WO2018173782A1 - Aimant permanent, machine dynamoélectrique et véhicule - Google Patents

Aimant permanent, machine dynamoélectrique et véhicule Download PDF

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WO2018173782A1
WO2018173782A1 PCT/JP2018/009078 JP2018009078W WO2018173782A1 WO 2018173782 A1 WO2018173782 A1 WO 2018173782A1 JP 2018009078 W JP2018009078 W JP 2018009078W WO 2018173782 A1 WO2018173782 A1 WO 2018173782A1
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permanent magnet
phase
type
atomic
rotating electrical
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PCT/JP2018/009078
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Japanese (ja)
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直幸 眞田
利英 高橋
桜田　新哉
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株式会社 東芝
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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
    • H01F1/058—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IVa elements, e.g. Gd2Fe14C
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • 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
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
    • 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
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
    • H01F1/0596—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2 of rhombic or rhombohedral Th2Zn17 structure or hexagonal Th2Ni17 structure
    • 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
    • H01F1/06—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 in the form of particles, e.g. powder
    • H01F1/08—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 in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/086—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 in the form of particles, e.g. powder pressed, sintered, or bound together sintered
    • 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
    • H01F7/00—Magnets
    • H01F7/02—Permanent magnets [PM]
    • H01F7/0231—Magnetic circuits with PM for power or force generation
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K1/00—Details of the magnetic circuit
    • H02K1/02—Details of the magnetic circuit characterised by the magnetic material
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • 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
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K2213/00—Specific aspects, not otherwise provided for and not covered by codes H02K2201/00 - H02K2211/00
    • H02K2213/03—Machines characterised by numerical values, ranges, mathematical expressions or similar information
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/72—Electric energy management in electromobility

Definitions

  • Embodiment relates to a permanent magnet, a rotating electrical machine, and a vehicle.
  • rare earth magnets such as Sm—Co magnets and Nd—Fe—B magnets are known. Rare earth magnets are used in electric devices such as motors, speakers, and measuring instruments, and also in vehicles such as hybrid electric vehicles (HEV) and electric vehicles (EV).
  • HEV hybrid electric vehicles
  • EV electric vehicles
  • BH max maximum magnetic energy product
  • a magnet material for obtaining a higher performance permanent magnet for example, a combination of a rare earth element and a transition metal element such as Fe is promising.
  • Sm-Fe-N-based materials have high saturation magnetization comparable to Nd-Fe-B-based materials and large magnetic anisotropy exceeding that of Nd-Fe-B-based materials. Has been.
  • the Sm—Fe—N based magnet material has a drawback that it is thermally decomposed by heating at a temperature of about 550 ° C. or higher, applying a densification process by sintering to obtain a high density results in Sm
  • the —Fe—N magnet material is thermally decomposed, and the ⁇ -Fe phase is precipitated.
  • the problem to be solved by the embodiment is to suppress a decrease in the coercive force of the permanent magnet.
  • the permanent magnet of the embodiment has a composition formula: RM Z N X (where R is at least one element selected from the group consisting of rare earth elements, Zr, Nb, and Hf, and M is at least one selected from the group consisting of Fe and Co).
  • X is an atomic ratio satisfying 0.5 ⁇ X ⁇ 2.0
  • Z is an atomic ratio satisfying 4 ⁇ Z ⁇ 13).
  • the permanent magnet includes a first phase having at least one crystal structure selected from Th 2 Ni 17 type, Th 2 Zn 17 type, and TbCu 7 type, and at least one crystal structure selected from MgCu 2 type and PuNi 3 type.
  • a second phase having: The volume ratio of the total amount of the second phase is 5% or less.
  • FIG. 1 is a diagram illustrating an example of an SEM (Scanning Electron Microscope) observation image of a cross section of a permanent magnet.
  • the structure shown in FIG. 1 has a main phase 1, a subphase 2, and an ⁇ -Fe phase 3.
  • the main phase 1 is the phase with the highest volume occupancy among the crystalline and amorphous phases in the permanent magnet.
  • the subphase 2 is a phase having a volume occupancy lower than that of the main phase 1.
  • the subphase 2 has a crystal phase different from the main phase 1 or an amorphous phase.
  • the ⁇ -Fe phase 3 is a different phase from the subphase 2. Note that the number of main phases 1, subphases 2, and ⁇ -Fe phases 3 is not limited to the numbers shown in FIG.
  • composition of the permanent magnet of the embodiment is represented by the following composition formula (1).
  • RM Z N X (1) (Wherein R is at least one element selected from the group consisting of rare earth elements, Zr, Nb, and Hf, M is at least one element selected from the group consisting of Fe and Co, and X is 0.5 ⁇ X ⁇ 2 .0, Z is an atomic ratio satisfying 4 ⁇ Z ⁇ 13)
  • R is at least one element selected from rare earth elements, zirconium (Zr), niobium (Nb), and hafnium (Hf).
  • rare earth elements include yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), and samarium (Sm).
  • Y yttrium
  • La lanthanum
  • Ce cerium
  • Pr praseodymium
  • Nd neodymium
  • Sm samarium
  • R one type of element may be used, or a plurality of types of elements may be used.
  • R imparts a large magnetic anisotropy and a high coercive force to the magnet. It is preferable that 50 atomic% or more of R is Sm. It is desirable that 70 atom% or more of R is Sm.
  • Nitrogen (N) is present in the crystal lattice of main phase 1 and subphase 2.
  • the crystal lattice expands and the electronic structure changes. Thereby, the Curie temperature, magnetic anisotropy, and saturation magnetization of the permanent magnet are improved.
  • the atomic ratio of nitrogen is 0.5 or more and 2.0 or less when R is 1. That is, X is an atomic ratio that satisfies 0.5 ⁇ X ⁇ 2.0. X is more preferably an atomic ratio satisfying 1.0 ⁇ X ⁇ 1.5.
  • X is less than 0.5, the effect of containing nitrogen in the permanent magnet cannot be sufficiently obtained.
  • X exceeds 2.0 the saturation magnetization of the permanent magnet is lowered.
  • a part of N may be substituted with at least one element selected from hydrogen (H), boron (B), and carbon (C).
  • the substitution element one kind of element or a plurality of kinds of elements may be used.
  • the substitution element exhibits the same effect as nitrogen described above. However, excessive substitution of nitrogen causes a decrease in the magnetic anisotropy of the permanent magnet. Therefore, it is preferable that 50 atomic% or less of nitrogen is substituted with the above element.
  • M is at least one element selected from iron (Fe) and cobalt (Co).
  • Fe iron
  • Co cobalt
  • M one type of element may be used, or a plurality of types of elements may be used.
  • M is an element mainly responsible for the magnetization of the permanent magnet. By containing M in a relatively large amount, the saturation magnetization of the permanent magnet can be increased. However, when the M content is excessive, the ⁇ -Fe phase and the like are precipitated, and the coercive force is lowered.
  • M is Fe.
  • 70 atomic% or more of M is more preferably Fe.
  • Fe in M contributes particularly to the improvement of the magnetization of the permanent magnet.
  • the permanent magnet contains Co as a part of M, the Curie temperature of the permanent magnet is increased, and the thermal stability of the permanent magnet is improved. Moreover, the coercive force of the permanent magnet is also increased.
  • Part of M is titanium (Ti), vanadium (V), tantalum (Ta), molybdenum (Mo), tungsten (W), manganese (Mn), nickel (Ni), zinc (Zn), and germanium (Ge) It may be substituted with at least one element selected from.
  • a substitution element one type of element may be used or a plurality of types of elements may be used.
  • An element substituting for a part of M contributes to improvement of magnetic properties, for example, coercive force. However, if a part of M is replaced too much, the magnetization of the permanent magnet decreases. Therefore, it is preferable that 20 atomic% or less of M, and further 10 atomic% or less of M is substituted with the above element.
  • a part of M may be substituted with at least one element selected from the group consisting of chromium (Cr) and silicon (Si).
  • Cr and Si increase the thermal decomposition temperature of the RMN permanent magnet.
  • Cr or Si mainly replaces sites occupied by M in the main phase.
  • Cr can improve the thermal stability of the crystal by changing the number of d electrons in the crystal.
  • Si can increase the thermal stability of the crystal by reducing the size of the crystal lattice.
  • Cr and Si By including Cr and Si in the permanent magnet, thermal decomposition of the RMN permanent magnet in the sintering process can be suppressed, and precipitation of the ⁇ -Fe phase can be suppressed. It is preferable that 20 atom% or less of M, more preferably 10 atom% or less of M is substituted with the above element.
  • the main phase 1 has at least one crystal structure selected from Th 2 Ni 17 type, Th 2 Zn 17 type, and TbCu 7 type (first phase).
  • the main phase 1 has an RMN phase such as Sm 2 (Fe, Cr, Si) 17 N 3 phase.
  • the subphase 2 has at least one crystal structure selected from cubic MgCu 2 type and hexagonal PuNi 3 type (second phase).
  • the subphase 2 has an RMN phase such as an Sm (Fe, Cr, Si) 2 N phase or an Sm (Fe, Cr, Si) 3 N phase.
  • the RMN phase having at least one crystal structure selected from MgCu 2 type and PuNi 3 type has at least one crystal structure selected from Th 2 Ni 17 type, Th 2 Zn 17 type, and TbCu 7 type. Since the thermal stability is lower than that of the RMN phase, the amount of ⁇ -Fe phase 3 deposited by thermal decomposition increases when the secondary phase 2 is present in a large amount, and the coercive force of the permanent magnet is lowered. Therefore, it is preferable that the secondary phase 2 and the ⁇ -Fe phase 3 in the permanent magnet are small.
  • the volume ratio of the total amount of subphase 2 in the permanent magnet is preferably 5% or less.
  • the volume ratio of the total amount of ⁇ -Fe phase 3 in the permanent magnet is preferably 5% or less.
  • the analysis of the composition of the permanent magnet is performed by, for example, inductively coupled plasma (ICP) emission spectroscopy.
  • ICP inductively coupled plasma
  • a powder alloy powder in which the magnet is pulverized with a jet mill, a ball mill, or the like, and a powder having a particle size of 10 ⁇ m or more is 3% by volume or less is used. Samples are taken 10 times at random from the obtained powder, and the sample is analyzed. The average value obtained by subtracting the maximum value and the minimum value from the analyzed measured value is taken as the composition of the permanent magnet.
  • the main phase 1, the sub-phase 2, and the ⁇ -Fe phase 3 are, for example, SEM-EDX (Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy), TEM-EDX (Transmission Electro-Semi-ElectroDemi-Semi-ElectroD-Electrical-Semi-ElectroXe-M-D It can be specified by the method. According to TEM-EDX, an electron beam is focused on a main phase part, a grain boundary phase part, etc., and the constituent element ratio of each part can be quantified, and the crystal structure can be identified.
  • SEM-EDX Sccanning Electron Microscope-Energy Dispersive X-ray Spectroscopy
  • TEM-EDX Transmission Electro-Semi-ElectroDemi-Semi-ElectroD-Electrical-Semi-ElectroXe-M-D It can be specified by the method. According
  • An example of a method for identifying the main phase 1, the sub phase 2, and the ⁇ -Fe phase 3 using SEM-EDX will be described below.
  • An SEM image having an observation area of 50 ⁇ m ⁇ 50 ⁇ m is acquired.
  • the continuous region where the ratio of R element to the total of R and M is 10 atomic% or more and less than 20 atomic% is the main phase 1
  • the continuous area where the R element ratio is 20 atomic% or more is the subphase 2
  • the R element ratio is A continuous region of less than 10 atomic% and an Fe ratio of 90 atomic% or more is defined as ⁇ -Fe phase 3, respectively.
  • the area ratio between the main phase 1 and ⁇ -Fe phase 3 and the subphase 2 defined according to the above is calculated as the volume ratio as it is and is defined as the volume ratio of the subphase 2 in the permanent magnet.
  • a value obtained by directly calculating the area ratio of the main phase 1 / subphase 2 and the ⁇ -Fe phase 3 as a volume ratio is defined as the volume ratio of the ⁇ -Fe phase 3 in the permanent magnet.
  • the volume ratio of the subphase 2 and the volume ratio of the ⁇ -Fe phase 3 were calculated by the method described above in five observation fields, and the averaged values of the subphase 2 of the permanent magnet were calculated.
  • the volume ratio is defined as the volume ratio of ⁇ -Fe phase 3.
  • the permanent magnet of the embodiment can suppress the precipitation of the ⁇ -Fe phase 3 by reducing the subphase 2 having low thermal stability, and can improve the density of the permanent magnet without reducing the coercive force.
  • the permanent magnet of the embodiment has a density of 6.5 g / cm 3 or more.
  • the density of the permanent magnet is calculated by the Archimedes method by measuring the mass of the permanent magnet in the air and in water. At this time, each sample is calculated 10 times, and the average value excluding the maximum value and the minimum value among the obtained density of the permanent magnet is defined as the density of the permanent magnet.
  • an alloy powder containing a predetermined amount of element is prepared.
  • the alloy powder is represented by the composition formula (2).
  • the alloy powder may contain at least one element selected from the group consisting of hydrogen, boron, and carbon.
  • the atomic ratio Z indicating the ratio of the total content of M other than R is a number satisfying 4 ⁇ Z ⁇ 13.
  • the alloy powder is prepared by, for example, grinding an alloy ingot obtained by casting a molten metal by an arc melting method or a high frequency melting method, or an alloy ribbon produced by a molten metal quenching method.
  • Other preparation methods of the alloy powder include mechanical alloying method, mechanical grinding method, gas atomization method, reduction diffusion method and the like.
  • the pulverization of the alloy ingot or the alloy ribbon is preferably performed so that the particle size of the alloy powder is 45 ⁇ m or less.
  • the particle size of the alloy powder is 45 ⁇ m or less, nitrogen can sufficiently penetrate into the inside of the particles in the nitriding treatment described later, so that the entire particles can be uniformly nitrided.
  • the pulverization of the alloy ingot, the alloy ribbon, or the like is performed using, for example, a jet mill or a ball mill.
  • the alloy ingot, the alloy ribbon, and the like are preferably pulverized in an inert gas atmosphere or the like.
  • a homogenization heat treatment is applied to the alloy powder or the alloy before pulverization. If the melting temperature of SmFe 3 is 1010 ° C. in the Fe—Sm binary phase diagram, it is conceivable to perform the homogenization heat treatment at a heat treatment temperature of 1000 ° C. or higher. However, in the permanent magnet of the embodiment, there is a high possibility that the state diagram is slightly changed by replacing part of Fe with M. Therefore, there is a possibility that the optimum heat treatment temperature is below 1000 ° C.
  • heat treatment is performed at a temperature higher than 900 ° C. and lower than 1000 ° C. for 10 to 100 hours in a vacuum or an inert gas atmosphere such as argon gas.
  • the heat treatment temperature is 900 ° C. or lower, element diffusion does not occur sufficiently and the alloy cannot be homogenized.
  • the heat treatment temperature is 1000 ° C. or higher, a phase having at least one crystal structure selected from cubic MgCu 2 type and hexagonal PuNi 3 type is formed in the alloy, and as a result, the coercive force of the permanent magnet decreases.
  • FIGS. 2 to 4 are diagrams illustrating examples of X-ray diffraction patterns obtained by X-ray diffraction measurement of permanent magnets manufactured by the manufacturing method according to the embodiment.
  • the heat treatment temperature of the homogenization heat treatment is 900 ° C. and the heat treatment time is 65 hours
  • a peak indicating a phase having a PuNi 3 type crystal structure is generated as shown in FIG.
  • the heat treatment temperature is 1000 ° C. and the heat treatment time is 65 hours
  • a peak indicating a phase having an MgCu 2 type crystal structure also referred to as an MgCu 2 phase
  • the heat treatment temperature of the homogenization heat treatment is a heat treatment time at 950 ° C. for 65 hours to a peak indicating the subphases PuNi 3 phase or MgCu 2 phase etc. as shown in FIG. 3 without obtaining a homogeneous main phase.
  • FIGS. 5 to 7 are diagrams showing examples of X-ray diffraction patterns obtained by X-ray diffraction measurement of permanent magnets manufactured by the manufacturing method of the embodiment.
  • Homogenization annealing step at a heat treatment time is 16 hours at 950 ° C., for 32 hours, as shown in FIGS. 5 and 6, there is no peak indicating the subphases PuNi 3 phase or MgCu 2 equality, homogeneous main phase Can be obtained.
  • the heat treatment time is 4 hours at the heat treatment temperature of the homogenization heat treatment is 950 ° C., does not proceed homogenization sufficiently as shown in FIG. 7, a peak indicating the subphases PuNi 3 phase or MgCu 2 phase etc. Will occur.
  • the heat treatment time of the homogenization heat treatment is preferably 10 hours or more.
  • the alloy powder is subjected to nitriding treatment.
  • heat treatment is performed at a temperature of 300 to 900 ° C. for 0.1 to 100 hours in a nitrogen gas atmosphere of 0.1 to 100 atm.
  • a nitrogen gas atmosphere pressure of 0.5 to 10 atm and a temperature of 450 to 750 ° C. for 2 to 24 hours.
  • the atmosphere during the nitriding treatment of the alloy powder may be nitrogen compound gas such as ammonia instead of nitrogen gas.
  • the nitriding reaction can also be controlled by using a gas in which nitrogen gas or nitrogen compound gas and hydrogen are mixed.
  • the alloy powder before nitriding treatment may contain carbon or boron, or carbon or boron may be contained using a carbon compound gas or boron compound gas. May be.
  • the alloy powder (nitriding alloy powder) subjected to nitriding treatment and the alloy powder for mixing are mixed and filled in a mold placed in an electromagnet, and the crystal axis is formed by pressing while applying a magnetic field.
  • a green compact in which is oriented is manufactured.
  • the green compact is sintered.
  • a sintering method it is preferable to use a discharge plasma sintering method.
  • spark plasma sintering it is thought that the current easily flows selectively on the surface of the powder particles, and the permanent magnet is densified while suppressing the thermal load on the main RMN phase. Suitable for
  • Sintering is preferably performed in a vacuum atmosphere or an inert gas atmosphere such as argon gas.
  • a dense permanent magnet can be obtained by setting the sintering temperature to 400 to 700 ° C. during spark plasma sintering. If it is less than 400 degreeC, a permanent magnet with sufficient density cannot be obtained. If the temperature exceeds 700 ° C., thermal decomposition of the permanent magnet proceeds, and an ⁇ -Fe phase or the like is generated in the permanent magnet, so that the magnetic properties of the permanent magnet are significantly deteriorated.
  • a permanent magnet can be obtained by the above process.
  • the magnetic properties of the obtained permanent magnet can be measured with a vibrating sample magnetometer.
  • the residual magnetization can be measured as follows. An external magnetic field is applied up to +1600 kA / m in a direction parallel to the magnetization direction oriented before sintering, the magnetic field is returned to zero, and the value of magnetization measured at that time is defined as the residual magnetization of the permanent magnet.
  • the same measurement is performed for a nickel standard sample (a sample whose absolute value of magnetization is known) similar to the sample to be measured, and the absolute value of magnetization is calibrated.
  • the permanent magnet of the first embodiment can be used for a rotating electrical machine, for example, a motor or a generator.
  • These rotating electrical machines are composed of at least a stator (stator) and a rotor (rotor).
  • FIG. 8 is a diagram illustrating a configuration example of a permanent magnet motor that is a rotating electrical machine using the permanent magnet of the embodiment.
  • the permanent magnet motor 21 includes a stator (stator) 22 and a rotor (rotor) 23.
  • a rotor 23 is disposed in the stator 22.
  • the stator 22 rotates the rotor 23.
  • the rotor 23 includes an iron core 24 and the permanent magnet 25 of the embodiment. Based on the characteristics of the permanent magnet 25 and the like, the permanent magnet motor 21 can be improved in efficiency, size, cost, and the like.
  • the permanent magnet motor 21 is suitable for a motor for a vehicle such as a hybrid vehicle or an electric vehicle that requires high motor output and miniaturization of the motor.
  • FIG. 9 is a diagram showing a configuration example of a variable magnetic flux motor that is a rotating electrical machine.
  • the variable magnetic flux motor 31 includes a stator 32 and a rotor 33.
  • a rotor 33 is disposed in the stator 32.
  • the rotor 33 includes an iron core 34, a fixed magnet 35, and a variable magnet 36.
  • the permanent magnet of the embodiment is used for the fixed magnet 35 and the variable magnet 36. At least one of the fixed magnet 35 and the variable magnet 36 may be used for the rotor 33.
  • the magnetic flux density (magnetic flux amount) of the variable magnet 36 can be changed.
  • D in FIG. 9 indicates the magnetization direction (direction from S to N) of the variable magnet 36.
  • the magnetization direction of the variable magnet 36 is referred to as the D axis.
  • the direction indicated by the D axis is different for each variable magnet 36.
  • the direction orthogonal to the D axis is called the Q axis.
  • the magnetic flux density (magnetic flux amount) of the variable magnet 36 is not affected by the Q-axis current that generates a magnetic field in the Q-axis direction orthogonal to the magnetization direction (D-axis direction) of the variable magnet 36.
  • the magnetic flux density (magnetic flux amount) of the variable magnet 36 can be changed only by a D-axis current that generates a magnetic field in the D-axis direction.
  • the rotor 33 is provided with a magnetizing winding (not shown). By passing a current through the magnetized winding, the magnetic field directly acts on the variable magnet 36.
  • the variable magnetic flux motor 31 can output a large torque even with a small device.
  • the variable magnetic flux motor 31 is suitable for a motor for a vehicle such as a hybrid vehicle or an electric vehicle that requires high motor output and miniaturization of the motor.
  • FIG. 10 is a diagram showing a configuration example of the generator.
  • the generator 41 includes a stator 42 using the permanent magnet of the embodiment, a rotor 43, a turbine 44, a shaft 45, and a brush 46.
  • the rotor 43 is connected to the turbine 44 via the shaft 45.
  • the turbine 44 is rotated by fluid supplied from the outside. Instead of the turbine 44, the shaft 45 may be rotated by transmitting dynamic rotation such as regenerative energy of a vehicle such as an automobile.
  • the shaft 45 is connected to a commutator (not shown) arranged on the opposite side of the turbine 44 from the rotor 43.
  • the electromotive force generated by the rotation of the rotor 43 is boosted to the system voltage and transmitted as the output of the generator 41 via the phase separation bus and the main transformer.
  • the brush 46 discharges the charge of the rotor 43.
  • the generator 41 may be either a normal generator or a variable magnetic flux generator.
  • the rotor 43 is charged by the shaft 44 due to static electricity of the turbine 44 or power generation.
  • the rotating electric machine may be mounted on, for example, a railway vehicle (an example of a vehicle) used for rail traffic.
  • FIG. 11 is a diagram illustrating an example of a railway vehicle 100 that includes the rotating electrical machine 101.
  • the rotating electrical machine 101 the motors shown in FIGS. 8 and 9 and the generator shown in FIG. 10 can be used.
  • the rotating electrical machine 101 uses, for example, power supplied from an overhead wire or power supplied from a secondary battery mounted on the railway vehicle 100 to drive power. May be used as an electric motor (motor) that outputs power, or may be used as a generator (generator) that converts kinetic energy into electric power and supplies electric power to various loads in the railway vehicle 100.
  • the railway vehicle can be run with energy saving.
  • the rotating electric machine may be mounted on a vehicle (another example of a vehicle) such as a hybrid vehicle or an electric vehicle.
  • FIG. 12 is a diagram illustrating an example of an automobile 200 that includes the rotating electrical machine 201.
  • the rotating electrical machine 201 the motors shown in FIGS. 8 and 9 and the generator shown in FIG. 10 can be used.
  • the rotating electrical machine 201 may be used as an electric motor that outputs the driving force of the automobile 200, or a generator that converts kinetic energy during travel of the automobile 200 into electric power.
  • the rotating electrical machine may be mounted on, for example, industrial equipment (industrial motor), air conditioning equipment (air conditioner / water heater compressor motor), wind power generator, or elevator (winding machine).
  • Example 1 The raw materials were prepared at a predetermined ratio so as to have an alloy powder composition shown in Table 1 and a composition of Sm (Cr 0.08 Si 0.03 Fe 0.89 ) 8.3 .
  • An alloy ingot was prepared by arc melting the raw material blended in an argon gas atmosphere.
  • the alloy ingot was heat-treated at 950 ° C. for about 3 days in an argon gas atmosphere to perform a homogenization heat treatment. Thereafter, the alloy ingot was pulverized in a mortar to obtain an alloy powder.
  • the alloy powder was sieved with a sieve having an opening of 25 ⁇ m.
  • the alloy powder was heat-treated at 700 ° C. for 4 hours in a nitrogen gas atmosphere at about 1 atm to obtain a nitride alloy powder.
  • the obtained nitride alloy powder was filled in a mold while orientation-pressing in a magnetic field, and then the powder was subjected to discharge plasma sintering under conditions of a pressure of 1.0 GPa and a sintering temperature of 600 ° C. to obtain a permanent magnet.
  • the composition of the permanent magnet was the magnet composition shown in Table 1.
  • Table 2 shows values of density, coercive force, and subphase volume ratio in the permanent magnet of Example 1.
  • the coercive force is shown as a relative value when the coercive force of the permanent magnet of Comparative Example 1 described later is 100.
  • the volume ratio of the secondary phase was 2% (see Table 2).
  • Examples 2 to 16 The raw materials were prepared at a predetermined ratio so that the alloy powder composition had the values shown in Table 1. Other than that, permanent magnets were produced in the same manner as in Example 1. The characteristics of the obtained permanent magnet were evaluated in the same manner as in Example 1. Table 2 shows values of density, coercive force, and subphase volume ratio in the permanent magnets of Examples 2 to 16.
  • Example 1 A permanent magnet was produced in the same manner as in Example 1 except that the homogenization heat treatment temperature was 1000 ° C. The characteristics of the obtained permanent magnet were evaluated in the same manner as in Example 1. Table 2 shows values of density, coercive force, and subphase volume ratio in the permanent magnet of Comparative Example 1.
  • the permanent magnets (Examples 1 to 16) having a low subphase volume ratio have a coercive force higher than that of Comparative Example 1 when the density is increased to the same level as in Comparative Example 1. It was. This is because the amount of the subphase having a lower thermal stability than the main phase is small, the amount of ⁇ -Fe phase generated by the thermal decomposition of the subphase is reduced, and the coercive force is improved.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Hard Magnetic Materials (AREA)
  • Permanent Field Magnets Of Synchronous Machinery (AREA)
  • Electric Propulsion And Braking For Vehicles (AREA)
  • Powder Metallurgy (AREA)

Abstract

Cette invention concerne un aimant permanent représenté par la formule de composition RMZNX. Ledit aimant permanent comprend : une première phase qui a au moins une structure cristalline sélectionnée parmi une structure de type Th2Ni17, une structure de type Th2Zn17 et une structure de type TbCu7 ; et une seconde phase qui a au moins une structure cristalline sélectionnée parmi une structure de type de MgCu2 et une structure de type PuNi3. La fraction volumique de la quantité totale de la seconde phase est inférieure ou égale à 5 %.
PCT/JP2018/009078 2017-03-22 2018-03-08 Aimant permanent, machine dynamoélectrique et véhicule WO2018173782A1 (fr)

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CN112530653A (zh) * 2019-09-17 2021-03-19 株式会社东芝 磁铁材料、永磁铁、旋转电机及车辆

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CN109273183B (zh) * 2018-10-19 2020-06-16 广东省稀有金属研究所 一种耐腐蚀单晶磁粉及其制备方法与应用
CN109273182B (zh) * 2018-10-19 2020-06-16 广东省稀有金属研究所 一种单晶磁粉及其制备方法与应用
CN109273184B (zh) * 2018-10-19 2020-08-04 广东省稀有金属研究所 一种低成本耐腐蚀的单晶磁粉及其制备方法与应用
CN109243745B (zh) * 2018-10-19 2020-08-04 广东省稀有金属研究所 一种耐高温耐腐蚀单晶磁粉及其制备方法与应用

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JP2005272925A (ja) * 2004-03-24 2005-10-06 Hitachi Metals Ltd Ｒ−ｔ−ｎ系磁粉およびその製造方法
JP2014223652A (ja) * 2013-05-16 2014-12-04 住友電気工業株式会社 希土類−鉄系合金材の製造方法、希土類−鉄系合金材、希土類−鉄−窒素系合金材の製造方法、希土類−鉄−窒素系合金材、及び希土類磁石
WO2016151619A1 (fr) * 2015-03-23 2016-09-29 株式会社 東芝 Matériau d'aimant, aimant permanent, moteur et génératrice

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JP2005272925A (ja) * 2004-03-24 2005-10-06 Hitachi Metals Ltd Ｒ−ｔ−ｎ系磁粉およびその製造方法
JP2014223652A (ja) * 2013-05-16 2014-12-04 住友電気工業株式会社 希土類−鉄系合金材の製造方法、希土類−鉄系合金材、希土類−鉄−窒素系合金材の製造方法、希土類−鉄−窒素系合金材、及び希土類磁石
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