WO2009104640A1 - 永久磁石の製造方法及び永久磁石 - Google Patents
永久磁石の製造方法及び永久磁石 Download PDFInfo
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- WO2009104640A1 WO2009104640A1 PCT/JP2009/052789 JP2009052789W WO2009104640A1 WO 2009104640 A1 WO2009104640 A1 WO 2009104640A1 JP 2009052789 W JP2009052789 W JP 2009052789W WO 2009104640 A1 WO2009104640 A1 WO 2009104640A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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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
- H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets
Definitions
- the present invention relates to a method for producing a permanent magnet, and in particular, Dy and Tb are diffused in the crystal grain boundary and / or crystal grain boundary phase of an Nd—Fe—B based sintered magnet, and a protective film by Ni plating, etc.
- the present invention relates to a method of manufacturing a permanent magnet having a high magnetic property that does not require a magnetic field and a permanent magnet manufactured by this manufacturing method.
- Nd-Fe-B based sintered magnets can be manufactured at low cost by being made of a combination of iron and Nd and B elements that are inexpensive and abundant in resources and can be stably supplied.
- neodymium magnets since it has high magnetic properties (the maximum energy product is about 10 times that of ferrite magnets), it is used in various products such as electronic equipment, and is also used in motors and generators for hybrid cars. is increasing.
- Such sintered magnets are mainly produced by a powder metallurgy method.
- Nd, Fe, and B are blended in a predetermined composition ratio.
- a rare earth element such as dysprosium is mixed to increase the coercive force.
- the alloy raw material is prepared by melting and casting, for example, coarsely pulverized by, for example, a hydrogen pulverization step, and then finely pulverized by, for example, a jet mill pulverization step (pulverization step) to obtain alloy raw material powder.
- the obtained alloy raw material powder is oriented in a magnetic field (magnetic field orientation), and compression molded in a state where a magnetic field is applied to obtain a compact.
- the compact is sintered under predetermined conditions to produce a sintered magnet (see Patent Document 1).
- the sintered magnet is mainly composed of iron and Nd
- the sintered magnet is easily oxidized.
- magnetic characteristics such as coercive force deteriorate.
- a protective film is formed on the surface of a sintered magnet by Ni plating or the like as a rust prevention measure to improve corrosion resistance and weather resistance.
- the sintered magnet is reacted for transporting the sintered magnet in order to perform a treatment such as Ni plating after the sintering, and the handling thereof is troublesome.
- the protective film is formed through a plurality of processing steps such as surface cleaning and Ni plating, the productivity is poor.
- the sintered magnet may be machined into a predetermined shape in order to finish it as a product.
- this processing may cause defects (cracks, etc.) or strains in the crystal grains of the sintered magnet.
- the magnetic properties are remarkably deteriorated. Therefore, it is necessary to improve or recover the magnetization and the coercive force depending on the use as a product.
- the present invention provides a method for producing a permanent magnet that can effectively improve or recover magnetic properties such as coercive force, and can produce a permanent magnet having corrosion resistance and weather resistance with high mass productivity and low cost. It is another object of the present invention to provide a permanent magnet.
- a method for manufacturing a permanent magnet includes heating an iron-boron-rare earth sintered magnet in a processing chamber, and performing the same or other processing.
- a metal evaporation material containing at least one of Dy and Tb disposed in the chamber is evaporated, and an inert gas is introduced into the processing chamber in which the sintered magnet is disposed while the metal evaporation material is evaporated, and
- the metal atoms are attached, and before the thin film composed of the attached metal atoms is formed, the metal atoms are The first step of diffusing into the crystal grain boundary and / or the grain boundary phase of the sintered magnet, and the process while cooling the process chamber by introducing a cooling gas into the process chamber in which the sintered magnet is disposed.
- the reaction gas is introduced into the chamber and the surface of the sintered magnet Characterized in that it comprises
- the crystal grain boundary and / or the grain boundary phase of the sintered magnet has a magnetic anisotropy of 4f electrons larger than Nd and has a negative Stevens factor similar to Nd.
- Dy and Tb that greatly improve the magnetocrystalline anisotropy of the main phase are uniformly introduced (vacuum vapor treatment).
- the partial pressure of the inert gas is controlled so that Dy and Tb diffuse into the grain boundaries and the grain boundary phase before the thin films of Dy and Tb are formed on the surface of the sintered magnet.
- the surface of the sintered magnet is not deteriorated, and excessive diffusion of Dy and Tb in the grain boundary in the region close to the surface of the sintered magnet is suppressed.
- the Dy rich phase is added to the grain boundary phase. (Phase containing Dy in the range of 5 to 80%), and Dy diffuses only near the surface of the crystal grains, thereby effectively improving or recovering the magnetization and coercive force, and finishing. The thing which does not need processing is obtained.
- the rich phase of Dy and Tb having extremely high corrosion resistance and weather resistance compared to Nd is formed inside the cracks of the crystal grains near the surface and the grain boundary phase.
- reactive gas was introduced during cooling, and the surface of the sintered magnet was covered with a reactive film different from the natural oxide film, etc. to passivate, so a protective film such as Ni plating was added in a further separate process. Without being formed, an easily handled permanent magnet having extremely strong corrosion resistance and weather resistance can be obtained. As a result, magnetic properties such as coercive force can be effectively improved or recovered, and permanent magnets having corrosion resistance and weather resistance can be manufactured with high mass productivity and low cost.
- the reaction gas is selected from water vapor gas, oxygen gas, nitrogen gas, carbon dioxide gas, sulfurous acid gas, nitrous oxide gas, ammonia gas, acetylene gas, propane gas, budan gas, and phosphine gas. May be used.
- the productivity is increased while improving the productivity.
- the magnetic properties of the magnet may be further improved.
- the method for manufacturing a permanent magnet includes heating an iron-boron-rare earth sintered magnet in a processing chamber, Evaporating a metal evaporation material including at least one of Dy and Tb disposed in the processing chamber, and introducing an inert gas into the processing chamber in which the sintered magnet is disposed while the metal evaporation material is evaporated;
- the metal atoms are attached by controlling the partial pressure of the inert gas to adjust the supply amount of the evaporated metal atoms to the surface of the sintered magnet, and before the thin film composed of the attached metal atoms is formed, the metal
- a second step of forming a thin film It is characterized in.
- Dy and Tb are uniformly introduced into the crystal grain boundaries and / or crystal grain boundary phases of the sintered magnet, as in the first embodiment.
- the metal evaporation material is evaporated, and the evaporated metal atoms are attached to the surface of the sintered magnet to form a thin film made of the metal atoms.
- the surface of the sintered magnet is covered with a Dy film or Tb film having extremely high corrosion resistance and weather resistance as compared with Nd, and a permanent magnet with further improved corrosion resistance and weather resistance can be obtained.
- the Dy film is formed after Dy and Tb are uniformly diffused in the crystal grain boundary and / or the grain boundary phase of the sintered magnet, the magnetic properties of the improved or recovered permanent magnet deteriorate. It is not a thing.
- the rich phase of Dy and Tb having extremely high corrosion resistance and weather resistance compared to Nd is formed inside the cracks of the crystal grains near the surface and the grain boundary phase.
- a protective film such as Ni plating is not formed in a further separate process, and it is a permanent material that has extremely strong corrosion resistance and weather resistance and is easy to handle. A magnet is obtained. As a result, magnetic properties such as coercive force can be effectively improved or recovered, and permanent magnets having corrosion resistance and weather resistance can be manufactured with high mass productivity and low cost.
- the second step may be performed by evacuating the processing chamber. That is, a thin film of Dy or Tb is formed by changing the vapor pressure of the metal evaporation material to increase the supply amount of metal atoms evaporated on the magnet surface.
- a thin film made of a metal evaporation material can be easily realized in the same processing chamber, and the first step and the second step can be continuously performed, so that productivity can be further improved.
- the magnetic properties of the permanent magnet may be further improved.
- the sintered metal is used to prevent the metal evaporation material from directly attaching to the sintered magnet when the metal evaporation material is evaporated.
- the magnet and the metal evaporation material are arranged in the same processing chamber, it is preferable to arrange the sintered magnet and the metal evaporation material so as not to contact each other.
- the permanent magnet of this invention is a permanent magnet produced using the manufacturing method of the permanent magnet of any one of Claim 1 thru
- the said metal atom is The sintered magnet diffuses in the grain boundaries and / or grain boundary phases of the sintered magnet with a distribution in which the concentration decreases from the magnet surface toward the center thereof, and at least one metal atom of Dy and Tb on the surface. Exists uniformly (in other words, there is no region enriched with metal atoms of Dy or Tb on the surface) and the oxygen concentration is uniform (in other words, the portion where the oxygen concentration is high is locally And the entire surface of the sintered magnet is covered with a reaction film (the surface is passivated).
- the Nd—Fe—B based sintered magnet S as a starting material is manufactured as follows. That is, industrial pure iron, metallic neodymium, and low carbon ferroboron are blended and dissolved using a vacuum induction furnace so that Fe, Nd, and B have a predetermined composition ratio, and then quenched by a rapid cooling method such as a strip casting method. First, an alloy raw material of 05 mm to 0.5 mm is prepared.
- an alloy raw material having a thickness of about 5 mm to 10 mm may be produced by a centrifugal casting method, and Dy, Tb, Co, Cu, Nb, Zr, Al, Ga, etc. may be added at the time of blending. .
- the total content of rare earth elements is increased to more than 28.5%, and an ingot that does not produce ⁇ iron is obtained.
- the produced alloy raw material is coarsely pulverized by a known hydrogen pulverization step, and then finely pulverized in a nitrogen gas atmosphere by a jet mill pulverization step to obtain an alloy raw material powder having an average particle size of 3 to 10 ⁇ m.
- This alloy raw material powder is compression molded into a predetermined shape in a magnetic field using a known compression molding machine. Then, the molded body taken out from the compression molding machine is stored in a sintering furnace (not shown), and sintered (sintering process) for a predetermined time at a predetermined temperature (for example, 1050 ° C.) in a vacuum. Get.
- the produced primary sintered body is housed in a vacuum heat treatment furnace (not shown) and heated to a predetermined temperature in a vacuum atmosphere.
- the heating temperature is set to 900 ° C. or higher and lower than the sintering temperature.
- the pressure in the furnace is set to a pressure of 10 ⁇ 3 Pa or less. At pressures higher than 10 ⁇ 3 Pa, rare earth elements cannot be evaporated efficiently.
- the vapor pressure of Nd is 10 ⁇ 3 Pa
- the vapor pressure of Fe is 10 ⁇ 5 Pa
- the vapor pressure of B is 10 ⁇ 13 Pa.
- the rare earth elements in the rare earth-rich phase of the primary sintered body evaporate.
- the ratio of the Nd-rich phase is reduced, and the sintered magnet S is produced in which the maximum energy product ((BH) max) and the residual magnetic flux density (Br) exhibiting magnetic characteristics are improved.
- the vacuum vapor processing apparatus 1 includes a vacuum chamber 3 that can be held at a reduced pressure to a predetermined pressure (for example, 1 ⁇ 10 ⁇ 5 Pa) through a vacuum exhaust unit 2 such as a turbo molecular pump, a cryopump, or a diffusion pump.
- a heating means 4 composed of a heat insulating material 41 surrounding a processing box, which will be described later, and a heating element 42 arranged inside the heat insulating material 41.
- the heat insulating material 41 is made of, for example, Mo
- the heating element 42 is an electric heater having a filament (not shown) made of Mo.
- the filament is energized from a power supply (not shown) and is insulated by resistance heating.
- the space 5 surrounded by the material 41 and in which the processing box is installed can be heated.
- a mounting table 6 made of Mo is provided, and at least one processing box 7 can be mounted.
- the processing box 7 includes a rectangular parallelepiped box portion 71 whose upper surface is opened and a lid portion 72 that is detachable from the upper surface of the opened box portion 71.
- a flange 72a bent downward is formed on the outer peripheral edge of the lid portion 72 over the entire circumference.
- the processing chamber 70 has a higher pressure (for example, 5 ⁇ 10 ⁇ 4 Pa) than the vacuum chamber 3. The pressure is reduced to. As a result, the inside of the processing chamber 70 can be appropriately reduced to a predetermined vacuum pressure without the need for additional evacuation means.
- the sintered magnet S and the metal evaporating material v are stacked up and down with a spacer 8 interposed therebetween so that the both are stored.
- the spacer 8 is configured by assembling a plurality of wires 81 (for example, ⁇ 0.1 to 10 mm) in a lattice shape so as to have an area smaller than the transverse cross section of the box portion 71, and the outer peripheral edge portion thereof is substantially perpendicular. Is bent upward. The height of the bent portion is set to be higher than the height of the sintered magnet S to be vacuum-steamed, and a space is secured between the metal evaporation material v installed on the upper side.
- a plurality of sintered magnets S are juxtaposed at equal intervals on the horizontal portion of the spacer 8.
- the metal evaporating material v As the metal evaporating material v, Dy and Tb that greatly improve the magnetocrystalline anisotropy of the main phase, or an alloy in which a metal that further enhances the coercive force such as Nd, Pr, Al, Cu, and Ga is mixed. (The mass ratio of Dy and Tb is 50% or more) is used, and after the above metals are mixed at a predetermined mixing ratio, for example, after being melted in an arc melting furnace, a plate having a predetermined thickness is formed. . In this case, the metal evaporation material v has an area that is supported by the entire upper circumference of the spacer 8 that is bent.
- the spacer 8 which mounted the sintered magnet S is mounted on the upper side, and also in the upper part where the spacer 8 was bent.
- Another plate-shaped metal evaporation material v is installed so as to be supported.
- the metal evaporation material v and the spacer 8 in which a plurality of sintered magnets S are juxtaposed are alternately stacked in a hierarchical manner up to the upper end of the processing box 7. Note that the metal evaporating material v can be omitted because the lid portion 72 is located close to the uppermost spacer 8.
- mass productivity can be increased by increasing the number of sintered magnets S accommodated in one processing box 7 (increasing the loading capacity).
- mass productivity can be increased by increasing the number of sintered magnets S accommodated in one processing box 7 (increasing the loading capacity).
- a so-called sandwich structure in which the upper and lower sides of the sintered magnet S juxtaposed on the spacer 8 (same plane) is sandwiched between the plate-like metal evaporation materials v, all the sintering is performed in the processing chamber 70.
- the metal evaporation material v is located in the vicinity of the magnet S and the metal evaporation material v is evaporated, the evaporated metal atoms are supplied to and adhered to the surface of each sintered magnet S.
- the processing box 7 and the spacer 8 are made of Mo, W, Nb, V, Ta or alloys thereof (including rare earth-added Mo alloys, Ti-added Mo alloys), CaO, Y 2 O 3 , or rare earths. You may make from an oxide, or you may comprise from what formed these materials as the lining film
- the space between the metal evaporation material v and the sintered magnet S is increased.
- the interval is narrowed. If the metal evaporating material v is evaporated in such a state, there is a risk of being strongly influenced by the straightness of the evaporated metal atoms. That is, in the sintered magnet S, metal atoms are likely to locally adhere to the surface facing the metal evaporation material v, and the shadow of the wire 81 on the contact surface of the sintered magnet S with the spacer 8. It becomes difficult to supply Dy and Tb to the portion.
- the obtained permanent magnet M locally has a portion having a high coercive force and a portion having a low coercive force, and as a result, the squareness of the demagnetization curve is impaired.
- the inert gas introduction means has a gas introduction pipe 9 communicating with the space 5 surrounded by the cross-section material 41, and the gas introduction pipe 9 communicates with a gas source of an inert gas via a mass flow controller (not shown). .
- an inert gas such as He, Ar, Ne, Kr, N2 or the like is introduced in a constant amount.
- the introduction amount of the inert gas may be changed during the vacuum steam treatment (initially, the introduction amount of the inert gas is increased and then decreased or the introduction amount of the inert gas is initially reduced. Less, then more, or repeat these).
- the inert gas may be introduced, for example, after the metal evaporating material v starts evaporation or after reaching a set heating temperature, and may be introduced for a predetermined time during or around the set vacuum vapor processing time.
- a valve 10 whose degree of opening and closing can be adjusted is provided in the exhaust pipe leading to the vacuum exhaust means 2 so that the partial pressure of the inert gas in the vacuum chamber 3 can be adjusted. preferable.
- the inert gas introduced into the space 5 is also introduced into the processing box 7.
- the inert gas evaporates in the processing box 7.
- the metal atoms diffused and the amount of metal atoms adhering directly to the surface of the sintered magnet S is reduced and supplied to the surface of the sintered magnet S from a plurality of directions. For this reason, even when the space
- the sintered magnet S and the plate-shaped metal evaporation material v are alternately stacked via the spacer 8, and both are first installed in the box part 71 (Thereby, inside the process chamber 70). And the sintered magnet S and the metal evaporation material v are spaced apart). And after attaching the cover part 72 to the upper surface which the box part 71 opened, the process box 7 is installed on the table 6 in the space 5 enclosed by the heating means 4 in the vacuum chamber 3 (refer FIG. 1).
- the vacuum chamber 3 is evacuated and depressurized until the pressure reaches a predetermined pressure (for example, 1 ⁇ 10 ⁇ 4 Pa) via the vacuum evacuation means 2 (at this time, the processing chamber 70 has, for example, 5 ⁇ 10 ⁇ 3
- a predetermined pressure for example, 1 ⁇ 10 ⁇ 4 Pa
- the heating means 4 is activated to heat the processing chamber 70.
- the Dy in the processing chamber 70 is heated to substantially the same temperature as the processing chamber 70 to start evaporation, and a Dy vapor atmosphere is formed in the processing chamber 70.
- the gas introduction means is operated to introduce the inert gas into the vacuum chamber 3 with a constant introduction amount.
- an inert gas is also introduced into the processing box 7, and the metal atoms evaporated in the processing chamber 70 are diffused by the inert gas.
- the sintered magnets S and Dy are arranged so as not to contact each other, so that Dy does not directly adhere to the sintered magnet S in which the surface Nd-rich phase is melted. Then, the Dy atoms in the Dy vapor atmosphere diffused in the processing box are supplied from a plurality of directions, directly or repeatedly, toward the substantially entire surface of the sintered magnet S heated to substantially the same temperature as Dy. The adhered Dy is uniformly diffused to the crystal grain boundary and / or the grain boundary phase of the sintered magnet S.
- the Dy adhered and deposited on the surface of the sintered magnet S is recrystallized.
- the surface of the permanent magnet M is remarkably deteriorated (the surface roughness is deteriorated and finishing is required), and it adheres to the surface of the sintered magnet S heated to substantially the same temperature during processing.
- the dissolved Dy is dissolved and excessively diffused in the grain boundary in the region close to the surface of the sintered magnet S, so that the magnetic properties cannot be effectively improved or recovered.
- the average composition of the sintered magnet surface S adjacent to the thin film becomes a Dy rich composition.
- the surface of the magnet S is melted (that is, the main phase is melted and the amount of the liquid phase is increased).
- the vicinity of the surface of the sintered magnet S melts and collapses, and the unevenness increases.
- Dy excessively penetrates into the crystal grains together with a large amount of liquid phase, and the maximum energy product and the residual magnetic flux density showing the magnetic characteristics are further lowered.
- the heating means 4 is controlled so that the temperature in the processing chamber 70 is 800 ° C. to 1050 ° C., preferably 850 ° C.
- the temperature was set in the range of 950 ° C. to 950 ° C. (for example, when the processing chamber temperature is 900 ° C. to 1000 ° C., the saturated vapor pressure of Dy is about 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 1 Pa).
- the diffusion rate of Dy atoms adhering to the surface of the sintered magnet S to the grain boundaries and / or grain boundary layers is increased. It becomes slow and cannot be uniformly distributed by diffusing into the crystal grain boundary and / or the grain boundary phase of the sintered magnet before the thin film is formed on the surface of the sintered magnet S.
- the vapor pressure of Dy increases, and there is a risk that Dy atoms in the vapor atmosphere are excessively supplied to the surface of the sintered magnet S.
- Dy diffuses into the crystal grains and when Dy diffuses into the crystal grains, the magnetization in the crystal grains is greatly reduced, so that the maximum energy product and the residual magnetic flux density are further lowered.
- the opening / closing degree of the valve 11 was changed so that the partial pressure of the inert gas introduced into the vacuum chamber 3 was 3 Pa to 50000 Pa.
- the partial pressure of the inert gas introduced into the vacuum chamber 3 was 3 Pa to 50000 Pa.
- Dy and Tb are locally attached to the sintered magnet S, and the squareness of the demagnetization curve is deteriorated.
- the pressure exceeds 50000 Pa evaporation of Dy is suppressed, and the processing time becomes excessively long.
- the partial pressure of an inert gas such as Ar is adjusted to control the evaporation amount of Dy, and by introducing the inert gas, the evaporated Dy atoms are diffused in the processing box 7 to obtain a sintered magnet.
- Dy atoms adhering to the surface of the sintered magnet S are efficiently diffused to the grain boundaries and / or grain boundary phases of the sintered magnet S before being deposited on the surface of the sintered magnet S to form a Dy layer (thin film).
- First step vacuum steam treatment
- the grain boundary phase has a Dy-rich phase (a phase containing Dy in the range of 5 to 80%), and Dy diffuses only near the surface of the crystal grain, effectively improving magnetization and coercivity. Or, it recovers and, in addition, it is excellent in productivity that does not require finishing.
- the metal atoms evaporated in the processing box 7 are diffused and present, and the sintered magnet S is placed on a spacer 8 in which thin wires 81 are assembled in a lattice shape. Even when the distance between the Dy and the Dy is narrow, the evaporated Dy wraps around to the shadowed portion of the wire 81 and adheres. As a result, the presence of locally high coercivity portions and low portions can be suppressed, and the squareness of the demagnetization curve can be prevented from being impaired even when the sintered magnet S is subjected to the above vacuum vapor treatment. High mass productivity can be achieved.
- the operation of the heating unit 4 is stopped and the introduction of the inert gas by the gas introduction unit is temporarily stopped.
- an inert gas is introduced again (for example, 100 kPa), and the evaporation of the metal evaporation material v is stopped. Note that the evaporation may be stopped by increasing only the introduction amount without stopping the introduction of the inert gas.
- the temperature in the processing chamber 70 is temporarily lowered to 500 ° C., for example.
- the heating means 4 is operated again while stopping the introduction of the inert gas and evacuating, so that the temperature in the processing chamber 70 is 450 ° C. to 650 ° C.
- heat treatment is performed for a predetermined time (heat treatment step).
- an inert gas is introduced (for example, Ar is introduced at atmospheric pressure), and the inside of the processing chamber 70 is cooled.
- a cooling fan and a gas circulation path may be provided in the vacuum chamber 3, and the cooling fan may be operated to cool the processing box and thus the magnet in the processing chamber.
- a predetermined reaction gas is added to the inert gas introduced through the gas introduction pipe 9 and introduced.
- the reaction gas is selected from water vapor gas, oxygen gas, nitrogen gas, carbon dioxide gas, sulfurous acid gas, nitrous oxide gas, ammonia gas, acetylene gas, propane gas, budan gas, and phosphine gas.
- the reaction gas has a predetermined time between the temperature of the processing chamber 70 and the temperature at which the Dy adhering to the processing box 7 or the spacer 8 reacts (for example, 100 ° C.) from the heat treatment temperature (450 ° C. to 650 ° C.). Introduced and formed with a film thickness of 1 to 3000 nm (second step: see the lower diagram of FIG. 3).
- the surface of the magnet that has been subjected to the vacuum vapor treatment by the reaction with the reaction gas is covered with the reaction film and passivated, and the permanent magnet M having corrosion resistance and weather resistance is obtained.
- the pressure in the processing chamber 70 is increased, so that heat conduction is improved and the cooling rate in the processing chamber 70 is increased, and furthermore, a cooling process of the sintered magnet is used.
- the processing time can be shortened and the production can be increased.
- the rich phase of Dy having extremely high corrosion resistance and weather resistance as compared with Nd is present inside the cracks of the crystal grains near the surface and the crystal grains.
- the reaction gas was introduced during cooling and the sintered magnet surface was covered with the reaction film to passivate it, so that a protective film such as Ni plating could not be formed in a further separate process.
- a protective film such as Ni plating could not be formed in a further separate process.
- a surface deteriorated layer is formed by performing a heat treatment for diffusion after forming a film of Dy. Therefore, when this surface deteriorated layer is removed by machining, the oxygen content in the vicinity of the magnet surface
- the magnet surface is not a polished surface
- oxygen is present almost evenly in the magnet (the portion where the oxygen concentration is high is locally localized). not exist).
- the entire surface of the sintered magnet S is covered with a reaction film (the surface is passivated).
- the manufacturing method of the Nd—Fe—B-based sintered magnet S as the starting material, the first step, and the vacuum vapor processing apparatus that performs the first step are the same as those in the first embodiment. Detailed description is omitted here.
- the first step and the second step are continuously performed using the above-described vacuum vapor processing apparatus.
- the sintered magnet S and the plate-like metal evaporation material v are alternately stacked via the spacers 8 and installed in the box part 71, and the lid part 72 is placed on the upper surface of the box part 71 that is opened.
- the processing box 7 is set on the table 6 in the space 5 surrounded by the heating means 4 in the vacuum chamber 3 (see FIG. 1).
- the vacuum chamber 3 is evacuated and depressurized until it reaches a predetermined pressure (for example, 1 ⁇ 10 ⁇ 4 Pa) through the vacuum evacuation means 2, and when the vacuum chamber 3 reaches the predetermined pressure, the heating means 4 is activated.
- the processing chamber 70 is heated.
- the Dy in the processing chamber 70 is heated to substantially the same temperature as the processing chamber 70 to start evaporation, and a Dy vapor atmosphere is formed in the processing chamber 70.
- the gas introduction means is operated to introduce the inert gas into the vacuum chamber 3 with a constant introduction amount.
- an inert gas is also introduced into the processing box 7, and the metal atoms evaporated in the processing chamber 70 are diffused by the inert gas.
- the heating means 4 is controlled so that the temperature in the processing chamber 70 is 800 ° C. to 1050 ° C., preferably 850 ° C. to 950 ° C. (For example, when the processing chamber temperature is 900 ° C. to 1000 ° C., the saturated vapor pressure of Dy is about 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 1 Pa). At the same time, the degree of opening and closing of the valve 11 is changed so that the partial pressure of the inert gas introduced into the vacuum chamber 3 becomes 3 Pa to 50000 Pa.
- the partial pressure of an inert gas such as Ar is adjusted to control the evaporation amount of Dy, and the Dy atoms evaporated by the introduction of the inert gas are contained in the processing box 7.
- the diffusion rate is increased by attaching Dy atoms to the entire surface while suppressing the supply amount of Dy atoms to the sintered magnet S and heating the sintered magnet S in a predetermined temperature range.
- the Dy atoms attached to the surface of the sintered magnet S are deposited on the surface of the sintered magnet S to form a Dy layer (thin film), / Or can be efficiently diffused in the grain boundary phase and uniformly distributed (first step (vacuum vapor treatment): see the upper diagram in FIG. 4).
- the inert gas of the inert gas by the gas introduction unit is kept while the heating unit 4 is operated.
- the operation is stopped, and the vacuum chamber 3 and thus the processing chamber 70 is evacuated.
- the pressure in the processing chamber 70 is lowered (5 ⁇ 10 ⁇ 3 Pa)
- the vapor pressure of Dy increases and a large amount of evaporated Dy atoms is supplied to the magnet surface.
- a Dy layer (thin film) having a thickness of 0.1 to 1 ⁇ m is formed on the magnet surface (second step: see the lower diagram in FIG. 4).
- the operation of the heating means 4 is stopped and the vacuum is exhausted.
- an inert gas is introduced again (for example, 100 kPa), and the evaporation of the metal evaporation material v is stopped. Note that evaporation may be stopped by increasing only the introduction amount without stopping the vacuum exhaust.
- the temperature in the processing chamber 70 is temporarily lowered to 500 ° C., for example.
- the heating means 4 is operated again while stopping the introduction of the inert gas and evacuating, so that the temperature in the processing chamber 70 is 450 ° C. to 650 ° C.
- heat treatment is performed (heat treatment step).
- the processing chamber 70 is cooled, and the permanent magnet M manufactured through the first to third steps is taken out from the processing chamber 70 together with the processing box 7.
- the rich phase of Dy having extremely high corrosion resistance and weather resistance compared to Nd is present inside the cracks of the crystal grains near the surface and the grain boundaries.
- a protective film such as Ni plating is not formed in a further separate process.
- an easily handled permanent magnet M having extremely strong corrosion resistance and weather resistance can be obtained.
- magnetic properties such as coercive force can be effectively improved or recovered, and permanent magnets having corrosion resistance and weather resistance can be manufactured with high mass productivity and low cost.
- the spacer 8 is described as an example of a structure in which wires are assembled in a lattice shape.
- the present invention is not limited to this, and the passage of evaporated metal atoms is not limited thereto.
- the spacer 8 may be formed of a so-called expanded metal regardless of its form.
- the processing chamber 70 may be heated in the range of 900 ° C. to 1150 ° C. At a temperature lower than 900 ° C., the vapor pressure that can supply Tb atoms to the surface of the sintered magnet S is not reached. On the other hand, at a temperature exceeding 1150 ° C., Tb is excessively diffused in the crystal grains, thereby reducing the maximum energy product and the residual magnetic flux density.
- a vacuum chamber 3 is provided via a vacuum exhaust means 2. Is reduced to a predetermined pressure (for example, 1 ⁇ 10 ⁇ 5 Pa), and the processing chamber 70 is depressurized to a pressure (for example, 5 ⁇ 10 ⁇ 4 Pa) approximately half an order higher than that of the vacuum chamber 3, and then held for a predetermined time. It may be. At that time, the heating means 4 may be operated to heat the inside of the processing chamber 70 to, for example, 100 ° C. and hold it for a predetermined time.
- a predetermined pressure for example, 1 ⁇ 10 ⁇ 5 Pa
- a pressure for example, 5 ⁇ 10 ⁇ 4 Pa
- the processing unit 7 is configured by attaching the lid 72 to the upper surface of the box 71.
- the processing box 7 is isolated from the vacuum chamber 3, and the vacuum chamber 3 is decompressed.
- the process chamber 70 is not limited to this as long as the process chamber 70 is decompressed.
- the upper surface opening thereof is opened.
- the processing chamber 70 may be sealed in the vacuum chamber 3 and may be configured to be maintained at a predetermined pressure independently of the vacuum chamber 3.
- an evaporation chamber in which only the metal evaporating material v is installed is connected to the processing box via the communication path, and the evaporation chamber is heated separately from the processing chamber to evaporate the metal evaporating material V, and then sintered.
- the magnet S may be supplied.
- the oxygen content of the sintered magnet S is 3000 ppm.
- it is preferably 2000 ppm or less, more preferably 1000 ppm or less.
- Example 1 a permanent magnet M was obtained by performing the first step and the second step on the next sintered magnet S using the vacuum vapor processing apparatus 1 shown in FIG.
- the sintered magnet S a commercially available 40H sintered magnet (composition ratio: 28.5 (Nd + Pr) -3Dy-0.05Co-0.05Cu-0.01Zr-0.05Ga-1.1B-Bal.Fe) was obtained, processed into a 10 ⁇ 10 ⁇ 10 mm cube, and the surface was washed.
- the operation of the heating means 4 was temporarily stopped and the introduction of argon gas was temporarily stopped by the gas introduction means.
- argon gas was reintroduced to atmospheric pressure, and the temperature in the processing chamber 70 was once lowered to, for example, 500 ° C.
- the heating means 4 was actuated again, the temperature in the processing chamber 70 was set to a range of 480 ° C., the processing time was set to 4 hours, and heat treatment was performed.
- a mixed gas in which a reaction gas is added to the argon gas at a predetermined concentration is introduced into the processing chamber up to atmospheric pressure, and the cooling fan provided in the vacuum chamber is operated to circulate the mixed gas in the processing chamber. Then, a reaction film was formed on the surface of the magnet while cooling the magnet until the temperature in the processing chamber dropped to 60 ° C. At this time, the thickness of the reaction film was 10 to 750 nm.
- FIG. 5 shows the average value of the magnetic characteristics (measured by a BH curve tracer) when the above-mentioned vacuum vapor treatment and reaction film formation treatment were performed while changing the kind and concentration of the reaction gas, and the durability test. It is a table
- the sintered magnet before the vacuum vapor treatment is rusted in a short time of 2 hours, whereas the coercive force is improved (24.5 kOe) by applying the vacuum vapor treatment, It can be seen that the time until rust is generated is 10 times or more, and if a reaction film is formed on the magnet surface by introducing a reaction gas during cooling, the time until rust is generated is 100. More than double, depending on the type of gas, 240 times longer It can be seen that the corrosion resistance is improved.
- Example 2 a permanent magnet M was obtained by performing the first step and the second step on the next sintered magnet S using the vacuum vapor processing apparatus 1 shown in FIG.
- the sintered magnet S a commercially available 45H sintered magnet (composition ratio: 25.5 (Nd + Pr + Ho) -3.5Dy-1Co-0.15Cu-0.15Ti-0.05Sn-0.95B-Bal.Fe) was obtained, processed into a 7 ⁇ 7 ⁇ 7 mm cube, and the surface was washed.
- the vacuum chamber 3 was depressurized to 1 Pa while the heating means 4 was operated, and then a Dy film was formed for 0.5 hour. Then, the operation of the heating unit 4 was stopped, and the temperature in the processing chamber 70 was once lowered to 400 ° C., for example. And the heating means 4 was operated again, the temperature in the process chamber 70 was set to 480 degreeC, and the heat processing was performed for 4 hours. Finally, the processing chamber 70 was cooled to room temperature in He gas.
- FIG. 6 shows the average value of the magnetic properties (measured by a BH curve tracer) of the permanent magnet obtained in Example 2 and the results of the durability test (rusting time in a moisture resistance tester (temperature 80 ° C., humidity 90%) ( It is a table
- the Dy film is continuously formed after the vacuum vapor treatment, the time until rust is generated is 180 times longer, and the corrosion resistance is drastically improved. At that time, it can be seen that the magnetic identification such as the coercive force is substantially equivalent as compared with the case where only the vacuum steam treatment is performed. Further, when the thickness of the central flat portion of the Dy film was measured using an electron microscope, it was confirmed that an average Dy film of 0.5 ⁇ m was formed.
- Sectional drawing which shows schematically the vacuum processing apparatus which implements the process of this invention. The perspective view explaining typically loading of the sintered magnet and metal evaporation material to a processing box. Sectional drawing which illustrates typically the cross section of the permanent magnet produced in 1st Embodiment. Sectional drawing which illustrates typically the cross section of the permanent magnet produced by 2nd Embodiment. 2 is a table showing the magnetic characteristics of the permanent magnet produced in Example 1. 6 is a table showing the magnetic characteristics of the permanent magnet produced in Example 2.
- Vacuum steam processing device Vacuum exhaust means 3 Vacuum chamber 4 Heating means 7 Processing box 71 Box 72 Lid 8 Spacer 81 Wire 9 Gas introduction pipe (gas introduction means) S sintered magnet M Permanent magnet v Metal evaporation material
Abstract
Description
2 真空排気手段
3 真空チャンバ
4 加熱手段
7 処理箱
71 箱部
72 蓋部
8 スペーサー
81 線材
9 ガス導入管(ガス導入手段)
S 焼結磁石
M 永久磁石
v 金属蒸発材料
Claims (8)
- 処理室内に鉄-ホウ素-希土類系の焼結磁石を配置して加熱すると共に、同一または他の処理室内に配置したDy、Tbの少なくとも一方を含む金属蒸発材料を蒸発させ、前記金属蒸発材料が蒸発している間で前記焼結磁石が配置された処理室内に不活性ガスを導入し、前記不活性ガスの分圧を制御して蒸発した金属原子の焼結磁石表面への供給量を調節して金属原子を付着させ、前記付着した金属原子からなる薄膜が形成される前に前記金属原子を焼結磁石の結晶粒界及び/または結晶粒界相に拡散させる第1工程と、
前記焼結磁石が配置されている処理室内に冷却ガスを導入して前記処理室を冷却する間で前記処理室に反応ガスを導入し、焼結磁石表面を反応膜で覆って不動態化する第2工程とを含むことを特徴とする永久磁石の製造方法。 - 前記反応ガスとして、水蒸気ガス、酸素ガス、窒素ガス、炭酸ガス、亜硫酸ガス、亜酸化窒素ガス、アンモニアガス、アセチレンガス、プロパンガス、ブダンガス及びホスフィンガスの中から選択されたものを用いることを特徴とする請求項1記載の永久磁石の製造方法。
- 前記第1工程と第2工程との間で、前記第1工程での加熱温度より低い温度で前記焼結磁石に対し熱処理を施す熱処理工程を含むことを特徴とする請求項1または請求項2記載の永久磁石の製造方法。
- 処理室内に鉄-ホウ素-希土類系の焼結磁石を配置して加熱すると共に、同一または他の処理室内に配置したDy、Tbの少なくとも一方を含む金属蒸発材料を蒸発させ、前記金属蒸発材料が蒸発している間で前記焼結磁石が配置された処理室内に不活性ガスを導入し、前記不活性ガスの分圧を制御して蒸発した金属原子の焼結磁石表面への供給量を調節して金属原子を付着させ、前記付着した金属原子からなる薄膜が形成される前に前記金属原子を焼結磁石の結晶粒界及び/または結晶粒界相に拡散させる第1工程と、
前記金属蒸発材料を蒸発させ、蒸発した金属原子を焼結磁石表面に付着させ、前記金属原子からなる薄膜を形成する第2工程とを含むことを特徴とする永久磁石の製造方法。 - 前記焼結磁石を配置した処理室内で第1工程を実施した後に、前記処理室を真空排気することで第2工程を行うことを特徴とする請求項4記載の永久磁石の製造方法。
- 前記第2工程後、前記第1工程での加熱温度より低い温度で前記焼結磁石に対し熱処理を施す熱処理工程を含むことを特徴とする請求項4または請求項5記載の永久磁石の製造方法。
- 前記焼結磁石と金属蒸発材料とを同一の処理室内に配置する場合、焼結磁石及び金属蒸発材料を相互に接触しないように配置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1項に記載の永久磁石の製造方法。
- 請求項1乃至請求項3のいずれに記載の永久磁石の製造方法を用いて作製された永久磁石であって、前記金属原子が焼結磁石の結晶粒界及び/または結晶粒界相に磁石表面からその中心に向かって含有濃度が薄くなる分布を持って拡散していると共に、その表面にDy及びTbの少なくとも一方の金属原子が均一に存在し、かつ、酸素濃度が均一であり、前記焼結磁石表面の全体が反応膜で覆われていることを特徴とする永久磁石。
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JP2011138884A (ja) * | 2009-12-28 | 2011-07-14 | Hitachi Metals Ltd | 表面改質されたR−Fe−B系焼結磁石の製造方法 |
WO2012043061A1 (ja) * | 2010-09-30 | 2012-04-05 | 日立金属株式会社 | R-t-b系焼結磁石の製造方法 |
CN103351832A (zh) * | 2013-07-18 | 2013-10-16 | 东莞市芙蓉化工有限公司 | 一种不含硫元素的聚丙烯酸酯乳液压敏胶及其制备方法 |
JP2018056188A (ja) * | 2016-09-26 | 2018-04-05 | 信越化学工業株式会社 | R−Fe−B系焼結磁石 |
JP2020535311A (ja) * | 2018-02-01 | 2020-12-03 | 福建省長汀金龍希土有限公司Fujian Changting Golden Dragon Rare−Earth Co., Ltd. | 粒界拡散と熱処理を連続的に行う装置及び方法 |
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