd和Dy，T主要为Fe和Co，M中包括80wt％以上的Ga和20wt％以下的Cu。
同时，对对比例2.2和对比例2.4的烧结磁铁进行FE-EPMA检测，在烧结磁铁的晶界中观测到R 6-T 13-M相，R 6-T 13-M相占晶界总体积的75％以上，但M中Ga的含量小于80wt％。
对对比例2.1和对比例2.3的烧结磁铁进行FE-EPMA进行检测，在烧结磁铁的晶界中观测到R 6-T 13-M相，R 6-T 13-M相小于晶界总体积的75％。
实施例三
原料配制过程：准备纯度99.8％的Nd、Dy，工业用Fe-B，工业用纯Fe，纯度99.9％的Co、Cu、Ti、Ga、Ni、Nb、Mn。
熔炼过程：取配制好的原料放入氧化铝制的坩埚中，在高频真空感应熔炼炉中在5×10 -2Pa的真空中进行真空熔炼。
铸造过程：在真空熔炼后的熔炼炉中通入Ar气体使气压达到4.5万Pa后，进行铸造，以10 2℃/秒～10 4℃/秒的冷却速度获得急冷合金。
氢破粉碎过程：在室温下将放置急冷合金的氢破用炉抽真空，而后向氢破用炉内通入纯度为99.9％的氢气，维持氢气压力0.12MPa，充分吸氢后，边抽真空边升温，充分脱氢，之后进行冷却，取出氢破粉碎后的粉末。
微粉碎工序：在氧化气体含量200ppm以下的氮气气氛下，在粉碎室压力为0.42MPa的压力下对氢破粉碎后的粉末进行2小时的气流磨粉碎，得到细粉。氧化气体指的是氧或水分。
在气流磨粉碎后的粉末中添加硬脂酸锌，硬脂酸锌的添加量为混合后粉末重量的0.1％，再用V型混料机充分混合。
磁场成形过程：使用直角取向型的磁场成型机，在1.5T的取向磁场中，在0.45ton/cm 2的成型压力下，将上述添加了硬脂酸锌的粉末一次成形成边长为25mm的立方体，一次成形后退磁。
为使一次成形后的成形体不接触到空气，将其进行密封，再使用二次成形机(等静压成形机)在1.2ton/cm 2的压力下进行二次成形。
烧结过程：将各成形体搬至烧结炉进行烧结，烧结在5×10 -4Pa的真空下，在300℃和700℃的温度下各保持1.5小时后，以1050℃的温度烧结，之后通入Ar气体使气压达到大 气压后，循环冷却至室温。
热处理过程：烧结体在高纯度Ar气中，890℃进行3.5小时一级热处理后，再进行550℃温度进行3.5小时二级热处理后，冷却至室温后取出。
加工过程：将烧结体加工成直径20mm、厚度5mm的磁铁，厚度方向为磁场取向方向，获得烧结磁铁。
各实施例和各对比例的烧结体制成的磁铁直接进行ICP-OES检测和磁性能检测，评定其磁特性。各实施例和各对比例磁铁的成分和评价结果如表6、表7中所示：
表6 各元素的配比(wt％)
Figure PCTCN2019091536-appb-000007
表7 实施例的磁性能评价情况
Figure PCTCN2019091536-appb-000008
Figure PCTCN2019091536-appb-000009
作为结论我们可以得出：
对于低TRE(总稀土含量)低B系烧结磁铁而言，在Ga含量小于0.3wt％之时，由于Ga含量过少，Co、Cu、Ti的协同添加，形成的R 6-T 13-M相中M含有Ga含量低于80％，对烧结磁铁性能的提升不明显，相对地，在Ga含量超过0.5wt％之时，由于Ga含量过多，生成了其他R-Ga-Cu相(如R 6-T 2-M 2相)，且该相在晶界中的体积分数高于25％，Co、Cu、Ti的协同添加，在晶界中未形成足够的R 6-T 13-M相，同样对烧结磁铁性能的提升不明显，而对于Ga在0.3wt％-0.5wt％来说，Co、Cu、Ti的协同添加，确保在晶界中生成75％以上的R 6-T 13-M相，且M中Ga含量大于80％，Cu含量低于20％，对烧结磁铁性能的提升更为明显。
同时，对于低TRE(总稀土含量)低B系烧结磁铁而言，保持Ga、Cu、Co、Ti在权利要求范围内，当Dy含量低于1％时，Hcj的提升更明显，如实施例3.3与对比例3.2比较，烧结磁铁的Hcj提升了3.7kOe。而实施例3.4中，当Dy含量大于1％时，Ga、Cu、Co、Ti协同添加作用下，烧结磁铁的Hcj比对比例3.3中烧结磁铁的Hcj仅提升2.8kOe。
对于低TRE(总稀土含量)低B系烧结磁铁而言，在Ti含量小于0.02wt％之时，由于Ti含量过少，很难进行高温烧结，烧结不够致密，所以烧结磁铁的Br下降，Cu、Ga、Co的协同添加，在烧结不充分情况下，后续热处理也无法在晶界中形成足够的R 6-T 13-M，相对烧结磁铁性能的提升不明显，相对地，在Ti含量超过0.2wt％之时，由于Ti含量过多，容易形成TiBx相，从而消耗掉一部分B含量，B含量不足导致R 2-T 17相增加，Cu、Ga、Co的协同添加，在晶界中未形成足够的R 6-T 13M相，同样对烧结磁铁性能的提升不明显，而对于Ti在0.02wt％-0.2wt％来说，Cu、Ga、Co的协同添加，磁铁可以充分烧结，在后续 热处理中可以确保在晶界中生成75％以上的R 6-T 13-M相，且M中Ga含量大于80％，Cu含量低于20％，对烧结磁铁性能的提升更为明显。
同样地，对实施例3.1-3.8的烧结磁铁进行FE-EPMA进行检测，可以观察到占晶界总体积的75％以上组成的R 6-T 13-M相，R为Nd和Dy，T主要为Fe和Co，M中包括80wt％以上的Ga和20wt％以下的Cu。
另外，对对比例3.1进行FE-EPMA检测，在烧结磁铁的晶界中观测到R 6-T 13-M相，R 6-T 13-M相占晶界总体积的75％以上，但M中Ga的含量小于80wt％。
对对比例3.2、3.3、3.4、3.5进行FE-EPMA检测，在烧结磁铁的晶界中观测到R 6-T 13-M相，R 6-T 13-M相小于晶界总体积的75％。
上述实施例仅用来进一步说明本发明的几种具体的实施方式，但本发明并不局限于实施例，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均落入本发明技术方案的保护范围内。

Claims (8)

  1. 一种低B含量的R-Fe-B系烧结磁铁，其含有R 2Fe 14B型主相，所述的R为包括Nd的至少一种稀土元素，其特征在于，所述烧结磁铁包括如下成分：
    28.5wt％-31.5wt％的R，
    0.86wt％-0.94wt％的B，
    0.2wt％-1wt％的Co，
    0.2wt％-0.45wt％的Cu，
    0.3wt％-0.5wt％的Ga，
    0.02wt％-0.2wt％的Ti，以及
    61wt％-69.5wt％的Fe，
    所述烧结磁铁具有占晶界总体积75％以上的R 6-T 13-δM 1+δ系相，T选自Fe或Co的至少一种，M中包括80wt％以上的Ga和20wt％以下的Cu，δ为-0.14-0.04。
  2. 根据权利要求1中所述的一种低B含量的R-Fe-B系烧结磁铁，其特征在于：所述成分中包括5.0wt％以下的X和以及不可避免的杂质，X为选自Zn、Al、In、Si、Ti、V、Cr、Mn、Ni、Ge、Zr、Nb、Mo、Pd、Ag、Cd、Sn、Sb、Hf、Ta或W中的至少1种元素，在X包括Nb、Zr或Cr中的至少一种之时，Nb、Zr和Cr的总含量在0.20wt％以下。
  3. 根据权利要求2中所述的一种低B含量的R-Fe-B系烧结磁铁，其特征在于：Fe为余量。
  4. 根据权利要求2中所述的一种低B含量的R-Fe-B系烧结磁铁，其特征在于：所述不可避免的杂质包括O，且所述烧结磁铁的O含量为0.5wt％以下。
  5. 根据权利要求1中所述的一种低B含量的R-Fe-B系烧结磁铁，其特征在于：所述烧结磁铁为经过热处理之后的烧结磁铁。
  6. 根据权利要求1或2中所述的一种低B含量的R-Fe-B系烧结磁铁，其特征在于，由如下的步骤制得：将烧结磁铁的原料成分熔融液以10 2℃/秒-10 4℃/秒的冷却速度制备成急冷合金的工序；将所述烧结磁铁用合金吸氢破碎，之后再通过微粉碎制成细粉的工序；用磁场成形法或热压热变形获得成形体，并在真空或惰性气体中以900℃-1100℃的温度对所述成形体进行烧结，之后进行热处理获得。
  7. 根据权利要求1中所述的一种低B含量的R-Fe-B系烧结磁铁，其特征在于：所述R中，Dy、Tb、Gd或Ho的含量为1％以下。
  8. 一种低B含量的R-Fe-B系烧结磁铁的制备方法，其含有R 2Fe 14B型主相，所述的R为包括Nd的至少一种稀土元素，其特征在于，所述烧结磁铁包括如下成分：
    28.5wt％-31.5wt％的R，
    0.86wt％-0.94wt％的B，
    0.2wt％-1wt％的Co，
    0.2wt％-0.45wt％的Cu，
    0.3wt％-0.5wt％的Ga，
    0.02wt％-0.2wt％的Ti，以及
    61wt％-69.5wt％的Fe，
    并采用如下的方式制得：将烧结磁铁原料成分熔融液以10 2℃/秒-10 4℃/秒的冷却速度制备成烧结磁铁用合金的工序；将所述烧结磁铁用合金吸氢破碎，之后再通过微粉碎制成细粉的工序；用磁场成形法获得成形体，并在真空或惰性气体中以900℃-1100℃的温度对所述成形体进行烧结，之后进行热处理获得。
PCT/CN2019/091536 2018-06-19 2019-06-17 一种低B含量的R-Fe-B系烧结磁铁及其制备方法 Ceased WO2019242581A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DK19822708.4T DK3745430T3 (da) 2018-06-19 2019-06-17 R-fe-b-baseret sintret magnet med lavt b-indhold og fremgangsmåde til fremstilling deraf
JP2020551894A JP7379362B2 (ja) 2018-06-19 2019-06-17 低Ｂ含有Ｒ－Ｆｅ－Ｂ系焼結磁石及び製造方法
EP19822708.4A EP3745430B1 (en) 2018-06-19 2019-06-17 R-fe-b-based sintered magnet with low b content and preparation method therefor
ES19822708T ES2905485T3 (es) 2018-06-19 2019-06-17 Imán sinterizado a base de R-Fe-B con bajo contenido de B y método de preparación del mismo
US16/964,645 US11993836B2 (en) 2018-06-19 2019-06-17 R-FE-B-based sintered magnet with low B content and preparation method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810629609.3 2018-06-19
CN201810629609.3A CN110619984B (zh) 2018-06-19 2018-06-19 一种低B含量的R-Fe-B系烧结磁铁及其制备方法

Publications (1)

Publication Number Publication Date
WO2019242581A1 true WO2019242581A1 (zh) 2019-12-26

Family

ID=68920142

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/091536 Ceased WO2019242581A1 (zh) 2018-06-19 2019-06-17 一种低B含量的R-Fe-B系烧结磁铁及其制备方法

Country Status (8)

Country Link
US (1) US11993836B2 (zh)
EP (1) EP3745430B1 (zh)
JP (1) JP7379362B2 (zh)
CN (1) CN110619984B (zh)
DK (1) DK3745430T3 (zh)
ES (1) ES2905485T3 (zh)
TW (1) TWI704238B (zh)
WO (1) WO2019242581A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021247619A3 (en) * 2020-06-01 2022-01-20 US Metals Refining Group, Inc. Production of magnetic materials
JP2023504930A (ja) * 2019-12-31 2023-02-07 フージャン チャンティン ゴールデン ドラゴン レア－アース カンパニー リミテッド ネオジム鉄ホウ素永久磁石材料、製造方法、並びに応用
JP2023504931A (ja) * 2019-12-31 2023-02-07 フージャン チャンティン ゴールデン ドラゴン レア－アース カンパニー リミテッド Ｒ－ｔ－ｂ系焼結磁石及びその製造方法
CN120299895A (zh) * 2025-06-11 2025-07-11 国瑞科创稀土功能材料(赣州)有限公司 一种R-Fe-B系永磁材料及其制备方法

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110428947B (zh) * 2019-07-31 2020-09-29 厦门钨业股份有限公司 一种稀土永磁材料及其原料组合物、制备方法和应用
CN111048273B (zh) * 2019-12-31 2021-06-04 厦门钨业股份有限公司 一种r-t-b系永磁材料、原料组合物、制备方法、应用
CN111091945B (zh) * 2019-12-31 2021-09-28 厦门钨业股份有限公司 一种r-t-b系永磁材料、原料组合物、制备方法、应用
CN111312463B (zh) * 2020-02-29 2022-05-03 厦门钨业股份有限公司 一种稀土永磁材料及其制备方法和应用
CN111243812B (zh) * 2020-02-29 2022-04-05 厦门钨业股份有限公司 一种r-t-b系永磁材料及其制备方法和应用
CN111243808B (zh) * 2020-02-29 2022-02-01 厦门钨业股份有限公司 一种钕铁硼材料及其制备方法和应用
CN111524673A (zh) * 2020-04-30 2020-08-11 福建省长汀金龙稀土有限公司 钕铁硼磁体材料、原料组合物及其制备方法和应用
CN111540557B (zh) * 2020-04-30 2021-11-05 福建省长汀金龙稀土有限公司 一种钕铁硼磁体材料、原料组合物及制备方法、应用
CN111524674A (zh) * 2020-04-30 2020-08-11 福建省长汀金龙稀土有限公司 一种钕铁硼磁体材料、原料组合物及制备方法、应用
WO2022181808A1 (ja) * 2021-02-26 2022-09-01 日本電産株式会社 モータ、駆動システム、掃除機、無人飛行体、電動航空機
JP2022132032A (ja) * 2021-02-26 2022-09-07 日本電産株式会社 ネオジム磁石、ネオジム磁石の製造方法
JP2022132088A (ja) * 2021-02-26 2022-09-07 日本電産株式会社 モータ、駆動システム、掃除機、無人飛行体、電動航空機
CN114284017B (zh) * 2021-12-15 2025-06-13 烟台正海磁性材料股份有限公司 一种r-t-b类钕铁硼磁体及其制备方法和应用
CN119763968A (zh) * 2024-12-30 2025-04-04 宁波科宁达工业有限公司 一种低成本磁体及其制备方法
CN120280249B (zh) * 2025-06-11 2025-09-09 江西理工大学 一种低硼系R-Fe-B永磁材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013008756A1 (ja) 2011-07-08 2013-01-17 昭和電工株式会社 Ｒ－ｔ－ｂ系希土類焼結磁石用合金、ｒ－ｔ－ｂ系希土類焼結磁石用合金の製造方法、ｒ－ｔ－ｂ系希土類焼結磁石用合金材料、ｒ－ｔ－ｂ系希土類焼結磁石、ｒ－ｔ－ｂ系希土類焼結磁石の製造方法およびモーター
CN103890868A (zh) * 2011-10-28 2014-06-25 Tdk株式会社 R-t-b系烧结磁铁
CN105453195A (zh) 2013-08-12 2016-03-30 日立金属株式会社 R-t-b系烧结磁体及r-t-b系烧结磁体的制造方法
CN106448985A (zh) * 2015-09-28 2017-02-22 厦门钨业股份有限公司 一种复合含有Pr和W的R‑Fe‑B系稀土烧结磁铁

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY149353A (en) * 2007-03-16 2013-08-30 Shinetsu Chemical Co Rare earth permanent magnet and its preparations
JP5107198B2 (ja) * 2008-09-22 2012-12-26 株式会社東芝 永久磁石および永久磁石の製造方法並びにそれを用いたモータ
EP3059743B1 (en) * 2011-12-27 2020-11-25 Daido Steel Co., Ltd. Ndfeb system sintered magnet
PH12013000103B1 (en) * 2012-04-11 2015-09-07 Shinetsu Chemical Co Rare earth sintered magnet and making method
CN103050267B (zh) * 2012-12-31 2016-01-20 厦门钨业股份有限公司 一种基于细粉热处理的烧结Nd-Fe-B系磁铁制作方法
JP6303480B2 (ja) * 2013-03-28 2018-04-04 Tdk株式会社 希土類磁石
CN105453194B (zh) * 2013-08-12 2018-10-16 日立金属株式会社 R－t－b系烧结磁体
WO2016133067A1 (ja) 2015-02-17 2016-08-25 日立金属株式会社 Ｒ－ｔ－ｂ系焼結磁石の製造方法
CN106024235B (zh) * 2015-03-30 2020-01-17 日立金属株式会社 R－t－b系烧结磁体
RU2697265C2 (ru) * 2015-03-31 2019-08-13 Син-Эцу Кемикал Ко., Лтд. Спеченный магнит R-Fe-B и способ его изготовления
US10923256B2 (en) * 2015-06-25 2021-02-16 Hitachi Metals, Ltd. R-T-B-based sintered magnet and method for producing same
JP6693392B2 (ja) * 2015-11-18 2020-05-13 信越化学工業株式会社 Ｒ−（Ｆｅ，Ｃｏ）−Ｂ系焼結磁石及びその製造方法
US10672546B2 (en) * 2016-02-26 2020-06-02 Tdk Corporation R-T-B based permanent magnet
JP6541038B2 (ja) * 2016-03-28 2019-07-10 日立金属株式会社 Ｒ−ｔ−ｂ系焼結磁石

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013008756A1 (ja) 2011-07-08 2013-01-17 昭和電工株式会社 Ｒ－ｔ－ｂ系希土類焼結磁石用合金、ｒ－ｔ－ｂ系希土類焼結磁石用合金の製造方法、ｒ－ｔ－ｂ系希土類焼結磁石用合金材料、ｒ－ｔ－ｂ系希土類焼結磁石、ｒ－ｔ－ｂ系希土類焼結磁石の製造方法およびモーター
CN103890868A (zh) * 2011-10-28 2014-06-25 Tdk株式会社 R-t-b系烧结磁铁
CN105453195A (zh) 2013-08-12 2016-03-30 日立金属株式会社 R-t-b系烧结磁体及r-t-b系烧结磁体的制造方法
CN106448985A (zh) * 2015-09-28 2017-02-22 厦门钨业股份有限公司 一种复合含有Pr和W的R‑Fe‑B系稀土烧结磁铁

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023504930A (ja) * 2019-12-31 2023-02-07 フージャン チャンティン ゴールデン ドラゴン レア－アース カンパニー リミテッド ネオジム鉄ホウ素永久磁石材料、製造方法、並びに応用
JP2023504931A (ja) * 2019-12-31 2023-02-07 フージャン チャンティン ゴールデン ドラゴン レア－アース カンパニー リミテッド Ｒ－ｔ－ｂ系焼結磁石及びその製造方法
JP7312916B2 (ja) 2019-12-31 2023-07-21 フージャン チャンティン ゴールデン ドラゴン レア－アース カンパニー リミテッド Ｒ－ｔ－ｂ系焼結磁石及びその製造方法
JP7312915B2 (ja) 2019-12-31 2023-07-21 フージャン チャンティン ゴールデン ドラゴン レア－アース カンパニー リミテッド ネオジム鉄ホウ素永久磁石材料、製造方法、並びに応用
WO2021247619A3 (en) * 2020-06-01 2022-01-20 US Metals Refining Group, Inc. Production of magnetic materials
CN120299895A (zh) * 2025-06-11 2025-07-11 国瑞科创稀土功能材料(赣州)有限公司 一种R-Fe-B系永磁材料及其制备方法

Also Published As

Publication number Publication date
JP7379362B2 (ja) 2023-11-14
JP2021516870A (ja) 2021-07-08
TW202000944A (zh) 2020-01-01
EP3745430B1 (en) 2021-12-22
ES2905485T3 (es) 2022-04-08
EP3745430A4 (en) 2021-05-12
EP3745430A1 (en) 2020-12-02
US20210054484A1 (en) 2021-02-25
TWI704238B (zh) 2020-09-11
CN110619984B (zh) 2021-12-07
CN110619984A (zh) 2019-12-27
US11993836B2 (en) 2024-05-28
DK3745430T3 (da) 2022-01-17

Similar Documents

Publication Publication Date Title
TWI704238B (zh) 低B含量的R-Fe-B系燒結磁鐵及其製備方法
JP6440880B2 (ja) 低ｂの希土類磁石
CN110428947B (zh) 一种稀土永磁材料及其原料组合物、制备方法和应用
EP4016559B1 (en) Neodymium-iron-boron magnet material, raw material composition, preparation method therefor and use thereof
WO2021042864A1 (zh) 一种稀土永磁材料、原料组合物、制备方法、应用、电机
CN110021466A (zh) 一种R-Fe-B-Cu-Al系烧结磁铁及其制备方法
CN110323053B (zh) 一种R-Fe-B系烧结磁体及其制备方法
CN111326306B (zh) 一种r-t-b系永磁材料及其制备方法和应用
WO2015149685A1 (zh) 一种含W的R‐Fe‐B‐Cu系烧结磁铁及急冷合金
TWI730930B (zh) R-t-b系永磁材料、原料組合物、製備方法、應用
TW202121451A (zh) 釹鐵硼磁體材料、原料組合物及製備方法和應用
TWI742969B (zh) R-t-b系永磁材料、原料組合物、製備方法、應用
TWI750964B (zh) R-t-b系永磁材料、原料組合物、製備方法、應用
CN108695032B (zh) R-t-b系烧结磁铁
EP4354471A1 (en) Auxiliary alloy casting piece, high-remanence and high-coercive force ndfeb permanent magnet, and preparation methods thereof
WO2016155674A1 (zh) 一种含有Ho和W的稀土磁铁

Legal Events

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

Ref document number: 19822708

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019822708

Country of ref document: EP

Effective date: 20200723

ENP Entry into the national phase

Ref document number: 2019822708

Country of ref document: EP

Effective date: 20200723

ENP Entry into the national phase

Ref document number: 2020551894

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE