WO2013137135A1 - 希土類永久磁石、希土類永久磁石の製造方法及び希土類永久磁石の製造装置 - Google Patents
希土類永久磁石、希土類永久磁石の製造方法及び希土類永久磁石の製造装置 Download PDFInfo
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- WO2013137135A1 WO2013137135A1 PCT/JP2013/056434 JP2013056434W WO2013137135A1 WO 2013137135 A1 WO2013137135 A1 WO 2013137135A1 JP 2013056434 W JP2013056434 W JP 2013056434W WO 2013137135 A1 WO2013137135 A1 WO 2013137135A1
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- sintering
- permanent magnet
- earth permanent
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- rare earth
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Images
Classifications
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- 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
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- 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
- B22F3/14—Both compacting and sintering simultaneously
-
- 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
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- 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
-
- 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
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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
- H01F1/06—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F7/00—Magnets
- H01F7/02—Permanent magnets [PM]
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- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- 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
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- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the present invention relates to a rare earth permanent magnet, a method for manufacturing a rare earth permanent magnet, and a manufacturing apparatus.
- a powder sintering method is used as a manufacturing method of the permanent magnet.
- the powder sintering method first, raw materials are roughly pulverized, and magnet powder is manufactured by finely pulverizing with a jet mill (dry pulverization) or a wet bead mill (wet pulverization). Thereafter, the magnet powder is put into a mold and press-molded into a desired shape while applying a magnetic field from the outside. Then, it is manufactured by sintering a solid magnet powder formed into a desired shape at a predetermined temperature (for example, 800 ° C. to 1150 ° C. for Nd—Fe—B magnets) (for example, Japanese Patent Laid-Open No. 2-266503). ).
- a predetermined temperature for example, 800 ° C. to 1150 ° C. for Nd—Fe—B magnets
- the present invention has been made to solve the problems in the prior art, and in the case of mass-producing permanent magnets having the same shape, the uniformity of the shape of each permanent magnet can be improved and the production efficiency can be improved. It is an object of the present invention to provide a raised rare earth permanent magnet, a rare earth permanent magnet manufacturing method and a manufacturing apparatus.
- a method for producing a rare earth permanent magnet includes a step of pulverizing a magnet raw material into magnet powder, a step of molding the pulverized magnet powder into a molded body, and pressurizing the molded body.
- the sintering die of the binding apparatus is characterized in that an inflow hole into which a part of the pressed compact is introduced is formed in at least one direction.
- the method for producing a rare earth permanent magnet according to the present invention is characterized in that the pressure sintering apparatus includes a plurality of sintering dies, and the plurality of molded bodies are pressure sintered simultaneously.
- the method for producing a rare earth permanent magnet according to the present invention is characterized in that the inflow hole is a hole having a diameter of 1 mm to 5 mm.
- the method for producing a rare earth permanent magnet according to the present invention is characterized in that the inflow hole is provided on a surface opposed to a pressure direction when performing pressure sintering.
- the method for producing a rare earth permanent magnet according to the present invention is characterized in that, in the step of pressure-sintering the compact, sintering is performed by uniaxial pressure sintering.
- the method for producing a rare earth permanent magnet according to the present invention is characterized in that in the step of pressure-sintering the compact, sintering is performed by electric current sintering.
- a mixture in which the pulverized magnet powder and a binder are mixed is generated, and the mixture is formed into a sheet shape.
- a green sheet is produced as the molded body by molding.
- the rare earth permanent magnet manufacturing apparatus is configured to sinter a compact formed of a magnet raw material pulverized into magnet powder in a sintering mold of a pressure sintering apparatus and perform pressure sintering.
- An apparatus for producing a rare earth permanent magnet wherein a sintering die of the pressure sintering apparatus is formed with an inflow hole into which a part of the pressed molded body flows in at least one direction.
- the rare earth permanent magnet manufacturing apparatus is characterized in that the pressure sintering apparatus includes a plurality of sintering dies, and the plurality of molded bodies are pressure sintered simultaneously.
- the inflow hole is a hole having a diameter of 1 mm to 5 mm.
- the rare earth permanent magnet manufacturing apparatus is characterized in that the inflow hole is provided on a surface opposed to a pressing direction when performing pressure sintering.
- the rare earth permanent magnet manufacturing apparatus is characterized in that when the compact is subjected to pressure sintering, it is sintered by uniaxial pressure sintering.
- the rare earth permanent magnet manufacturing apparatus is characterized in that when the compact is pressure sintered, it is sintered by electric current sintering.
- the rare earth permanent magnet manufacturing apparatus is characterized in that the compact is a green sheet obtained by molding a mixture of the pulverized magnet powder and a binder into a sheet shape.
- the rare earth permanent magnet according to the present invention includes a step of pulverizing a magnet raw material into magnet powder, a step of molding the pulverized magnet powder into a molded body, and a sintered mold of a pressure sintering apparatus. And the step of sintering the molded body placed on the sintering mold of the pressure sintering apparatus by pressure sintering, and the sintering mold of the pressure sintering apparatus is An inflow hole into which a part of the pressurized molded body flows is formed in at least one direction.
- the sintering mold of the pressure sintering apparatus for heating and sintering the compact is a compact of the compact that is pressed in at least one direction. Since an inflow hole into which a part flows is formed, the uniformity of the shape of each permanent magnet can be improved when mass-producing permanent magnets having the same shape. Moreover, it becomes possible to improve manufacturing efficiency by eliminating the need for correction after sintering. In particular, even if there is a variation in the filling amount filled in the sintering mold for pressure sintering, the uniformity of the shape of the permanent magnet can be ensured. Further, even when the amount of filling into the sintering mold is excessive, the pressure applied to the molded body does not become higher than necessary, and there is no possibility that defects or the like occur during sintering.
- the pressure sintering apparatus includes a plurality of sintering dies, and a plurality of molded bodies are pressure sintered simultaneously. Further improvement is possible. In addition, it is possible to prevent variation in shape between the permanent magnets sintered at the same time.
- the inflow hole is a hole having a diameter of 1 mm to 5 mm, pressure sintering can be appropriately performed by making the inflow hole in an appropriate shape. In addition, it is possible to maintain the effect of the shape uniformity in the sintered permanent magnet.
- the inflow hole is provided on the surface facing the pressing direction when performing pressure sintering, so that the effect of shape uniformity can be further improved.
- the permanent magnet after sintering can be easily removed from the sintered mold.
- the permanent magnet shrinks uniformly due to sintering by uniaxial pressure sintering. As a result, it is possible to prevent deformation such as warpage or dent in the sintered permanent magnet.
- the compact by pressure sintering in the step of sintering the compact by pressure sintering, it is sintered by current sintering, so that rapid heating and cooling are possible. It becomes possible to sinter in a low temperature range. As a result, it is possible to shorten the temperature rise and holding time in the sintering process, and it is possible to produce a dense sintered body that suppresses the grain growth of the magnet particles.
- the permanent magnet is composed of a magnet obtained by mixing magnet powder and a binder and sintering a molded green sheet, so that the shrinkage due to sintering becomes uniform.
- deformation such as warping and dent after sintering does not occur, and pressure unevenness at the time of pressing is eliminated, so that it is not necessary to carry out correction processing after sintering, which is conventionally performed, and simplifies the manufacturing process. be able to.
- a permanent magnet can be formed with high dimensional accuracy. As a result, it becomes possible to further improve the uniformity of the shape of the permanent magnet after sintering by combining with sintering by a pressure sintering apparatus having an inflow hole.
- the sintering mold of the pressure sintering apparatus for heating and sintering the molded body is a part of the pressed molded body in at least one direction. Since the inflow hole into which the inflow is formed is formed, the uniformity of the shape of the individual permanent magnets can be improved when mass-producing permanent magnets having the same shape. Moreover, it becomes possible to improve manufacturing efficiency by eliminating the need for correction after sintering. In particular, even if there is a variation in the filling amount filled in the sintering mold for pressure sintering, the uniformity of the shape of the permanent magnet can be ensured. Further, even when the amount of filling into the sintering mold is excessive, the pressure applied to the molded body does not become higher than necessary, and there is no possibility that defects or the like occur during sintering.
- the inflow hole is a hole having a diameter of 1 mm to 5 mm, pressure sintering can be appropriately performed by making the inflow hole in an appropriate shape. In addition, it is possible to maintain the effect of the shape uniformity in the sintered permanent magnet.
- the inflow hole is provided on the surface facing the pressing direction when performing pressure sintering, so that the effect of shape uniformity can be further improved.
- the permanent magnet after sintering can be easily removed from the sintered mold.
- the rare earth permanent magnet manufacturing apparatus in the step of sintering the compact by pressure sintering, the permanent magnet shrinks uniformly due to sintering by uniaxial pressure sintering. As a result, it is possible to prevent deformation such as warpage or dent in the sintered permanent magnet.
- the rare earth permanent magnet manufacturing apparatus in the step of sintering the compact by pressure sintering, since it is sintered by current sintering, rapid heating and cooling are possible, It becomes possible to sinter in a low temperature range. As a result, it is possible to shorten the temperature rise and holding time in the sintering process, and it is possible to produce a dense sintered body that suppresses the grain growth of the magnet particles.
- the permanent magnet is composed of a magnet obtained by mixing magnet powder and a binder and sintering a molded green sheet, so that the shrinkage due to sintering becomes uniform.
- deformation such as warping and dent after sintering does not occur, and pressure unevenness at the time of pressing is eliminated, so that it is not necessary to carry out correction processing after sintering, which is conventionally performed, and simplifies the manufacturing process. be able to.
- a permanent magnet can be formed with high dimensional accuracy. As a result, it becomes possible to further improve the uniformity of the shape of the permanent magnet after sintering by combining with sintering by a pressure sintering apparatus having an inflow hole.
- the sintered body of the pressure sintering apparatus that is manufactured by heat-sintering the formed body and that heat-sinters the formed body is at least in one direction.
- the uniformity of the shape of each permanent magnet can be improved when mass-producing the same shape of permanent magnet.
- even if there is a variation in the filling amount filled in the sintering mold for pressure sintering the uniformity of the shape of the permanent magnet can be ensured. Further, even when the amount of filling into the sintering mold is excessive, the pressure applied to the molded body does not become higher than necessary, and there is no possibility that defects or the like occur during sintering.
- FIG. 1 is an overall view showing a permanent magnet according to the present invention.
- FIG. 2 is an explanatory view showing a manufacturing process of the permanent magnet according to the present invention.
- FIG. 3 is an explanatory view showing a green sheet forming process, in particular, of the manufacturing process of the permanent magnet according to the present invention.
- FIG. 4 is an explanatory view showing a green sheet heating process and a magnetic field orientation process in the manufacturing process of the permanent magnet according to the present invention.
- FIG. 5 is a diagram showing an example in which the magnetic field is oriented in the in-plane vertical direction of the green sheet.
- FIG. 6 is a diagram illustrating a heating device using a heat medium (silicone oil).
- FIG. 7 is an overall view of the SPS sintering apparatus.
- FIG. 1 is an overall view showing a permanent magnet according to the present invention.
- FIG. 2 is an explanatory view showing a manufacturing process of the permanent magnet according to the present invention.
- FIG. 3 is an explanatory
- FIG. 8 is a schematic diagram showing the internal structure of one sintering mold provided in the SPS sintering apparatus.
- FIG. 9 is a photograph showing the external shape of the permanent magnet manufactured in each of the example and the comparative example.
- FIG. 10 is a diagram showing a comparison result of the shapes of the permanent magnets manufactured in the example and the comparative example, respectively.
- FIG. 11 is a diagram comparing variations in the shape of a plurality of permanent magnets manufactured simultaneously in the example.
- FIG. 1 is an overall view showing a permanent magnet 1 according to the present invention.
- the permanent magnet 1 shown in FIG. 1 has a fan shape, but the shape of the permanent magnet 1 varies depending on the punched shape.
- the permanent magnet 1 according to the present invention is an Nd—Fe—B anisotropic magnet. The content of each component is Nd: 27 to 40 wt%, B: 0.8 to 2 wt%, and Fe (electrolytic iron): 60 to 70 wt%.
- FIG. 1 is an overall view showing a permanent magnet 1 according to the present embodiment.
- the permanent magnet 1 is a thin-film permanent magnet having a thickness of, for example, 0.05 mm to 10 mm (for example, 1 mm). Then, as will be described later, a compact (green sheet) molded in a sheet form is pressure-sintered from a compact molded by compacting or a mixture (slurry or compound) in which magnet powder and a binder are mixed. It is produced by.
- the pressure sintering for sintering the molded body for example, hot press sintering, hot isostatic pressing (HIP) sintering, ultrahigh pressure synthetic sintering, gas pressure sintering, discharge plasma ( SPS) sintering and the like.
- HIP hot isostatic pressing
- SPS discharge plasma
- a sintering method in which sintering is performed in a shorter time and at a lower temperature.
- SPS sintering is a sintering method in which a graphite sintering mold having a sintering object disposed therein is heated while being pressed in a uniaxial direction. Further, in SPS sintering, in addition to thermal and mechanical energy used for general sintering, electromagnetic energy by pulse energization and self-heating of the work piece are obtained by pulse current heating and mechanical pressure. The discharge plasma energy generated between the particles is used as a driving force for the sintering. Therefore, rapid heating / cooling is possible compared to atmosphere heating in an electric furnace or the like, and sintering can be performed in a lower temperature range.
- a molded body formed by compacting or a green sheet punched out into a desired product shape (for example, the fan shape shown in FIG. 1) is fired in the SPS sintering apparatus. Place in the mold.
- a plurality of (for example, nine) molded bodies are respectively arranged with respect to a plurality of (for example, nine) sintering molds provided in the SPS sintering apparatus as described later. And simultaneously sintering (see FIG. 7).
- the permanent magnet 1 when the permanent magnet 1 is manufactured by green sheet molding, a resin, a long-chain hydrocarbon, a fatty acid methyl ester, a mixture thereof, or the like is used as the binder mixed with the magnet powder. Furthermore, when a resin is used for the binder, it is preferable to use a polymer that does not contain an oxygen atom in the structure and has a depolymerization property. Further, when a green sheet is formed by hot melt molding as will be described later, a thermoplastic resin is used to perform magnetic field orientation in a state where the formed green sheet is heated and softened.
- the polymer which consists of 1 type, or 2 or more types of polymers or copolymers chosen from the monomer shown by the following general formula (1) corresponds.
- R1 and R2 represent a hydrogen atom, a lower alkyl group, a phenyl group or a vinyl group.
- polystyrene resin examples include polyisobutylene (PIB), which is a polymer of isobutylene, polyisoprene (isoprene rubber, IR), which is a polymer of isoprene, and polybutadiene (butadiene) that is a polymer of 1,3-butadiene.
- PIB polyisobutylene
- IR polyisoprene rubber
- IR isoprene rubber
- IR isoprene rubber
- butadiene butadiene
- Rubber, BR polystyrene as a polymer of styrene, styrene-isoprene block copolymer (SIS) as a copolymer of styrene and isoprene, butyl rubber (IIR) as a copolymer of isobutylene and isoprene, styrene and butadiene
- SIS styrene-isoprene block copolymer
- IIR butyl rubber
- SBS styrene-butadiene block copolymer which is a copolymer of 2-methyl-1-pentene, a polymer of 2-methyl-1-pentene, and a polymer of 2-methyl-1-butene.
- a 2-methyl-1-butene polymer resin a polymer of ⁇ -methylstyrene That there is ⁇ - methyl styrene polymer resin.
- the resin used for the binder may include a small amount of a polymer or copolymer of a monomer containing an oxygen atom (for example, polybutyl methacrylate, polymethyl methacrylate, etc.).
- a monomer that does not correspond to the general formula (1) may be partially copolymerized. Even in that case, it is possible to achieve the object of the present invention.
- thermoplastic resin that softens at 250 ° C. or lower, more specifically a thermoplastic resin having a glass transition point or a melting point of 250 ° C. or lower in order to appropriately perform magnetic field orientation. .
- a long chain hydrocarbon when used for the binder, it is preferable to use a long chain saturated hydrocarbon (long chain alkane) that is solid at room temperature and liquid at room temperature or higher. Specifically, it is preferable to use a long-chain saturated hydrocarbon having 18 or more carbon atoms.
- molding so that it may mention later is magnetic field orientation
- magnetic field orientation is performed in the state which heated the green sheet above melting
- fatty acid methyl ester when used as the binder, it is preferable to use methyl stearate or methyl docosanoate which is solid at room temperature and liquid at room temperature or higher.
- methyl stearate or methyl docosanoate which is solid at room temperature and liquid at room temperature or higher.
- magnetic field orientation magnetic field orientation is performed in the state which heated the green sheet above melting
- the amount of carbon and oxygen contained in the magnet can be reduced.
- the amount of carbon remaining in the magnet after sintering is 2000 ppm or less, more preferably 1000 ppm or less.
- the amount of oxygen remaining in the magnet after sintering is set to 5000 ppm or less, more preferably 2000 ppm or less.
- the amount of the binder added is an amount that appropriately fills the gaps between the magnet particles in order to improve the thickness accuracy of the sheet when the slurry or the heated and melted compound is formed into a sheet.
- the ratio of the binder to the total amount of magnet powder and binder is 1 wt% to 40 wt%, more preferably 2 wt% to 30 wt%, and even more preferably 3 wt% to 20 wt%.
- FIG. 2 is an explanatory view showing a manufacturing process of the permanent magnet 1 according to the present embodiment.
- an ingot made of a predetermined fraction of Nd—Fe—B (eg, Nd: 32.7 wt%, Fe (electrolytic iron): 65.96 wt%, B: 1.34 wt%) is manufactured. Thereafter, the ingot is roughly pulverized to a size of about 200 ⁇ m by a stamp mill or a crusher. Alternatively, the ingot is melted, flakes are produced by strip casting, and coarsely pulverized by hydrogen crushing. Thereby, coarsely pulverized magnet powder 10 is obtained.
- Nd—Fe—B eg, Nd: 32.7 wt%, Fe (electrolytic iron): 65.96 wt%, B: 1.34 wt
- the coarsely pulverized magnet powder 10 is finely pulverized by a wet method using a bead mill 11 or a dry method using a jet mill.
- the coarsely pulverized magnet powder 10 is finely pulverized in an organic solvent to a particle size within a predetermined range (for example, 0.1 ⁇ m to 5.0 ⁇ m), and the magnet powder is dispersed in the organic solvent. Disperse. Thereafter, the magnet powder contained in the organic solvent after the wet pulverization is dried by vacuum drying or the like, and the dried magnet powder is taken out.
- the solvent used for the pulverization is an organic solvent, but the type of the solvent is not particularly limited, alcohols such as isopropyl alcohol, ethanol and methanol, esters such as ethyl acetate, lower hydrocarbons such as pentane and hexane, Aromatics such as benzene, toluene and xylene, ketones, mixtures thereof and the like can be used.
- a hydrocarbon solvent that does not contain an oxygen atom in the solvent is used.
- coarsely pulverized magnet powder is (a) in an atmosphere composed of an inert gas such as nitrogen gas, Ar gas, and He gas having substantially 0% oxygen content.
- the oxygen concentration of substantially 0% is not limited to the case where the oxygen concentration is completely 0%, but may contain oxygen in such an amount that a very small amount of oxide film is formed on the surface of the fine powder. Means good.
- the magnet powder finely pulverized by the bead mill 11 or the like is molded into a desired shape.
- the molding of the magnet powder includes, for example, compaction molding that forms a desired shape using a mold and green sheet molding in which the magnet powder is once formed into a sheet shape and then punched into the desired shape.
- compaction molding that forms a desired shape using a mold and green sheet molding in which the magnet powder is once formed into a sheet shape and then punched into the desired shape.
- green sheet molding for example, hot melt coating for molding a compound in which magnet powder and a binder are mixed into a sheet, or slurry containing magnet powder, a binder, and an organic solvent is coated on a substrate. There is molding by slurry coating or the like to form a sheet.
- a powdery mixture (compound) 12 composed of magnet powder and binder is prepared by mixing a binder with magnet powder finely pulverized by a bead mill 11 or the like.
- the binder resin, long chain hydrocarbon, fatty acid methyl ester, a mixture thereof, or the like is used as described above.
- a resin a thermoplastic resin made of a depolymerizable polymer that does not contain an oxygen atom in the structure is used.
- a long-chain hydrocarbon when a long-chain hydrocarbon is used, the resin is solid at room temperature or above room temperature.
- the amount of the binder added is such that the ratio of the binder to the total amount of the magnet powder and the binder in the compound 12 after the addition is 1 wt% to 40 wt%, more preferably 2 wt% to 30 wt%, still more preferably 3 wt%. % To 20 wt%.
- the binder is added in an atmosphere made of an inert gas such as nitrogen gas, Ar gas, or He gas.
- the mixing of the magnet powder and the binder is performed, for example, by putting the magnet powder and the binder in an organic solvent and stirring with a stirrer. And the compound 12 is extracted by heating the organic solvent containing magnet powder and a binder after stirring, and vaporizing an organic solvent.
- the mixing of the magnet powder and the binder is preferably performed in an atmosphere made of an inert gas such as nitrogen gas, Ar gas, or He gas.
- an inert gas such as nitrogen gas, Ar gas, or He gas.
- the binder is added to the organic solvent and kneaded without taking out the magnet powder from the organic solvent used for pulverization, and then the organic solvent is volatilized to be described later. It is good also as a structure which obtains the compound 12.
- a green sheet is formed by forming the compound 12 into a sheet shape.
- the compound 12 in hot melt coating, the compound 12 is heated to melt the compound 12 to form a fluid, and then the coating is applied on the support substrate 13 such as a separator. Then, the long sheet-like green sheet 14 is formed on the support base material 13 by heat dissipation and solidifying.
- the temperature at which the compound 12 is heated and melted is 50 to 300 ° C., although it varies depending on the type and amount of the binder used. However, the temperature needs to be higher than the melting point of the binder to be used.
- magnet powder and a binder are disperse
- the coating method of the melted compound 12 is preferably a method having excellent layer thickness controllability such as a slot die method or a calendar roll method.
- a slot die method coating is performed by extruding a heated compound 12 in a fluid state by a gear pump and inserting the compound 12 into a die.
- the calendar roll method a certain amount of the compound 12 is charged into the gap between the two heated rolls, and the compound 12 melted by the heat of the roll is applied onto the support base 13 while rotating the roll.
- a silicone-treated polyester film is used as the support base material 13.
- the film is formed on the support substrate 13 by forming the compound 12 melted by extrusion molding into a sheet shape and extruding it onto the support substrate 13 instead of coating on the support substrate 13. It is good also as composition to do.
- FIG. 3 is a schematic view showing a process of forming the green sheet 14 by the slot die method.
- the die 15 used in the slot die system is formed by superimposing blocks 16 and 17 on each other, and a slit 18 and a cavity (liquid reservoir) 19 are formed by a gap between the blocks 16 and 17.
- the cavity 19 communicates with a supply port 20 provided in the block 17.
- the supply port 20 is connected to a coating liquid supply system constituted by a gear pump (not shown) or the like, and the metered fluid-like compound 12 is quantified in the cavity 19 via the supply port 20. Supplied by a pump or the like.
- the fluid-like compound 12 supplied to the cavity 19 is fed to the slit 18 and discharged from the discharge port 21 of the slit 18 with a predetermined application width with a uniform amount in the width direction at a constant amount per unit time.
- the support base material 13 is continuously conveyed at a preset speed as the coating roll 22 rotates.
- the ejected fluid compound 12 is applied to the support base material 13 with a predetermined thickness, and then heat-radiating and solidifying to form a long sheet-like green sheet 14 on the support base material 13. Is done.
- the sheet thickness of the green sheet 14 after coating is measured, and the gap D between the die 15 and the support base 13 is feedback-controlled based on the measured value. desirable. Further, the fluctuation of the amount of the fluid compound 12 supplied to the die 15 is reduced as much as possible (for example, suppressed to fluctuation of ⁇ 0.1% or less), and the fluctuation of the coating speed is reduced as much as possible (for example, ⁇ 0. It is desirable to suppress the fluctuation to 1% or less. Thereby, it is possible to further improve the thickness accuracy of the green sheet 14.
- the thickness accuracy of the formed green sheet 14 is within ⁇ 10%, more preferably within ⁇ 3%, and even more preferably within ⁇ 1% with respect to the design value (for example, 1 mm).
- the design value for example, 1 mm.
- the set thickness of the green sheet 14 is desirably set in the range of 0.05 mm to 20 mm. When the thickness is less than 0.05 mm, the productivity must be reduced because multiple layers must be stacked.
- the green sheet 14 is first softened by heating the green sheet 14 that is continuously conveyed together with the support base material 13.
- the temperature and time for heating the green sheet 14 vary depending on the type and amount of the binder used, but for example, 100 to 250 ° C. and 0.1 to 60 minutes. However, in order to soften the green sheet 14, it is necessary to set the temperature to be equal to or higher than the glass transition point or melting point of the binder used.
- a heating method for heating the green sheet 14 for example, there are a heating method using a hot plate and a heating method using a heat medium (silicone oil) as a heat source.
- magnetic field orientation is performed by applying a magnetic field to the in-plane direction and the length direction of the green sheet 14 softened by heating.
- the intensity of the applied magnetic field is 5000 [Oe] to 150,000 [Oe], preferably 10,000 [Oe] to 120,000 [Oe].
- the C axis (easy magnetization axis) of the magnet crystal included in the green sheet 14 is oriented in one direction.
- the magnetic field may be applied in the in-plane direction and the width direction of the green sheet 14. Moreover, it is good also as a structure which orientates a magnetic field simultaneously with respect to the several green sheet 14.
- a configuration in which a magnetic field is applied at the same time as the heating process may be performed, or a magnetic field may be applied after the heating process and before the green sheet solidifies. It is good also as performing the process to perform. Moreover, it is good also as a structure which magnetic field orientates before the green sheet 14 apply
- FIG. 4 is a schematic diagram showing a heating process and a magnetic field orientation process of the green sheet 14.
- FIG. 4 an example in which the magnetic field orientation process is performed simultaneously with the heating process will be described.
- heating and magnetic field orientation on the green sheet 14 coated by the slot die method described above are performed on the long sheet-like green sheet 14 that is continuously conveyed by a roll. That is, an apparatus for performing heating and magnetic field orientation is disposed on the downstream side of the coating apparatus (die or the like), and is performed by a process continuous with the above-described coating process.
- the solenoid 25 is disposed on the downstream side of the die 15 and the coating roll 22 so that the transported support base material 13 and the green sheet 14 pass through the solenoid 25.
- the hot plates 26 are arranged in a pair above and below the green sheet 14 in the solenoid 25.
- the green sheet 14 is heated by a pair of upper and lower hot plates 26 and an electric current is passed through the solenoid 25, so that the in-plane direction of the long green sheet 14 (that is, the sheet surface of the green sheet 14).
- a magnetic field in the longitudinal direction Thereby, the continuously conveyed green sheet 14 is softened by heating, and a magnetic field is applied to the in-plane direction and the length direction of the softened green sheet 14 (in the direction of arrow 27 in FIG. 4).
- the surface of the green sheet 14 can be prevented from standing upright by setting the direction in which the magnetic field is applied to the in-plane direction. Moreover, it is preferable that the heat dissipation and solidification of the green sheet 14 performed after the magnetic field orientation is performed in a transported state. Thereby, the manufacturing process can be made more efficient.
- a pair of magnetic field coils are arranged on the left and right of the green sheet 14 that is conveyed instead of the solenoid 25. And it becomes possible to generate a magnetic field in the in-plane direction and the width direction of the long sheet-like green sheet 14 by passing a current through each magnetic field coil.
- the magnetic field orientation can be set to the in-plane vertical direction of the green sheet 14.
- the magnetic field application device using a pole piece or the like is used.
- the magnetic field application device 30 using a pole piece or the like includes two ring-shaped coil portions 31 and 32 arranged in parallel so that the central axes are the same, and the coil portion 31. , 32 and two substantially cylindrical pole pieces 33, 34 respectively disposed in the ring holes, and are spaced apart from the conveyed green sheet 14 by a predetermined distance.
- FIG. 6 is a diagram showing an example of a heating device 37 using a heat medium.
- the heating device 37 forms a substantially U-shaped cavity 39 inside a flat plate member 38 serving as a heating element, and heat heated to a predetermined temperature (for example, 100 to 300 ° C.) in the cavity 39. It is set as the structure which circulates the silicone oil which is a medium.
- the heating device 37 is disposed in a pair above and below the green sheet 14 in the solenoid 25.
- the continuously conveyed green sheet 14 is heated and softened through the flat plate member 38 that is heated by the heat medium.
- the flat plate member 38 may be brought into contact with the green sheet 14 or may be arranged at a predetermined interval.
- a magnetic field is applied to the in-plane direction and the length direction (in the direction of arrow 27 in FIG. 4) of the green sheet 14 by the solenoid 25 arranged around the softened green sheet 14.
- An appropriate uniform magnetic field can be oriented.
- the heating device 37 using the heat medium as shown in FIG. 6 does not have a heating wire inside unlike the general hot plate 26, so even if it is placed in a magnetic field, There is no possibility that the heating wire vibrates or is cut, and the green sheet 14 can be appropriately heated.
- when performing control by electric current there is a problem that causes fatigue failure due to vibration of the heating wire when the power is turned on or off, but by using the heating device 37 using a heat medium as a heat source, Such a problem can be solved.
- the green sheet 14 when the green sheet 14 is formed from a liquid material having high fluidity such as slurry by a general slot die method or doctor blade method without using hot melt molding, a magnetic field gradient is generated.
- the magnetic powder contained in the green sheet 14 is attracted toward the stronger magnetic field, so that the slurry forming the green sheet 14 is closer to the liquid, that is, the thickness of the green sheet 14 is uneven. May occur.
- the compound 12 when the compound 12 is molded into the green sheet 14 by hot melt molding as in the present invention, the viscosity near room temperature reaches several tens of thousands Pa ⁇ s, and the magnetic powder tends to shift when passing through the magnetic field gradient. It does not occur. Furthermore, the viscosity of the binder is lowered by being transported and heated in a uniform magnetic field, and uniform C-axis orientation is possible only by the rotational torque in the uniform magnetic field.
- the thickness exceeds 1 mm.
- a liquid material having high fluidity such as a slurry containing an organic solvent by a general slot die method or doctor blade method without using hot melt molding
- the thickness exceeds 1 mm.
- foaming due to vaporization of the organic solvent contained in the slurry or the like at the time of drying becomes a problem.
- the drying time is prolonged to suppress foaming, the magnet powder is settled, and accordingly, the density distribution of the magnet powder is biased with respect to the direction of gravity, which causes warping after firing. Therefore, in the molding from the slurry, the upper limit value of the thickness is substantially regulated, so it is necessary to mold the green sheet with a thickness of 1 mm or less and then laminate it.
- the green sheet 14 subjected to magnetic field orientation is punched into a desired product shape (for example, a fan shape shown in FIG. 1), and a molded body 40 is formed.
- a non-oxidizing atmosphere (particularly a hydrogen atmosphere or hydrogen in the present invention) in which the molded body 40 is pressurized to atmospheric pressure, or a pressure higher or lower than atmospheric pressure (for example, 1.0 Pa or 1.0 MPa).
- an inert gas mixed gas atmosphere at a binder decomposition temperature for several hours (for example, 5 hours) to perform a calcination treatment.
- the supply amount of hydrogen during calcination is set to 5 L / min.
- decarbonization for reducing the amount of carbon in the molded body 40 is performed.
- the calcining treatment is performed under the condition that the carbon content in the molded body 40 is 2000 ppm or less, more preferably 1000 ppm or less. Accordingly, the entire permanent magnet 1 can be densely sintered by the subsequent sintering process, and the residual magnetic flux density and coercive force are not reduced.
- the binder decomposition temperature is determined based on the analysis results of the binder decomposition product and decomposition residue. Specifically, a temperature range is selected in which decomposition products of the binder are collected, decomposition products other than the monomers are not generated, and products due to side reactions of the remaining binder components are not detected even in the analysis of the residues. Although it varies depending on the type of the binder, it is set to 200 ° C. to 900 ° C., more preferably 400 ° C. to 600 ° C. (eg 600 ° C.).
- the calcining treatment is performed at the thermal decomposition temperature and binder decomposition temperature of the organic compound constituting the organic solvent. Thereby, the remaining organic solvent can be removed.
- the thermal decomposition temperature of the organic compound is determined depending on the type of the organic solvent to be used, but basically the thermal decomposition of the organic compound can be performed at the binder decomposition temperature.
- a sintering process for sintering the compact 40 that has been calcined by the calcining process is performed.
- the pressure sintering which sinters in the state which especially pressed the molded object 40 is used as a sintering method of the molded object 40.
- pressure sintering include hot press sintering, hot isostatic pressing (HIP) sintering, ultra-high pressure synthetic sintering, gas pressure sintering, and discharge plasma (SPS) sintering. is there.
- the SPS is uniaxial pressure sintering that pressurizes in a uniaxial direction and is sintered by current sintering.
- Sintering is preferably used.
- FIG. Specifically, the SPS sintering apparatus including a plurality of sintering dies is configured such that the compact 40 is placed in each sintering dies and pressure sintering is performed simultaneously.
- the pressure value is set to, for example, 0.01 MPa to 100 MPa, the pressure is increased to 940 ° C. at 10 ° C./min in a vacuum atmosphere of several Pa or less, and then held for 5 minutes. Is preferred. Thereafter, it is cooled and heat-treated again at 300 ° C. to 1000 ° C. for 2 hours. And the permanent magnet 1 is manufactured as a result of sintering.
- FIG. 7 is an overall view of the SPS sintering apparatus 45.
- FIG. 8 is a schematic view showing the internal structure of one sintering mold provided in the SPS sintering apparatus.
- the SPS sintering apparatus 45 includes a plurality of (9 pieces in FIG. 7) sintering dies 46 and is installed in a vacuum champ (not shown).
- each of the sintering dies 46 has a graphite main body portion 47 in which a cylindrical hole is formed, and a cylindrical hole formed in the main body portion 47.
- the upper punch 48 and the lower punch 49 are made of graphite.
- the molded bodies 40 are respectively installed in cylindrical space portions formed by the main body portion 47, the upper punch 48, and the lower punch 49.
- the upper punch 48 is formed with an inflow hole 50 through which a part of the pressed compact 40 flows. And even if there is variation in the height and volume of the molded body 40 before sintering by forming the inflow hole 50, when a part of the molded body 40 flows into the inflow hole 50 during pressurization, It becomes possible to finely adjust the variation. As a result, it is possible to improve the uniformity of the shape of the permanent magnet 1 after pressure sintering. In particular, as shown in FIG.
- the inflow hole 50 is preferably provided in a surface (for example, the upper punch 48 or the lower punch 49) facing the pressing direction when performing pressure sintering, but is provided in the other direction (for example, the main body 47). You may do it. Further, the inflow holes 50 may be provided at a plurality of locations. In addition, the size of the inflow hole 50 is not particularly limited. However, if it is too large, pressure sintering cannot be performed appropriately, and if it is too small, the above-described improvement in uniformity cannot be obtained. Therefore, it is desirable that the diameter is in the range of 1 mm to 5 mm.
- the inflow hole 50 may be a hole that penetrates to the outside of the sintering mold 46, or may be a hole that does not penetrate.
- the compact 40 is installed inside the sintering mold 46.
- the calcining process described above may also be performed in a state where the molded body 40 is installed in the sintering mold 46.
- a low-voltage and high-current DC pulse voltage / current is applied using the upper punch electrode 51 connected to the upper punch 48 and the lower punch electrode 52 connected to the lower punch 49.
- a load is applied to the upper punch 48 and the lower punch 49 from above and below using a pressure mechanism (not shown).
- a pressure mechanism not shown
- the upper punch 48 and the lower punch 49 that pressurize the compact 40 are configured so as to be integrated (that is, can be pressed simultaneously) between the respective sintering dies 46. Further, a plurality of molded bodies 40 may be arranged in one sintered mold 46. Specific sintering conditions are shown below. Pressure value: 1 MPa Sintering temperature: raised to 940 ° C. at 10 ° C./min and held for 5 minutes Atmosphere: vacuum atmosphere of several Pa or less
- the SPS sintering apparatus 45 that includes a plurality of sintering dies 46 and can simultaneously perform SPS sintering on a plurality of molded bodies 40 has been described.
- an SPS sintering apparatus that includes only the sintering mold 46 and that can perform SPS sintering only on one molded body 40 may be used. Even in such a case, it is possible to improve the uniformity of the shape between the permanent magnets that are sequentially manufactured.
- the binder polyisobutylene (PIB) was used. Further, the heated and melted compound was applied to the substrate by a slot die method to form a green sheet. Moreover, while heating the shape
- PIB polyisobutylene
- the green sheet punched into a desired shape after magnetic field orientation is calcined in a hydrogen atmosphere, and then SPS sintering (pressure value: 1 MPa, sintering temperature: increased to 940 ° C. at 10 ° C./min, 5 minutes) Sintered).
- SPS sintering uses the SPS sintering apparatus 45 provided with the several sintering type
- a plurality of compacts to be sintered simultaneously have slightly different filling amounts of magnet raw materials (specifically, four patterns of 6.65 g, 6.86 g, 7.14 g, and 7.35 g). Molded.
- As the inflow hole 50 an inflow hole 50 having a diameter of 2 mm was formed for each of the upper punch 48 and the lower punch 49. The other steps are the same as those described in the above [Permanent magnet manufacturing method].
- FIG. 9 is a photograph showing the external shape of a 7.35 g permanent magnet with the largest filling amount among the permanent magnets manufactured in the examples and comparative examples.
- the permanent magnet according to the embodiment can be densely sintered into a cylindrical shape without deformation such as warpage or dent even when the filling amount into the sintering mold 46 is large.
- a part of the molded body flows into the inflow holes 50 formed in the upper punch 48 and the lower punch 49 during SPS sintering, so that the pressure value to the molded body becomes higher than necessary. It can be seen that this can be prevented.
- the permanent magnet of the comparative example it can be seen that the pressurization value at the time of SPS sintering becomes higher than necessary due to the excessive filling amount, and the outer shell portion is defective.
- FIG. 10 is a diagram showing a comparison result comparing the shapes of a plurality of permanent magnets manufactured simultaneously in the example and the comparative example.
- FIG. 11 is a diagram showing variation (specific gravity) in the shape of a plurality of permanent magnets manufactured simultaneously in the example.
- the sintered permanent magnets can be densely sintered without any difference in specific gravity regardless of the filling amount of the sintering mold.
- the magnet raw material is pulverized into magnet powder
- the pulverized magnet powder is molded
- the molded magnet powder After the compact 40 is calcined, the permanent magnet 1 is manufactured by SPS sintering using the SPS sintering apparatus 45. Further, the sintering die 46 of the SPS sintering apparatus 45 is formed with an inflow hole 50 into which a part of the pressed compact 40 flows in at least one direction.
- the uniformity of the shape of the permanent magnet 1 can be ensured. Further, even when the filling amount into the sintering mold 46 becomes excessive, the pressure value applied to the molded body does not become higher than necessary, and there is no possibility that defects or the like occur during sintering. Moreover, since the SPS sintering apparatus 45 includes a plurality of sintering dies 46 and simultaneously pressurizes and sintering the plurality of molded bodies 40, the production efficiency of the permanent magnets can be further improved. In addition, it is possible to prevent variation in shape between the permanent magnets sintered at the same time.
- the inflow hole 50 is a hole having a diameter of 1 mm to 5 mm, by making the inflow hole 50 in an appropriate shape, pressure sintering can be performed appropriately, and permanent after the sintering. It is possible to maintain the effect of the uniformity of the shape of the magnet. Further, since the inflow hole 50 is provided on the surface facing the pressing direction when performing pressure sintering, it is possible to further improve the effect of the uniformity of the shape, and the permanent magnet after sintering. Removal from the sintering mold can be easily performed.
- the step of sintering the compact 40 by pressure sintering since sintering is performed by uniaxial pressure sintering, the shrinkage of the permanent magnet due to the sintering becomes uniform, so that the sintered permanent magnet warps. It is possible to prevent deformation such as dents and dents. Further, in the step of sintering the compact 40 by pressure sintering, since sintering is performed by electric current sintering, rapid temperature increase / cooling is possible, and sintering can be performed in a low temperature range. As a result, it is possible to shorten the temperature rise and holding time in the sintering process, and it is possible to produce a dense sintered body that suppresses the grain growth of the magnet particles.
- a permanent magnet is composed of a magnet obtained by mixing magnet powder and a binder and sintering a molded green sheet, so deformation due to sintering becomes uniform and deformation such as warpage and dent after sintering occurs.
- pressure unevenness during pressing is eliminated, there is no need to perform post-sintering correction processing, which has been conventionally performed, and the manufacturing process can be simplified.
- a permanent magnet can be formed with high dimensional accuracy. As a result, it becomes possible to further improve the uniformity of the shape of the permanent magnet after sintering by combining with sintering by a pressure sintering apparatus having an inflow hole.
- the pulverization conditions, kneading conditions, calcination conditions, sintering conditions, etc. of the magnet powder are not limited to the conditions described in the above examples.
- the magnet raw material is pulverized by wet pulverization using a bead mill, but may be pulverized by dry pulverization using a jet mill.
- the green sheet is formed by the slot die method, but other methods (for example, calendar roll method, comma coating method, extrusion molding, injection molding, mold molding, doctor blade method, etc.) can be used. It may be used to form a green sheet. Moreover, it is good also as producing a green sheet by producing
- a hydrogen atmosphere for example, a nitrogen atmosphere, a He atmosphere, or an Ar atmosphere.
- the calcination treatment may be omitted. Even in that case, the binder is thermally decomposed during the sintering, and a certain decarburizing effect can be expected.
- resin long chain hydrocarbon or fatty acid methyl ester is used as the binder, but other materials may be used.
- the permanent magnet may be manufactured by calcining and sintering a molded body formed by molding other than green sheet molding (for example, compaction molding). Even in that case, the effect of improving the shape uniformity of the permanent magnet by pressure sintering can be expected.
- the heating process and magnetic field orientation process of the green sheet 14 will be performed simultaneously, even if it performs a magnetic field orientation process after performing a heating process and before the green sheet 14 solidifies. good. Further, when the magnetic field orientation is performed before the coated green sheet 14 is solidified (that is, the green sheet 14 is already softened without performing the heating process), the heating process may be omitted. .
- the coating process by the slot die method, the heating process, and the magnetic field orientation process are performed by a series of continuous processes, but may be configured not to be performed by the continuous processes. Moreover, it is good also as performing by the process which divided
- the coated green sheet 14 can be cut to a predetermined length, and the green sheet 14 in a stationary state can be configured to perform magnetic field orientation by heating and applying a magnetic field. is there.
- the Nd—Fe—B type magnet is described as an example, but other magnets (for example, a cobalt magnet, an alnico magnet, a ferrite magnet, etc.) may be used.
- the Nd component is larger than the stoichiometric composition in the present invention, but it may be stoichiometric.
- the present invention can be applied not only to anisotropic magnets but also to isotropic magnets. In that case, the magnetic field orientation process for the green sheet 14 can be omitted.
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Abstract
Description
特に、加圧焼結の焼結型に充填される充填量にバラツキが有ったとしても、永久磁石の形状の均一性を確保することができる。また、焼結型への充填量が多くなり過ぎた場合であっても、成形体への加圧値が必要以上に高くなることなく、焼結時に欠損等が生じる虞もない。
特に、加圧焼結の焼結型に充填される充填量にバラツキが有ったとしても、永久磁石の形状の均一性を確保することができる。また、焼結型への充填量が多くなり過ぎた場合であっても、成形体への加圧値が必要以上に高くなることなく、焼結時に欠損等が生じる虞もない。
特に、加圧焼結の焼結型に充填される充填量にバラツキが有ったとしても、永久磁石の形状の均一性を確保することができる。また、焼結型への充填量が多くなり過ぎた場合であっても、成形体への加圧値が必要以上に高くなることなく、焼結時に欠損等が生じる虞もない。
先ず、本発明に係る永久磁石1の構成について説明する。図1は本発明に係る永久磁石1を示した全体図である。尚、図1に示す永久磁石1は扇型形状を備えるが、永久磁石1の形状は打ち抜き形状によって変化する。
本発明に係る永久磁石1はNd-Fe-B系の異方性磁石である。尚、各成分の含有量はNd:27~40wt%、B:0.8~2wt%、Fe(電解鉄):60~70wt%とする。また、磁気特性向上の為、Dy、Tb、Co、Cu、Al、Si、Ga、Nb、V、Pr、Mo、Zr、Ta、Ti、W、Ag、Bi、Zn、Mg等の他元素を少量含んでも良い。図1は本実施形態に係る永久磁石1を示した全体図である。
更に、バインダーに樹脂を用いる場合には、構造中に酸素原子を含まず、且つ解重合性のあるポリマーを用いるのが好ましい。また、後述のようにホットメルト成形によりグリーンシートを成形する場合には、成形されたグリーンシートを加熱して軟化した状態で磁場配向を行う為に、熱可塑性樹脂が用いられる。具体的には以下の一般式(1)に示されるモノマーから選ばれる1種又は2種以上の重合体又は共重合体からなるポリマーが該当する。
尚、バインダーに用いる樹脂としては、磁場配向を適切に行う為に250℃以下で軟化する熱可塑性樹脂、より具体的にはガラス転移点又は融点が250℃以下の熱可塑性樹脂を用いることが望ましい。
次に、本発明に係る永久磁石1の製造方法について図2を用いて説明する。図2は本実施形態に係る永久磁石1の製造工程を示した説明図である。
先ず、ビーズミル11等で微粉砕された磁石粉末にバインダーを混合することにより、磁石粉末とバインダーからなる粉末状の混合物(コンパウンド)12を作製する。ここで、バインダーとしては、上述したように樹脂や長鎖炭化水素や脂肪酸メチルエステルやそれらの混合物等が用いられる。例えば、樹脂を用いる場合には構造中に酸素原子を含まず、且つ解重合性のあるポリマーからなる熱可塑性樹脂を用い、一方、長鎖炭化水素を用いる場合には、室温で固体、室温以上で液体である長鎖飽和炭化水素(長鎖アルカン)を用いるのが好ましい。また、脂肪酸メチルエステルを用いる場合には、ステアリン酸メチルやドコサン酸メチル等を用いるのが好ましい。また、バインダーの添加量は、上述したように添加後のコンパウンド12における磁石粉末とバインダーの合計量に対するバインダーの比率が、1wt%~40wt%、より好ましくは2wt%~30wt%、更に好ましくは3wt%~20wt%となる量とする。尚、バインダーの添加は、窒素ガス、Arガス、Heガスなど不活性ガスからなる雰囲気で行う。尚、磁石粉末とバインダーとの混合は、例えば有機溶媒に磁石粉末とバインダーとをそれぞれ投入し、攪拌機で攪拌することにより行う。そして、攪拌後に磁石粉末とバインダーとを含む有機溶媒を加熱して有機溶媒を気化させることにより、コンパウンド12を抽出する。また、磁石粉末とバインダーとの混合は、窒素ガス、Arガス、Heガスなど不活性ガスからなる雰囲気で行うことが望ましい。また、特に磁石粉末を湿式法で粉砕した場合においては、粉砕に用いた有機溶媒から磁石粉末を取り出すことなくバインダーを有機溶媒中に添加して混練し、その後に有機溶媒を揮発させて後述のコンパウンド12を得る構成としても良い。
図3に示すようにスロットダイ方式に用いられるダイ15は、ブロック16、17を互いに重ね合わせることにより形成されており、ブロック16、17との間の間隙によってスリット18やキャビティ(液溜まり)19を形成する。キャビティ19はブロック17に設けられた供給口20に連通される。そして、供給口20はギアポンプ(図示せず)等によって構成される塗布液の供給系へと接続されており、キャビティ19には供給口20を介して、計量された流体状のコンパウンド12が定量ポンプ等により供給される。更に、キャビティ19に供給された流体状のコンパウンド12はスリット18へ送液されて単位時間一定量で幅方向に均一な圧力でスリット18の吐出口21から予め設定された塗布幅により吐出される。一方で、支持基材13はコーティングロール22の回転に伴って予め設定された速度で連続搬送される。その結果、吐出した流体状のコンパウンド12が支持基材13に対して所定厚さで塗布され、その後、放熱して凝固することにより支持基材13上に長尺シート状のグリーンシート14が成形される。
また、磁場配向した後に行うグリーンシート14の放熱及び凝固は、搬送状態で行うことが好ましい。それによって、製造工程をより効率化することが可能となる。
図6に示すように、加熱装置37は発熱体となる平板部材38の内部に略U字型の空洞39を形成し、空洞39内に所定温度(例えば100~300℃)に加熱された熱媒体であるシリコーンオイルを循環させる構成とする。そして、図4に示すホットプレート26の代わりに、加熱装置37をソレノイド25内においてグリーンシート14に対して上下一対に配置する。それによって、連続搬送されるグリーンシート14を、熱媒体により発熱された平板部材38を介して加熱し、軟化させる。尚、平板部材38はグリーンシート14に対して当接させても良いし、所定間隔離間させて配置しても良い。そして、軟化したグリーンシート14の周囲に配置されたソレノイド25によって、グリーンシート14の面内方向且つ長さ方向(図4の矢印27方向)に対して磁場が印加され、グリーンシート14に対して適切に均一な磁場を配向させることが可能となる。尚、図6に示すような熱媒体を用いた加熱装置37では、一般的なホットプレート26のように内部に電熱線を有さないので、磁場中に配置した場合であってもローレンツ力によって電熱線が振動したり切断される虞が無く、適切にグリーンシート14の加熱を行うことが可能となる。また、電流による制御を行う場合には、電源のON又はOFFで電熱線が振動することにより疲労破壊の原因となる問題が有るが、熱媒体を熱源とした加熱装置37を用いることによって、そのような問題を解消することが可能となる。
また、特に磁石原料を有機溶媒中で湿式粉砕により粉砕した場合には、有機溶媒を構成する有機化合物の熱分解温度且つバインダー分解温度で仮焼処理を行う。それによって、残留した有機溶媒についても除去することが可能となる。有機化合物の熱分解温度については、用いる有機溶媒の種類によって決定されるが、上記バインダー分解温度であれば基本的に有機化合物の熱分解についても行うことが可能となる。
図7に示すようにSPS焼結装置45は複数(図7では9個)の焼結型46を備え、真空チャンパー(図示せず)内に設置される。図7及び図8に示すように各焼結型46は、円筒形状の穴が形成されたグラファイト製の本体部47と、本体部47に形成された円筒形状の穴の上下に配置される同じくグラファイト製の上部パンチ48と下部パンチ49とから構成される。そして、本体部47と上部パンチ48と下部パンチ49とにより形成される円筒形状の空間部にそれぞれ成形体40が設置される。また、上部パンチ48には、加圧された成形体40の一部が流入する為の流入孔50が形成される。そして、流入孔50を形成することによって、焼結前の成形体40の高さや体積にバラツキがあったとしても、加圧時に流入孔50に成形体40の一部が流入することによって、そのバラツキを微調整することが可能となる。その結果、加圧焼結した後の永久磁石1の形状の均一性を向上させることが可能となる。特に、図7に示すように複数の成形体40の加圧焼結を同時に行う場合には、同時に焼結を行った複数の永久磁石1の形状の均一性を向上させることが可能となる。尚、流入孔50は加圧焼結を行う際の加圧方向に対向する面(例えば上部パンチ48や下部パンチ49)に設けることが望ましいが、それ以外の方向(例えば本体部47)に設けるようにしても良い。また、流入孔50は複数箇所に設けても良い。また、流入孔50の大きさは特に限定されないが、大きすぎると適切に加圧焼結できなくなり、小さすぎると上記均一性の向上の効果を得られない。従って、直径1mm~5mmの範囲とすることが望ましい。また、流入孔50は焼結型46の外部まで貫通させた孔であっても良いし、貫通させない孔であっても良い。
尚、具体的な焼結条件を以下に示す。
加圧値:1MPa
焼結温度:940℃まで10℃/分で上昇させ、5分保持
雰囲気:数Pa以下の真空雰囲気
(実施例)
実施例はNd-Fe-B系磁石であり、合金組成はwt%でNd/Fe/B=32.7/65.96/1.34とする。また、バインダーとしてはポリイソブチレン(PIB)を用いた。また、加熱溶融したコンパウンドをスロットダイ方式により基材に塗工してグリーンシートを成形した。また、成形したグリーンシートを200℃に加熱したホットプレートにより5分間加熱するとともに、磁場配向は、グリーンシートに対して面内方向且つ長さ方向に12Tの磁場を印加することにより行った。そして、磁場配向後に所望の形状に打ち抜いたグリーンシートを水素雰囲気で仮焼し、その後、SPS焼結(加圧値:1MPa、焼結温度:940℃まで10℃/分で上昇させ、5分保持)により焼結した。また、SPS焼結は図7に示すように複数個の焼結型46を備えたSPS焼結装置45を用い、複数の成形体に対して同時に焼結を行い、複数個の永久磁石を得た。尚、同時に焼結対象となる複数の成形体は、磁石原料の充填量がそれぞれ僅かに異なる(具体的には6.65g、6.86g、7.14g、7.35gの4パターン)ように成形した。流入孔50としては上部パンチ48及び下部パンチ49に対してそれぞれ直径2mmの流入孔50を形成した。尚、他の工程は上述した[永久磁石の製造方法]と同様の工程とする。
流入孔50が形成されていないSPS焼結装置45を用いてグリーンシートを焼結することにより永久磁石を製造した。他の条件は実施例と同様である。
ここで、図9は実施例と比較例において製造された永久磁石の内、充填量が最も多い7.35gの永久磁石の外観形状をそれぞれ示した写真である。図9に示すように実施例の永久磁石は、焼結型46への充填量が多い場合であっても反りや凹みなどの変形が生じることなく、円筒形状に緻密に焼結することできていることが分かる。即ち、実施例ではSPS焼結時に、上部パンチ48や下部パンチ49に形成された流入孔50へと成形体の一部が流入することによって成形体への加圧値が必要以上に高くなることを防止できていることが分かる。
一方、比較例の永久磁石は、充填量が多すぎることによってSPS焼結時の加圧値が必要以上に高くなり、外殻部分において欠損が生じていることが分かる。
図10に示すように、流入孔50を形成したSPS焼結装置45で焼結を行った実施例では、焼結後の複数の永久磁石間において大きな形状のバラツキは生じなかった。具体的には、図11に示すように、焼結型への充填量の大小に関わらず焼結後の永久磁石は比重に差が無く、緻密に焼結できていることが分かる。即ち、実施例ではSPS焼結時に、上部パンチ48や下部パンチ49に形成された流入孔50へと成形体の一部が流入することによって成形体の形状や密度が均一化されることが分かる。
一方、流入孔50の無いSPS焼結装置45で焼結を行った比較例では、焼結後の複数の永久磁石間において大きな形状のバラツキが生じた。
特に、SPS焼結装置45の焼結型46に充填される充填量にバラツキが有ったとしても、永久磁石1の形状の均一性を確保することができる。また、焼結型46への充填量が多くなり過ぎた場合であっても、成形体への加圧値が必要以上に高くなることなく、焼結時に欠損等が生じる虞もない。
また、SPS焼結装置45は複数の焼結型46を備え、複数個の成形体40を同時に加圧焼結するので、永久磁石の生産効率を更に向上させることが可能となる。また、同時に焼結した永久磁石間で形状のバラツキが生じることを防止することが可能となる。
また、流入孔50を直径1mm~5mmの孔とするので、流入孔50を適切な形状とすることで、加圧焼結を適切に行わせることが可能となるとともに、上記焼結後の永久磁石における形状の均一性の効果についても保持することが可能となる。
また、流入孔50は加圧焼結を行う際の加圧方向に対向する面に設けられるので、形状の均一性の効果をより向上させることが可能となるとともに、焼結後の永久磁石の焼結型からの取り外しについても容易に行うことができる。
また、成形体40を加圧焼結により焼結する工程では、一軸加圧焼結により焼結するので、焼結による永久磁石の収縮が均一となることにより、焼結後の永久磁石において反りや凹みなどの変形が生じることを防止できる。
また、成形体40を加圧焼結により焼結する工程では、通電焼結により焼結するので、急速昇温・冷却が可能となり、また、低い温度域で焼結することが可能となる。その結果、焼結工程での昇温・保持時間を短縮でき、磁石粒子の粒成長を抑制した緻密な焼結体の作製が可能となる。
また、磁石粉末とバインダーとを混合し、成形したグリーンシートを焼結した磁石により永久磁石を構成するので、焼結による収縮が均一となることにより焼結後の反りや凹みなどの変形が生じず、また、プレス時の圧力むらが無くなることから、従来行っていた焼結後の修正加工をする必要がなく、製造工程を簡略化することができる。それにより、高い寸法精度で永久磁石を成形可能となる。その結果、流入孔を備える加圧焼結装置による焼結と組み合わせることにより、焼結後の永久磁石の形状の均一性を更に向上させることが可能となる。
例えば、磁石粉末の粉砕条件、混練条件、仮焼条件、焼結条件などは上記実施例に記載した条件に限られるものではない。例えば、上記実施例ではビーズミルによる湿式粉砕により磁石原料を粉砕しているが、ジェットミルを用いた乾式粉砕により粉砕することとしても良い。また、上記実施例では、スロットダイ方式によりグリーンシートを形成しているが、他の方式(例えばカレンダーロール方式、コンマ塗工方式、押出成型、射出成型、金型成型、ドクターブレード方式等)を用いてグリーンシートを形成しても良い。また、有機溶媒に磁石粉末やバインダーを混合したスラリーを生成し、その後に生成したスラリーをシート状に成形することによってグリーンシートを作成することとしても良い。その場合にはバインダーとして熱可塑性樹脂以外を用いることも可能である。また、仮焼を行う際の雰囲気は非酸化性雰囲気であれば水素雰囲気以外(例えば窒素雰囲気、He雰囲気等、Ar雰囲気等)で行っても良い。
11 ビーズミル
12 コンパウンド
13 支持基材
14 グリーンシート
15 ダイ
25 ソレノイド
26 ホットプレート
37 加熱装置
40 成形体
45 SPS焼結装置
46 焼結型
47 本体部
48 上部パンチ
49 下部パンチ
50 流入孔
Claims (15)
- 磁石原料を磁石粉末に粉砕する工程と、
前記粉砕された磁石粉末を成形体に成形する工程と、
前記成形体を加圧焼結装置の焼結型に設置する工程と、
前記加圧焼結装置の焼結型に設置された前記成形体を加圧焼結により焼結する工程と、を有し、
前記加圧焼結装置の焼結型は少なくとも一方向に対して、加圧された前記成形体の一部が流入する流入孔が形成されることを特徴とする希土類永久磁石の製造方法。 - 前記加圧焼結装置は複数の焼結型を備え、
複数個の前記成形体を同時に加圧焼結することを特徴とする請求項1に記載の希土類永久磁石の製造方法。 - 前記流入孔は、直径1mm~5mmの孔であることを特徴とする請求項1に記載の希土類永久磁石の製造方法。
- 前記流入孔は、加圧焼結を行う際の加圧方向に対向する面に設けられることを特徴とする請求項1に記載の希土類永久磁石の製造方法。
- 前記成形体を加圧焼結する工程では、一軸加圧焼結により焼結することを特徴とする請求項1に記載の希土類永久磁石の製造方法。
- 前記成形体を加圧焼結する工程では、通電焼結により焼結することを特徴とする請求項1に記載の希土類永久磁石の製造方法。
- 前記磁石粉末を成形体に成形する工程では、
前記粉砕された磁石粉末とバインダーとが混合された混合物を生成し、
前記混合物をシート状に成形することにより前記成形体としてグリーンシートを作製することを特徴とする請求項1乃至請求項6のいずれかに記載の希土類永久磁石の製造方法。 - 磁石粉末に粉砕された磁石原料を成形した成形体を、加圧焼結装置の焼結型に設置して加圧焼結により焼結する希土類永久磁石の製造装置であって、
前記加圧焼結装置の焼結型は少なくとも一方向に対して、加圧された前記成形体の一部が流入する流入孔が形成されることを特徴とする希土類永久磁石の製造装置。 - 前記加圧焼結装置は複数の焼結型を備え、
複数個の前記成形体を同時に加圧焼結することを特徴とする請求項8に記載の希土類永久磁石の製造装置。 - 前記流入孔は、直径1mm~5mmの孔であることを特徴とする請求項8に記載の希土類永久磁石の製造装置。
- 前記流入孔は、加圧焼結を行う際の加圧方向に対向する面に設けられることを特徴とする請求項8に記載の希土類永久磁石の製造装置。
- 前記成形体を加圧焼結する際に、一軸加圧焼結により焼結することを特徴とする請求項8に記載の希土類永久磁石の製造装置。
- 前記成形体を加圧焼結する際に、通電焼結により焼結することを特徴とする請求項8に記載の希土類永久磁石の製造装置。
- 前記成形体は、前記粉砕された磁石粉末とバインダーとが混合された混合物をシート状に成形したグリーンシートであることを特徴とする請求項8乃至請求項13のいずれかに記載の希土類永久磁石の製造装置。
- 磁石原料を磁石粉末に粉砕する工程と、
前記粉砕された磁石粉末を成形体に成形する工程と、
前記成形体を加圧焼結装置の焼結型に設置する工程と、
前記加圧焼結装置の焼結型に設置された前記成形体を加圧焼結により焼結する工程と、により製造され、
前記加圧焼結装置の焼結型は少なくとも一方向に対して、加圧された前記成形体の一部が流入する流入孔が形成されることを特徴とする希土類永久磁石。
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Publication number | Publication date |
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JP5411956B2 (ja) | 2014-02-12 |
KR101601583B1 (ko) | 2016-03-08 |
EP2827349A1 (en) | 2015-01-21 |
US10014107B2 (en) | 2018-07-03 |
KR20140132403A (ko) | 2014-11-17 |
TWI598902B (zh) | 2017-09-11 |
CN104160462A (zh) | 2014-11-19 |
EP2827349B1 (en) | 2017-06-21 |
JP2013191605A (ja) | 2013-09-26 |
EP2827349A4 (en) | 2015-03-11 |
US20150084727A1 (en) | 2015-03-26 |
TW201346956A (zh) | 2013-11-16 |
CN104160462B (zh) | 2016-10-19 |
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