EP2801424B1 - Magnetische komponente, darin verwendetes weichmagnetisches metallpulver und herstellungsverfahren dafür - Google Patents

Magnetische komponente, darin verwendetes weichmagnetisches metallpulver und herstellungsverfahren dafür Download PDF

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EP2801424B1
EP2801424B1 EP13848104.9A EP13848104A EP2801424B1 EP 2801424 B1 EP2801424 B1 EP 2801424B1 EP 13848104 A EP13848104 A EP 13848104A EP 2801424 B1 EP2801424 B1 EP 2801424B1
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Prior art keywords
metal powder
soft magnetic
magnetic metal
iron
precursor
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French (fr)
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EP2801424A4 (de
EP2801424A1 (de
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Kazumasa IKARI
Masahiro Gotoh
Takayuki Yoshida
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Dowa Electronics Materials Co Ltd
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Dowa Electronics Materials Co Ltd
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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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/33—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 soft-magnetic materials mixtures of metallic and non-metallic particles; metallic particles having oxide skin
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
    • H01Q17/005—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems using woven or wound filaments; impregnated nets or clothes
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/20—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 soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—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 soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/24—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 soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
    • 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
    • H01F41/0206—Manufacturing of magnetic cores by mechanical means
    • H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder

Definitions

  • the present invention relates to a magnetic component used in a high frequency band, and a soft magnetic metal powder constituting the magnetic component and a manufacturing method of the soft magnetic metal powder.
  • a passive element has the properties determined on the basis of the physical properties of the used material in many cases. Accordingly, the properties thereof in a high frequency band are not easily improved.
  • the product properties of magnetic components such as inductors and antennas may be determined by physical properties including dielectric permittivity and magnetic permeability.
  • An inductor is a component that utilizes magnetic flux flowing in the body of the component. In order to obtain an inductor that can be utilized in a high frequency range, a magnetic material that not only maintains the magnetic permeability in a high frequency range but also has a reduced loss even in a high frequency range needs to be developed.
  • an antenna As a communication scheme or technology progresses, an antenna corresponding to a plurality of frequency bands is becoming necessary to be installed. Furthermore, it is desired that the occupied area of an antenna in an electronic device be as small as possible. It is known that the length of an antenna when receiving a certain frequency may be a length inversely proportional to the 1/2 power of the product of the real part of magnetic permeability and the real part of dielectric permittivity. In brief, in order to obtain a short antenna length, a magnetic material having high magnetic permeability in the frequency range used needs to be developed. Furthermore, since it is most important for an antenna to have a small loss, a magnetic body having a small loss in a high frequency range is needed.
  • a magnetic iron oxide represented by ferrite, a metal magnetic material which mainly includes iron, and an alloy thereof, (hereafter referred to as a "conventional magnetic material") is currently used.
  • the magnetic materials cannot be suitably used, because a loss attributable to these magnetic materials increases in a high frequency range of not lower than several hundred MHz. It is considered that this is because the particle diameter larger than the magnetic domain size causes movement of a magnetic domain wall when magnetization is reversed, resulting in generation of a large hysteresis loss. Another possible cause is that the particle diameter equal to or larger than the skin size causes generation of a large eddy current loss.
  • nano-order plate-like particles are proposed as metal magnetic particles used in an antenna in Patent Literature 1.
  • Patent Literature 1 Japanese Patent Application Laid-Open No. 2010-103427
  • JP 2011 162882 A describes a ferromagnetic metal powder and corresponding manufacturing method.
  • US 2010/035087 A1 describes a process for producing ferromagnetic metal particles.
  • Nano-order magnetic particles are used in a magnetic component used in a high frequency band, thereby to reduce a hysteresis loss. Furthermore, the magnetic particles have a size of not larger than a skin depth, so that an eddy current loss is also reduced. In brief, it is considered that the nano-order magnetic particles can be used to obtain a magnetic component having a low loss in a high frequency band.
  • an object of the present invention is to provide a magnetic component having a sufficiently low loss, and a nano-order soft magnetic metal powder used for obtaining the magnetic component and a manufacturing method thereof.
  • the soft magnetic metal powder has the following properties, wherein iron is a main ingredient, the average particle diameter thereof is not larger than 300 nm, the coercive force (Hc) thereof is 16 to 119 kA/m (200 to 1500 Oe), the saturation magnetization thereof is not less than 90 Am 2 /kg, and the volume resistivity thereof is not less than 1.0 x 10 1 ⁇ cm where the volume resistivity is measured by a four probe method in a state of vertically pressurizing 1.0 g of the soft magnetic metal powder at 64 MPa (20 kN).
  • the above-described soft magnetic metal powder has a core/shell structure, in which the core contains iron or an iron-cobalt alloy while the shell is a composite oxide containing at least one of iron, cobalt, aluminum, silicon, a rare-earth element (including Y), and magnesium.
  • the present invention provides an inductor and an antenna in which the above-described soft magnetic metal powder is used.
  • a method of manufacturing a soft magnetic metal powder according to claim 8 of the present invention includes:
  • the solution containing an iron ion is an aqueous solution of an iron compound and a cobalt compound.
  • the precursor obtained in the precursor forming step shows a spinel-type crystal structure by a powder X-ray diffraction method.
  • the precursor reducing step includes exposing the precursor to a reduction gas at a temperature of 250°C to 650°C.
  • the slow-oxidizing step is a step of exposing the metal powder to an inert gas containing oxygen at a temperature of 20°C to 150°C.
  • a magnetic component having a low loss in which the real part ⁇ ' of magnetic permeability at 1 GHz is not less than 1.5 and the loss factor is not more than 0.15, can be obtained.
  • a magnetic component, and a soft magnetic metal powder used in the magnetic component and a manufacturing method thereof according to the present invention will be described below.
  • this embodiment is intended to exemplify one embodiment of the present invention, and the contents described below can be modified as long as the gist of the present invention is not deviated.
  • the magnetic component according to the present invention is composed of a molded body obtained by compression molding the soft magnetic metal powder according to the present invention.
  • an antenna and a coil component will be exemplified.
  • Fig. 1 is a view illustrating one example of an antenna to which a magnetic material for high frequency is applied.
  • An antenna 10 illustrated in the drawing is configured to include a conductor plate 1, a radiation plate 4 disposed on the conductor plate 1, a power supply point 2 and a short circuit plate 3 for supplying power to the radiation plate 4, and a molded body 5.
  • the molded body 5 made of the soft magnetic metal powder is held between the conductor plate 1 and the radiation plate 4.
  • FIG. 2 is a view illustrating one example of a coil component in which a magnetic material for high frequency is used.
  • a coil component 12 illustrated in Fig. 2 is configured to include an electrode 6, a flange 7, a winding wire 8 and a winding core 9.
  • the winding core 9 that is a molded body of the soft magnetic metal powder is shaped as an elongated columnar rectangular parallelepiped, and the cross section in the minor axis direction of the rectangular parallelepiped has a rectangular shape.
  • the flange 7 has a rectangular cross section larger than the rectangular cross section of the winding core 9, and is configured to be a rectangular parallelepiped having a thinner thickness in the major axis direction of the winding core 9.
  • the flange 7 may also be formed with the molded body of the soft magnetic metal powder.
  • the soft magnetic metal powder according to the present invention contains Fe (iron), or Fe and Co (cobalt), and at least one of Al (aluminum), Si (silicon), a rare-earth element (including Y (yttrium)) and Mg (magnesium) (hereinafter referred to as "Al and the like") in Fe, or Fe and Co.
  • the contained amount of Al and the like to the total sum of Fe and Co is not more than 20 at%.
  • Al or the like is solid-dissolved in Fe, or Fe and Co.
  • the precursor is reduced to produce a metal powder.
  • Fe and Co which are easily reduced, exist inside the particle in a large amount, while aluminum oxide or the like, which is not reduced, exists on the surface of the particle in a large amount.
  • the surface of the metal powder is oxidized to form an insulating film containing Al and the like.
  • the electric resistance of the particle constituting the metal powder becomes high. Accordingly, in a magnetic component formed from the metal powder, a loss based on an eddy current loss and the like is improved. Furthermore, when the contained amount of Al is increased, an oxidized film containing a large amount of Al on the surface layer can be formed. Accordingly, the electric resistance of the particle becomes high, and the eddy current loss can be reduced. Thus, tan ⁇ becomes smaller.
  • other than Al or the like, Fe, or Fe and Co can be remained on the surface.
  • Co/Fe atomic ratio When Co is contained, the contained amount of Co to Fe in terms of atomic ratio (hereinafter referred to as a "Co/Fe atomic ratio") is 0 to 60 at%.
  • the Co/Fe atomic ratio is more preferably 5 to 55 at%, and further preferably 10 to 50 at%.
  • the soft magnetic metal powder is likely to have high saturation magnetization and stable magnetic properties.
  • Al and the like also have a sintering prevention effect, preventing the particle from becoming large due to sintering during heat processing.
  • Al and the like are considered to be one of "sintering prevention elements".
  • Al and the like are non-magnetic components. Therefore, it is not preferable that an excessively large amount of Al and the like be contained, because magnetic properties are diluted.
  • the contained amount of Al and the like to the total sum of Fe and Co is preferably 1 at% to 20 at%, more preferably 3 at% to 18 at%, and further preferably 5 at% to 15 at%.
  • the method of manufacturing a soft magnetic metal powder according to the present invention includes a precursor forming step of forming a precursor, and a precursor reducing step of reducing the obtained precursor into a soft magnetic metal powder.
  • the manufacturing method may further include a slow-oxidizing step of, following to the precursor reducing step, slightly forming an oxidized film on' the surface of the soft magnetic metal powder so that handling of the powder becomes easy.
  • the precursor forming step is a wet process, while the precursor reducing step and the slow-oxidizing step are dry processes.
  • an aqueous solution containing an element (s) as a raw material is oxidized to cause an oxidation reaction, resulting in obtaining particles (a precursor) composed of the element(s) as a raw material.
  • the precursor reducing step the precursor is reduced to remove oxygen contained in the precursor forming step, to obtain a soft magnetic metal powder composed of the element(s) as a raw material.
  • the slow-oxidizing step an oxidized film is slightly formed on the surface of the obtained soft magnetic metal powder.
  • the nano-order (soft magnetic) metal powder has high activity and is easily oxidized even at normal temperature. By forming the oxidized film on the surface, the powder can stably exist even in air.
  • a water-soluble iron compound is suitably used as a raw material.
  • the water-soluble iron compound iron sulfate, iron nitrate and iron chloride may be preferably used, and iron sulfate may be further preferably used.
  • the reaction is performed by allowing a gas containing oxygen to flow through an aqueous solution of the iron compound, or by adding an aqueous solution of an oxidizing agent such as hydrogen peroxide, so that iron oxide is formed.
  • the oxidation reaction may be performed in an environment in which divalent iron (Fe 2+ ) and trivalent iron (Fe 3+ ) coexist.
  • divalent iron Fe 2+
  • trivalent iron Fe 3+
  • an existence ratio between the divalent iron and the trivalent iron is important for controlling the final particle size of the precursor.
  • the existence ratio by mol of Fe 2+ /Fe 3+ is 1 to 300, preferably 10 to 150, and further preferably 15 to 100.
  • Trivalent iron may be provided by adding a trivalent iron compound, or oxidizing divalent iron to produce trivalent iron.
  • cobalt may be added to iron.
  • a water-soluble cobalt compound may be used. This is because the reaction is based on wet system.
  • water-soluble cobalt cobalt sulfate, cobalt nitrate, cobalt chloride and the like may be preferably used, and cobalt sulfate may be further preferably used.
  • Cobalt may be added preferably before a nucleus is formed, and more preferably together with an iron material. Cobalt can also be added after the end of the oxidation reaction for deposition.
  • the oxidation for growing a nucleus is preferably performed by blowing air or oxygen into the aqueous solution. This is because the flow rate and the flow velocity can be easily controlled, and a uniform oxidation reaction can be caused in the solution even when a larger manufacturing apparatus is used, by additionally providing an air outlet to the apparatus. Oxidation can also be caused by a method of adding an oxidizing agent.
  • an element such as aluminum, silicon, a rare-earth element (including Y) and magnesium may be added as a raw material.
  • water-soluble compounds thereof may also be preferably used. These elements may be added after iron or iron and cobalt are added in a reaction vessel, during the oxidation reaction so as to be solid dissolved in the precursor, or after the end of the oxidation reaction for deposition. These elements may be added at once or continuously.
  • the precursor obtained through the wet process described above is continued to be subjected to the treatment in a dry process.
  • the precursor is subjected to a thermal reduction treatment by exposing the precursor to a reducing gas such as carbon monoxide, acetylene or hydrogen at a temperature of 250°C to 650°C.
  • a reducing gas such as carbon monoxide, acetylene or hydrogen
  • the multi-stage reduction means that a reduction treatment of retaining a treatment object at a predetermined temperature for a predetermined time is performed a plurality of times while changing the temperature.
  • the properties of the resultant metal magnetic powder can be controlled.
  • water vapor may be preferably added in a reducing gas.
  • An alloy magnetic particle powder is obtained after the thermal reduction.
  • the alloy magnetic particle powder When the alloy magnetic particle powder is handled as it is in the air, it may be rapidly oxidized. Therefore, an oxide layer is formed in the following slow-oxidizing step.
  • the obtained powder is treated while gradually increasing the amount of an oxidizing gas in an inert gas, at a temperature of 20 to 300°C for a predetermined time, so as to produce an oxide layer on the surface of the particle.
  • the reduced powder be cooled to a temperature at which the slow-oxidizing step is performed, and slow oxidation be performed at that temperature.
  • the oxide layer may be formed on the surface of the particle with a weak oxidizing gas at this temperature for performing a stabilization treatment.
  • water vapor may also be added in the weak oxidizing gas for the slow-oxidizing process. By adding water vapor, a more dense film can be formed.
  • the soft magnetic metal powder which has been subjected to the slow-oxidizing step and obtained as described above was studied on the powder properties and composition by the method shown below.
  • the average particle diameter was determined as follows: photographing an image of the metal magnetic powder observed in the bright field (for example, at a magnification of 58000) using a transmission electron microscopy (JEM-100CX Mark-II type manufactured by JEOL Ltd.) with an acceleration voltage of 100 kV; enlarging the photographed image (for example, 9 times in vertical and horizontal magnifications), randomly selecting 300 monodispersed particles from a plurality of photographs, measuring the particle diameter for each particle, and calculating an average of the measured particle diameters.
  • the BET specific surface area was determined by the BET method using 4 Sorb US manufactured by Yuasa Ionics Inc.
  • an index ( ⁇ s) for evaluating weather resistance of the soft magnetic metal powder was determined by retaining the soft magnetic metal powder in a constant temperature and humidity container at a set temperature of 60°C and a relative humidity of 90% for one week, measuring the saturation magnetizations ⁇ s before and after retaining the soft magnetic metal powder under the constant temperature and humidity, and calculating (pre-preservation ⁇ s - post-preservation ⁇ s) /pre-preservation ⁇ s x 100(%).
  • the composition of the soft magnetic metal powder was determined by performing mass analysis of the whole particle containing a metal magnetic phase and an oxidized film.
  • Co, Al, Y, Mg, and Si were quantified using a high frequency induction plasma emission spectrometer ICP (IRIS/AP) manufactured by Nippon Jarrell-Ash Co. Ltd.
  • Fe was quantified using Hiranuma Automatic Titrator (COMTIME-980) manufactured by Hiranuma Sangyo Co., Ltd.
  • Oxygen was quantified using NITROGEN/OXYGEN DETERMETER (TC-436 type) manufactured by LECO Corporation. These quantified results were provided based on mass%. Therefore, the results were appropriately converted to atom% (art%), to calculate a Co/Fe atomic ratio and an Al/(Fe + Co) atomic ratio.
  • the volume resistivity of the soft magnetic metal powder was determined by measuring 1.0 g of the powder in a state of being vertically pressurized at 64 MPa (20 kN) by the four probe method, using a powder resistance measuring unit (MCP-PD51) manufactured by Mitsubishi Chemical Analytech Co., Ltd. and a low-resistance powder measuring system software (MCP-PDLGPWIN) manufactured by Mitsubishi Chemical Analytech Co., Ltd.
  • MCP-PD51 powder resistance measuring unit
  • MCP-PDLGPWIN low-resistance powder measuring system software manufactured by Mitsubishi Chemical Analytech Co., Ltd.
  • thermosetting resin any publicly known thermosetting resin can be used.
  • thermosetting resin can be selected from a phenol resin, an epoxy resin, an unsaturated polyester resin, an isocyanate compound, a melamine resin, a urea resin, a silicone resin and the like.
  • epoxy resin one or a mixture of a mono-epoxy compound and a polyvalent epoxy compound is used.
  • examples of the mono-epoxy compound may include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.
  • Examples of the polyvalent epoxy compound may include a bisphenol-type epoxy resin obtained by glycidylating bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromo bisphenol A, tetrachloro bisphenol A, and tetrafluoro bisphenol A; an epoxy resin obtained by glycidylating other divalent phenols such as biphenol, dihydroxy naphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene; an epoxy resin obtained by glycidylating trisphenols such as 1,1,1-tris(4-hydroxyphenyl) methane and 4,4-(1-(4-(1-(4-hydroxy phenyl)-1-methyl ethyl)phenyl)ethylidene)bisphenol; an epoxy resin obtained by g
  • the polyvalent epoxy resin is preferable from the viewpoint of improving storage stability.
  • a glycidyl-type epoxy resin is preferable since productivity is remarkably high, and the epoxy resin obtained by glycidylating polyvalent phenols is more preferable since a cured product has excellent adhesion and heat resistance.
  • the bisphenol-type epoxy resin is further preferable, and an epoxy resin obtained by glycidylating bisphenol A and an epoxy resin obtained by glycidylating bisphenol F are particularly preferable.
  • the resin is preferably in a liquid form.
  • the epoxy equivalent is preferably not less than 300 in order to maintain the composition in a solid form.
  • the mixed ratio of the soft magnetic metal powder and the epoxy resin in terms of metal/resin is preferably 30/70 to 99/1, more preferably 50/50 to 95/5, and further preferably 70/30 to 90/10 at a mass ratio. This is because too little resin does not form a molded body, while too much resin does not provide desired magnetic properties.
  • the soft magnetic metal powder according to the present invention can be compression molded into a predetermined shape.
  • the molded article to be supplied has a shape exemplified in Fig. 1 and Fig. 2 .
  • the soft magnetic metal powder was molded into a doughnut shape in the example below, and the molded doughnut-shaped article was evaluated for properties as a magnetic component.
  • the soft magnetic metal powder and the epoxy resin were weighted at a weight ratio of 80:20, and the soft magnetic metal powder was dispersed in the epoxy resin using a vacuum agitation defoaming mixer (V-mini 300) manufactured by EME Co., Ltd. to prepare a paste.
  • the paste was dried on a hot plate at 60°C for 2 hours to obtain a soft magnetic metal powder-resin complex.
  • the complex was pulverized to prepare a powder of the complex. Then, 0.2 g of the complex powder was put in a doughnut-shaped container, and subjected to a load of 1 t by a hand press machine. Thus, a toroidal-shaped molded body having an outer diameter of 7 mm and an inner diameter of 3 mm was obtained.
  • a real part ( ⁇ ') of magnetic permeability, an imaginary part ( ⁇ ") of magnetic permeability, and tan ⁇ representing a loss factor were measured at 0.5 to 3 GHz, using a network analyzer (E8362C) manufactured by Agilent Technologies Inc. and a coaxial-type S-parameter method sample holder kit (product model No. : CSH2-APC7, sample dimension: 7.0 mm to 3.04 mm in diameter x 5 mm) manufactured by Kanto Electronic Application and Development Inc.
  • the precursor reducing step was performed.
  • the precursor powder in which Al was solid-dissolved in Fe was put in a basket having a ventilation function, and the basket was placed in a through-type reducing furnace.
  • a reduction treatment was conducted while allowing a hydrogen gas to flow through at 500°C for 60 minutes. After the reduction treatment was finished, a powder of metal iron (a soft magnetic metal powder) was obtained.
  • the atmosphere in the furnace was changed from hydrogen to nitrogen, and the temperature in the furnace was reduced to 80°C at a temperature drop rate of 20°C/min while allowing nitrogen to flow.
  • a gas with a mixed ratio of air to N 2 of 1/125 was added in the furnace in order to inhibit the metal iron powder from being rapidly oxidized, to form an oxidized film in the mixed atmosphere of oxygen and nitrogen. Then a supply of air was gradually increased to raise the oxygen concentration in the atmosphere.
  • the flow rate of added air to be finally supplied was 1/25 relative to N 2 .
  • a total amount of the gas to be introduced in the furnace was maintained constant by adjusting the flow rate of nitrogen.
  • This slow-oxidizing treatment was conducted in the atmosphere of maintaining the temperature at approximately 80°C.
  • Example 2 After that, the same procedure as in Example 1 was repeated to obtain a soft magnetic metal powder (having a surface oxidized film in which Fe is partly replaced with Co).
  • Example 2 The same procedure as in Example 2 was repeated, except that the mixed ratio between 1 mol/L ferrous sulfate (special grade reagent) aqueous solution and a 1 mol/L cobalt sulfate (special grade reagent) solution in Example 2 was changed to be 8:5.
  • an increase of ⁇ ' usually shifts the resonance frequency to the lower frequency side, so that tan ⁇ tends to deteriorate (become larger).
  • an increase of a Co amount for raising ⁇ ' did not cause tan ⁇ to deteriorate (become larger). It is considered that this is because inclusion of Co enabled formation of a more dense oxidized film, so that the volume resistivity of the powder increased, resulting in a reduced eddy current loss. That is, it was found that there is an effect that inclusion of Co improves ⁇ ' without deteriorating (increasing) tan ⁇ .
  • Example 5 the same procedure as in Example 4 was repeated, except that the amount of aluminum sulfate in Example 4 was changed to the amount described in Table 1.
  • FIG. 3 A TEM photograph of the particles obtained in Example 7 is shown in Fig. 3 .
  • This TEM image was photographed with an acceleration voltage of 100 kV applied, and the contrast was adjusted so that the core part appears black.
  • Fig. 3 shown as an observed example there is a spherical portion which appears dark in the center of a spherical particle, and a thin portion which appears substantially transparent around the spherical portion.
  • the soft magnetic metal powder obtained in the present invention includes a core portion formed from metal and a shell portion formed from an oxidized film.
  • the composition of the core/shell particle may be analyzed by a method such as ICP emission analysis, ESCA, TEM-EDX, XPS, and SIMS.
  • ESCA the transition of the composition from the particle surface in the depth direction can be observed. Therefore, the core portion formed from metal and the shell portion formed from an oxide can be recognized.
  • TEM-EDX the particle is irradiated with EDX-rays with the beam focused, and is semi-quantified, so that the composition of the particle can be roughly observed. Therefore, the core portion formed from metal and the shell portion formed from an oxide can be recognized (for example, see paragraph [0078] of Japanese Patent Application Laid-Open No. 2006-128535 ).
  • Example 9 the same procedure as in Example 8 was repeated, except that the reduction temperature in Example 8 was changed to the temperature described in Table 1.
  • the reduction temperature differs among Examples 7, 9, and 10. It was found that the example at a higher temperature has a higher ⁇ ' value. It is considered that this is because an increase of the reduction temperature promotes the reduction and the alloying of Fe and Co.
  • Example 2 The same procedure as in Example 2 was repeated, except that the reduction temperature by the hydrogen gas in the through-type reducing furnace in Example 2 was changed to 600°C.
  • the soft magnetic metal powder according to the present invention can be used not only in inductors and antennas but also in soft magnetic applications such as magnetic heads, lower layer members of magnetic recording media, iron cores of electromagnets, transformer cores, antennas, electromagnetic shield members, and wave absorbers.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Soft Magnetic Materials (AREA)

Claims (12)

  1. Weichmagnetisches Metallpulver, umfassend Eisen als einen Hauptbestandteil, wobei
    ein durchschnittlicher Teilchendurchmesser davon nicht größer als 300 nm ist, eine Koerzitivkraft (Hc) davon 16 bis 119 kA/m (200 bis 1500 Oe) beträgt,
    eine Sättigungsmagnetisierung davon nicht weniger als 90 Am2/kg beträgt, und dadurch gekennzeichnet, dass
    ein Durchgangswiderstand davon nicht weniger als 1,0 x 101 Ω·cm beträgt, wobei der Durchgangswiderstand durch ein Vier-Sonden-Verfahren in einem Zustand von vertikaler Unterdrucksetzung von 1,0 g des weichmagnetischen Metallpulvers bei 64 MPa (20 kN) gemessen wird.
  2. Weichmagnetisches Metallpulver nach Anspruch 1, welches eine Kern/Schale-Struktur aufweist, in welcher der Kern Eisen oder eine Eisen-Cobalt-Legierung enthält und die Schale eine Kompositoxid ist, das mindestens eines von Eisen, Cobalt, Aluminium, Silicium, einem Seltenerdelement (einschließend Y) und Magnesium enthält.
  3. Weichmagnetisches Metallpulver nach Anspruch 2, wobei ein Eisen-Cobalt-Verhältnis in der Eisen-Cobalt-Legierung Co/Fe = 0,0 bis 0,6 hinsichtlich des Atomverhältnisses beträgt.
  4. Weichmagnetisches Metallpulver nach einem der Ansprüche 1 bis 3, umfassend Aluminium, und wobei ein Atomverhältnis von Aluminium zu einer Gesamtsumme von Fe und Co Al/(Summe von Fe und Co) = 0,01 bis 0,30 beträgt.
  5. Weichmagnetisches Metallpulver nach einem der Ansprüche 1 bis 4, wobei, wenn das weichmagnetische Metallpulver und ein Epoxidharz in einem Massenverhältnis von 80:20 gemischt werden und unter Druck gegossen werden, es gilt, dass µ' > 1,5 und µ" < 0,5 und tanδ < 0,15 bei einer Frequenz von 1 GHz, und dass µ' > 1,5 und µ" < 1,5 und tanδ < 0,5 bei einer Frequenz von 2 GHz, wobei ein Realteil der komplexen magnetischen Permeabilität davon µ' ist, ein Imaginärteil davon µ" ist und ein Verlustfaktor davon tan δ (= µ"/µ') ist.
  6. Induktor, gebildet durch Verwenden des weichmagnetischen Metallpulvers nach einem der Ansprüche 1 bis 5.
  7. Antenne, gebildet durch Verwenden des weichmagnetischen Metallpulvers nach einem der Ansprüche 1 bis 5.
  8. Verfahren zur Herstellung eines weichmagnetischen Metallpulvers nach Anspruch 1, umfassend
    einen Vorläuferbildungsschritt des Hinzufügens einer wässrigen Lösung von mindestens einem von Aluminium, Silicium, einem Seltenerdelement (einschließend Y) und Magnesium zu einer Lösung, enthaltend ein Eisenion, wobei die Lösung Fe2+ und Fe3+ als Eisenionen enthält, während des Einblasens eines Gases, enthaltend Sauerstoff, zum Bilden eines Vorläufers, enthaltend mindestens eines von Aluminium, Silicium, einem Seltenerdelement (einschließend Y) und Magnesium, wobei das Verhältnis Fe2+/Fe3+ auf 1-300 Mol eingestellt ist;
    einen Vorläuferreduzierungsschritt des Reduzierens des Vorläufers zum Erhalten eines Metallpulvers; und
    einen Langsamoxidierungsschritt des Weiterumsetzens des Metallpulvers, erhalten in dem Vorläuferreduzierungsschritt, mit Sauerstoff zum Bilden eines oxidierten Films auf der Oberfläche des Metallpulvers.
  9. Verfahren zur Herstellung eines weichmagnetischen Metallpulvers nach Anspruch 8, wobei die Lösung, enthaltend ein Eisenion, eine wässrige Lösung einer Eisenverbindung und einer Cobaltverbindung ist.
  10. Verfahren zur Herstellung eines weichmagnetischen Metallpulvers nach Anspruch 8 oder 9, wobei der Vorläufer, erhalten in dem Vorläuferbildungsschritt, eine spinellartige Kristallstruktur bei einem Pulverröntgendiffraktionsverfahren aufzeigt.
  11. Verfahren zur Herstellung eines weichmagnetischen Metallpulvers nach einem der Ansprüche 8 bis 10, wobei der Vorläuferreduzierungsschritt Aussetzen des Vorläufers einem Reduktionsgas bei einer Temperatur von 250°C bis 650°C einschließt.
  12. Verfahren zur Herstellung eines weichmagnetischen Metallpulvers nach einem der Ansprüche 8 bis 11, wobei der Langsamoxidierungsschritt ein Schritt des Aussetzens des Metallpulvers einem Inertgas, enthaltend Sauerstoff, bei einer Temperatur von 20°C bis 150°C ist.
EP13848104.9A 2013-03-13 2013-03-13 Magnetische komponente, darin verwendetes weichmagnetisches metallpulver und herstellungsverfahren dafür Not-in-force EP2801424B1 (de)

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JP6963950B2 (ja) * 2017-09-22 2021-11-10 Ｄｏｗａエレクトロニクス株式会社 鉄粉およびその製造方法並びにインダクタ用成形体およびインダクタ
JP7097702B2 (ja) * 2018-01-17 2022-07-08 Ｄｏｗａエレクトロニクス株式会社 Ｆｅ－Ｃｏ合金粉並びにそれを用いたインダクタ用成形体およびインダクタ
JP7201417B2 (ja) * 2018-01-17 2023-01-10 Ｄｏｗａエレクトロニクス株式会社 シリコン酸化物被覆鉄粉およびその製造方法並びにそれを用いたインダクタ用成形体およびインダクタ
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