WO2014141318A1 - Composant magnétique, poudre de métal magnétique doux utilisée dans celui-ci, et son procédé de production - Google Patents

Composant magnétique, poudre de métal magnétique doux utilisée dans celui-ci, et son procédé de production Download PDF

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WO2014141318A1
WO2014141318A1 PCT/JP2013/001638 JP2013001638W WO2014141318A1 WO 2014141318 A1 WO2014141318 A1 WO 2014141318A1 JP 2013001638 W JP2013001638 W JP 2013001638W WO 2014141318 A1 WO2014141318 A1 WO 2014141318A1
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Prior art keywords
metal powder
soft magnetic
magnetic metal
precursor
iron
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PCT/JP2013/001638
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English (en)
Japanese (ja)
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和正 碇
後藤　昌大
吉田　貴行
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Ｄｏｗａエレクトロニクス株式会社
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Priority to KR1020147008494A priority Critical patent/KR101496626B1/ko
Priority to CN201380003390.1A priority patent/CN103999170B/zh
Priority to EP13848104.9A priority patent/EP2801424B1/fr
Priority to US14/372,342 priority patent/US20150104664A1/en
Priority to PCT/JP2013/001638 priority patent/WO2014141318A1/fr
Priority to TW102112474A priority patent/TWI471876B/zh
Publication of WO2014141318A1 publication Critical patent/WO2014141318A1/fr
Priority to US14/850,109 priority patent/US20160001371A1/en

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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, a soft magnetic metal powder constituting the magnetic component, and a method for producing the soft magnetic metal powder.
  • these devices are being reduced in size and power consumption for the purpose of being used as mobile devices. Therefore, individual components are required to have characteristics in the high frequency band and low loss. However, among the components that make up equipment, the characteristics of passive elements are often determined based on the physical properties of the material, and it is not easy to improve the characteristics in the high frequency band.
  • the product characteristics of magnetic parts such as inductors and antennas are determined by physical characteristics such as permittivity and permeability.
  • An inductor is a component that uses magnetic flux flowing in the body of the component. In order to obtain an inductor that can be used in a high frequency band, it is necessary to develop a magnetic material that not only possesses magnetic permeability in the high frequency region but also has a small loss in the high frequency region.
  • the antenna length for receiving a predetermined frequency may be a length inversely proportional to the 1/2 power of the product of the real part of the magnetic permeability and the real part of the dielectric constant. That is, in order to shorten the antenna length, a magnetic material having high permeability in the frequency range to be used must be developed. Furthermore, since it is most important that the antenna has a small loss, a magnetic material having a small loss in the high frequency region is required.
  • conventional magnetic materials magnetic iron oxides typified by ferrite, metal magnetic materials centered on iron and their alloys (hereinafter referred to as “conventional magnetic materials”) are used as magnetic materials used in such inductors and antennas.
  • the loss due to these magnetic materials increases, so that it cannot be suitably used.
  • the cause is that the particle diameter is larger than the magnetic domain size, which causes the domain wall to move when the magnetization is reversed, resulting in a large hysteresis loss, and the large eddy current loss due to the particle diameter being larger than the skin size. This is thought to be due to the occurrence of
  • Patent Document 1 proposes nano-order flat particles as metal magnetic particles used for an antenna.
  • nano-order magnetic particles for magnetic components used in the high frequency band is intended to reduce hysteresis loss associated with the movement of the domain wall by reversing the magnetization in smaller units where the domain wall is formed. Furthermore, the eddy current loss is also reduced by making the magnetic particles smaller than the skin size. In other words, it is considered that nano-order magnetic particles may be able to obtain a low-loss magnetic component in the high frequency band.
  • an object of the present invention is to provide a magnetic component having a sufficiently low loss, a nano-order soft magnetic metal powder for obtaining the magnetic component, and a manufacturing method thereof.
  • the above problem can be solved by forming a magnetic part using soft magnetic metal powder having a specific configuration.
  • the soft magnetic metal powder is Iron as the main component, An average particle size of 300 nm or less,
  • the coercive force (Hc) is 16 to 119 kA / m (200 to 1500 Oe),
  • the saturation magnetization is 90 Am 2 / kg or more,
  • the volume resistivity measured by a four-point probe method is 1.0 ⁇ 10 1 ⁇ ⁇ cm or more.
  • the soft magnetic metal powder is further The soft magnetic metal powder forms a core / shell structure, the core contains iron or iron-cobalt alloy, the shell contains at least one of iron, cobalt, aluminum, silicon, rare earth elements (including Y), and magnesium. It is a complex oxide.
  • the soft magnetic metal powder is
  • the soft magnetic metal powder is When the soft magnetic metal powder and the epoxy resin are mixed at a mass ratio of 80:20 and pressure-molded,
  • the real part of the complex permeability is ⁇ ′
  • the imaginary part is ⁇ ′′
  • the present invention also provides an inductor and an antenna using the soft magnetic metal powder.
  • the method for producing the soft magnetic metal powder of the present invention comprises: While blowing an oxygen-containing gas into a solution containing iron ions, at least one aqueous solution of aluminum, silicon, rare earth elements (including Y), and magnesium is added, and aluminum, silicon, rare earth elements (including Y) are added.
  • a precursor forming step of forming a precursor containing at least one kind of magnesium A precursor reduction step of reducing the precursor to form a metal powder; And a gradual oxidation step in which oxygen is further applied to the metal powder obtained in the precursor reduction step to form an oxide film on the surface of the metal powder.
  • the solution containing iron ions is an aqueous solution of an iron compound and a cobalt compound.
  • the precursor obtained in the precursor forming step exhibits a spinel crystal structure by a powder X-ray diffraction method.
  • the precursor reduction step is characterized in that the precursor is exposed to a reducing gas at a temperature of 250 ° C. to 650 ° C.
  • the gradual oxidation step is a step of exposing the metal powder to a gas containing oxygen in an inert gas at a temperature of 20 ° C. to 150 ° C.
  • the soft magnetic metal powder of the present invention it is possible to obtain a low-loss magnetic component in which ⁇ ′, which is the real part of the magnetic permeability at 1 GHz, is 1.5 or more and the loss coefficient is 0.15 or less.
  • the magnetic component of the present invention the soft magnetic metal powder used for the magnetic component, and the manufacturing method thereof will be described.
  • this embodiment exemplifies one embodiment of the present invention, and the following contents can be changed without departing from the gist of the present invention.
  • the magnetic component of the present invention is constituted by a molded body obtained by compression molding the soft magnetic metal powder of the present invention.
  • examples of the magnetic component include an antenna and a coil component.
  • FIG. 1 is a diagram showing an example of an antenna to which a high-frequency magnetic material is applied.
  • the illustrated antenna 10 includes a radiation plate 4 disposed on a conductor plate 1, and includes a feeding point 2 and a short-circuit plate 3 for feeding power to the radiation plate 4, and the antenna 10 is soft between the conductor plate 1 and the radiation plate 4. It has a structure in which the compact 5 made of magnetic metal powder is sandwiched. By providing such a structure, the wavelength can be shortened and the antenna 10 can be downsized.
  • FIG. 2 is a diagram showing an example of a coil component configured using a high-frequency magnetic material.
  • the illustrated coil component 12 includes an electrode 6, a flange 7, a winding 8, and a winding core 9.
  • the core 9 that is a compact of the soft magnetic metal powder is an elongated columnar rectangular parallelepiped, and the cross section in the minor axis direction of the rectangular parallelepiped has a rectangular cross section.
  • the flange 7 has a rectangular cross section larger than the rectangular cross section of the core 9, and has a rectangular parallelepiped structure with a small thickness in the major axis direction of the core 9.
  • the collar 7 may also be formed of a soft magnetic metal powder compact.
  • the soft magnetic metal powder of the present invention includes at least Fe (iron), Fe and Co (cobalt), Al (aluminum), Si (silicon), rare earth elements (including Y (yttrium)), and Mg (magnesium).
  • Fe iron
  • Fe and Co cobalt
  • Al aluminum
  • Si silicon
  • rare earth elements including Y (yttrium)
  • Mg magnesium
  • Al etc. One kind (hereinafter referred to as “Al etc.”) is included.
  • the content of Al, etc. with respect to the total of Fe and Co is within a range of 20 at% or less.
  • Al or the like is dissolved in Fe or Fe and Co, and the precursor is then reduced to form a metal powder.
  • the reduced metal powder contains a large amount of Fe and Co that are easily reduced inside the particle, and a large amount of aluminum oxide that is not reduced exists on the surface of the particle.
  • an insulating film containing Al or the like is formed by oxidizing the surface of the metal powder.
  • the electric resistance of the particles constituting the metal powder is increased, and the loss based on eddy current loss or the like is improved when the magnetic component is formed.
  • an oxide film containing a large amount of Al can be formed on the surface layer, and since the electrical resistance of the particles is increased, eddy current loss can be reduced and tan ⁇ is reduced.
  • not only Al etc. but Fe or Fe and Co may remain on the surface.
  • the Co content is 0 to 60 at% in terms of atomic ratio of Co to Fe (hereinafter referred to as “Co / Fe atomic ratio”). More preferably, the Co / Fe atomic ratio is 5 to 55 at%, more preferably 10 to 50 at%. Within such a range, the soft magnetic metal powder has a high saturation magnetization and can easily obtain stable magnetic characteristics.
  • Al and the like also have a sintering preventing effect, and suppress the coarsening of particles due to sintering during heat treatment.
  • Al and the like are treated as one of “sintering prevention elements”.
  • Al or the like is a non-magnetic component, and if it is contained too much, the magnetic properties are diluted, which is not preferable.
  • the content of Al or the like with respect to the total of Fe and Co is preferably 1 at% to 20 at%, more preferably 3 at% to 18 at%, and even more preferably 5 at% to 15 at%.
  • the method for producing a soft magnetic metal powder of the present invention includes a precursor forming step for forming a precursor and a precursor reducing step for reducing the obtained precursor to form a soft magnetic metal powder. Further, after the precursor reduction step, a gradual oxidation step in which an oxide film is slightly formed on the surface of the soft magnetic metal powder may be added for easy handling.
  • the precursor formation process is a wet process, and the precursor reduction process and the gradual oxidation process are dry processes.
  • the precursor forming step is a step of obtaining particles (precursor) composed of the element as a raw material by oxidizing the aqueous solution containing the element as the raw material to cause an oxidation reaction.
  • the precursor reduction step is a step of reducing the precursor to remove oxygen contained in the precursor formation step to obtain a soft magnetic metal powder made of the element as a raw material.
  • the gradual oxidation step is a step of forming a slight oxide film on the surface of the obtained soft magnetic metal powder.
  • Nano-order (soft magnetic) metal powder has high activity and is easily oxidized at room temperature. When an oxide film is formed on the surface, it can be stably present even in air.
  • a water-soluble iron compound is preferably used as a raw material.
  • the water-soluble iron compound iron sulfate, iron nitrate, iron chloride and the like can be preferably used, and iron sulfate is more preferably used.
  • the reaction is carried out by forming an iron oxide by passing a gas containing oxygen through an aqueous solution of an iron compound or adding an aqueous solution of an oxidizing agent such as hydrogen peroxide.
  • the oxidation reaction is preferably performed in an environment in which divalent iron (Fe 2+ ) and trivalent iron (Fe 3+ ) coexist.
  • divalent iron Fe 2+
  • trivalent iron Fe 3+
  • the abundance ratio of divalent iron and trivalent iron is important for controlling the particle size of the final precursor, and Fe 2+ / Fe 3+ is preferably in a range of 1 to 300 in terms of molar ratio, preferably Is in the range of 10 to 150, more preferably in the range of 15 to 100.
  • Trivalent iron may be produced by adding a trivalent iron compound or by oxidizing divalent iron.
  • cobalt may be added to iron.
  • a water-soluble cobalt compound is preferably used. This is because the reaction is performed wet.
  • water-soluble cobalt cobalt sulfate, cobalt nitrate, cobalt chloride and the like can be preferably used, and cobalt sulfate is more preferably used.
  • Cobalt is preferably added before nucleation, and more preferably at the same time as the iron raw material. In addition, it can also be added and deposited after completion of the oxidation reaction.
  • the oxidation for growing the nuclei it is preferable to blow air or oxygen into the aqueous solution. This is because the flow rate and flow velocity can be easily adjusted, and even if the manufacturing apparatus is enlarged, the solution can be uniformly oxidized by adding the outlets. In addition, it can also oxidize by the method of adding an oxidizing agent.
  • elements such as aluminum, silicon, rare earth elements (including Y), and magnesium may be added to the raw materials. These elements are also preferably water-soluble compounds. These elements are preferably added after iron or iron and cobalt are added to the reaction vessel, and can be added in the middle of the oxidation reaction to be dissolved in the precursor, or added after the end of the oxidation reaction. It may be deposited.
  • the addition method may be one-time addition or continuous addition.
  • ⁇ Precursor reduction process> The precursor obtained through the wet process as described above is continuously processed in the dry process.
  • the precursor is exposed to a reducing gas such as carbon monoxide, acetylene, or hydrogen at a temperature of 250 ° C. to 650 ° C. to perform a heat reduction treatment.
  • a reducing gas such as carbon monoxide, acetylene, or hydrogen
  • multistage reduction refers to performing a reduction process of holding an object to be processed at a predetermined temperature for a predetermined time a plurality of times while changing the temperature. By appropriately controlling the holding temperature and time, it is possible to control the properties of the finished metal magnetic powder.
  • a reducing gas added with water vapor As an atmosphere for this reduction treatment, it is also preferable to use a reducing gas added with water vapor.
  • the gradual oxidation step is a step of forming an oxide layer on the particle surface by treating the inert gas at a temperature of 20 to 300 ° C. for a predetermined time while gradually increasing the amount of oxidizing gas.
  • the powder after the reduction is cooled to a temperature at which this gradual oxidation step is performed, and gradual oxidation is preferably performed at that temperature, and the surface of the particles is oxidized by a weak oxidizing gas at this temperature.
  • a physical layer It is preferable to form a physical layer and perform a stabilization treatment.
  • a weakly oxidizing gas with a slow oxidation treatment added with water vapor may be used, and the addition of water vapor is preferable because a denser film can be formed. .
  • the powder characteristics and composition of the soft magnetic metal powder obtained after the slow oxidation step thus obtained were examined by the following method.
  • the average particle diameter is an image obtained by observing the metal magnetic powder in a bright field at a accelerating voltage of 100 kV using a transmission electron microscope (JEM-100CXMark-II type manufactured by JEOL Ltd.) (for example, 58000 times magnification) ) And taking a picture (for example, the vertical and horizontal magnification is 9 times), randomly selecting 300 monodisperse particles from a plurality of photographs, measuring the particle size of each particle, Obtained from the average value.
  • JEM-100CXMark-II type manufactured by JEOL Ltd. for example, 58000 times magnification
  • a picture for example, the vertical and horizontal magnification is 9 times
  • ⁇ Evaluation of magnetic properties and weather resistance of soft magnetic metal powder As the magnetic properties (bulk properties) of the obtained soft magnetic metal powder, a VSM device (VSM-7P) manufactured by Toei Kogyo Co., Ltd. was used, with an external magnetic field of 10 kOe (795.8 kA / m) and a coercive force Hc. (Oe and kA / m), saturation magnetization ⁇ s (Am 2 / kg), and squareness ratio SQ were measured. Further, as an index ( ⁇ s) for evaluating the weather resistance of the soft magnetic metal powder, the soft magnetic metal powder is kept in a constant temperature and humidity container at a set temperature of 60 ° C. and a relative humidity of 90% for one week, and the constant temperature and humidity are maintained. The saturation magnetization ⁇ s before and after holding was measured and determined according to ( ⁇ before storage ⁇ after storage) / ⁇ s before storage ⁇ 100 (%).
  • composition of the soft magnetic metal powder particles was determined by mass analysis of the entire particle including the metal magnetic phase and the oxide film.
  • Co, Al, Y, Mg, and Si were quantified using a high frequency induction plasma emission analyzer ICP (IRIS / AP) manufactured by Nippon Jarrell Ash.
  • ICP IRIS / AP
  • a Hiranuma automatic titration apparatus (COMTIME-980) manufactured by Hiranuma Sangyo Co., Ltd. was used.
  • oxygen was quantified using NITRROGEN / OXYGEN DETERMETER (TC-436 type) manufactured by LECO Corporation. Since these quantitative results are given as mass%, the Co / Fe atomic ratio and Al / (Fe + Co) atomic ratio were determined by appropriately converting to atomic% (at%).
  • volume resistivity of soft magnetic metal powder is measured using a powder resistance measurement unit (MCP-PD51) manufactured by Mitsubishi Chemical Analytech Co., Ltd. and a low resistance powder measurement system software (MCP-PDLGPWIN) manufactured by Mitsubishi Chemical Analytech Co., Ltd. Then, 1.0 g of powder was measured by a four-probe method in a state where the powder was vertically pressurized at 64 MPa (20 kN).
  • MCP-PD51 powder resistance measurement unit
  • MCP-PDLGPWIN low resistance powder measurement system software
  • thermosetting resin can be selected from phenol resin, epoxy resin, unsaturated polyester resin, isocyanate compound, melamine resin, urea resin, silicone resin and the like.
  • epoxy resin either a monoepoxy compound, a polyvalent epoxy compound, or a mixture thereof is used.
  • Examples of the monoepoxy compound include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxyl glycidyl ether, glycidyl acetate, glycidyl butyrate Glycidyl hexoate, glycidyl benzoate and the like.
  • polyvalent epoxy compound examples include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol A.
  • Bisphenol-type epoxy resin obtained by glycidylation of bisphenols such as tetrafluorobisphenol A; epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) fe E) Ethylidene) Epoxy resins glycidylated with trisphenols such as bisphenol; Epoxy resins glycidylated with tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; Phenol novolac, Cresol Novolak type epoxy resin obtained by glycidylation of novolaks such as novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol
  • a polyvalent epoxy compound is preferable from the viewpoint of enhancing storage stability.
  • productivity is overwhelmingly high, so glycidyl-type epoxy resins are preferable, and more preferably epoxy obtained by glycidylation of polyhydric phenols because of excellent adhesion and heat resistance of cured products. It is preferable to use a resin.
  • a bisphenol type epoxy resin is more 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 300 or more.
  • the mixing ratio of the soft magnetic metal powder and the epoxy resin is preferably 30/70 to 99/1, more preferably 50/50 to 95/5, and even more preferably 70 in terms of mass ratio when expressed in terms of metal / resin. / 30 to 90/10. This is because if the amount of the resin is too small, a molded body is not obtained, and if the amount is too large, desired magnetic properties cannot be obtained.
  • the soft magnetic metal powder of the present invention can be formed into an arbitrary shape by compression molding. What is supplied in practical use is the shape illustrated in FIGS. 1 and 2. However, in the following examples, it was molded into a donut shape, and the characteristics as a magnetic part were evaluated.
  • the soft magnetic metal powder and the epoxy resin were weighed at a weight ratio of 80:20, and dispersed in an epoxy resin using a vacuum agitation / defoaming mixer (V-mini300) manufactured by EME Co., Ltd. to obtain a paste.
  • This paste was dried on a hot plate at 60 ° C. for 2 hours to obtain a soft magnetic metal powder-resin composite.
  • This composite is pulverized to prepare a composite powder. 0.2 g of this composite powder is placed in a donut-shaped container, and a load of 1 t is applied by a hand press machine. A 3 mm toroidal shaped body was obtained.
  • precursor particles in which Al was dissolved in Fe were obtained.
  • the precursor was filtered and washed with water by a conventional method, and then dried at 110 ° C. to obtain a precursor dry solid (also referred to as precursor powder).
  • a precursor reduction step was performed.
  • the precursor powder in which Al is dissolved in Fe is put into a bucket that can be ventilated, the bucket is placed in a penetration type reduction furnace, and reduction treatment is performed at 500 ° C. for 60 minutes while ventilating hydrogen gas. gave. After the reduction treatment, metallic iron powder (soft magnetic metal powder) was obtained.
  • the atmosphere in the furnace was converted from hydrogen to nitrogen, and the temperature in the furnace was lowered to 80 ° C. at a temperature lowering rate of 20 ° C./min in a state where nitrogen was passed.
  • a gas mixed with an air amount of 1/125 with respect to N 2 is added into the furnace so that the metal iron powder is not rapidly oxidized, and oxygen / nitrogen is added.
  • the oxygen concentration in the atmosphere was increased by forming an oxide film in the mixed atmosphere and gradually increasing the supply amount of air.
  • the final soft magnetic metal powder (having a surface oxide film) was obtained.
  • Various physical properties and bulk characteristics of the obtained soft magnetic metal powder are shown in Table 2, and high frequency characteristics of a molded body using the soft magnetic metal powder are shown in Table 3.
  • the conditions of the composition and the precursor reduction step and the gradual oxidation step are shown in Table 1 including other examples.
  • a 1 mol / L ferrous sulfate (special grade reagent) aqueous solution and a 1 mol / L cobalt sulfate (special grade reagent) solution were mixed at
  • Example 2 Thereafter, the same procedure as in Example 1 was repeated to obtain a soft magnetic metal powder (a part of Fe having a surface oxide film substituted with Co). Various physical properties and bulk characteristics of the obtained soft magnetic metal powder are shown in Table 2, and high frequency characteristics of a molded body using the soft magnetic metal powder are shown in Table 3.
  • Example 3 In Example 2, the same procedure as in Example 2 was repeated except that the mixing ratio of the 1 mol / L ferrous sulfate (special grade reagent) aqueous solution and the 1 mol / L cobalt sulfate (special grade reagent) solution was changed to 8: 5. It was. Various physical properties and bulk characteristics of the obtained soft magnetic metal powder are shown in Table 2, and high frequency characteristics of a molded body using the soft magnetic metal powder are shown in Table 3.
  • Examples 1 to 3 are considered. Compared with Example 1 containing no Co, Examples 2 and 3 containing Co resulted in higher ⁇ ′. It can be considered that by containing Co and making an FeCo alloy, the magnetic moment is increased and the saturation magnetization is increased, thereby increasing the magnetic permeability. In other words, the inclusion of Co has the effect of increasing ⁇ ′.
  • Table 2 Various physical properties and bulk characteristics of the obtained soft magnetic metal powder are shown in Table 2, and high frequency characteristics of a molded body using the soft magnetic metal powder are shown in Table 3.
  • Example 5 to 8 For Examples 5 to 8, the same procedure as in Example 4 was repeated except that the amount of aluminum sulfate in Example 4 was changed to the amount shown in Table 1. Various physical properties and bulk characteristics of the obtained soft magnetic metal powder are shown in Table 2, and high frequency characteristics of a molded body using the soft magnetic metal powder are shown in Table 3.
  • Examples 4 to 8 are considered. It has been found that increasing the amount of Al contained has the effect of reducing tan ⁇ .
  • a precursor containing Fe, Co, and Al when a precursor containing Fe, Co, and Al is reduced, Fe and Co that are easily reduced are present inside the particle, and aluminum oxide that is not easily reduced is present on the particle surface. An oxide film containing Al is formed. For this reason, when the amount of Al to be included is increased, an oxide film containing more aluminum oxide is formed on the particle surface, so that the volume resistivity of the particles is increased, eddy current loss is reduced, and tan ⁇ is It seems to have become smaller.
  • Example 7 a TEM photograph of the powder obtained in Example 7 is shown in FIG.
  • This TEM image was taken with an acceleration voltage of 100 kV, and the contrast was adjusted so that the core portion appeared black.
  • FIG. 3 shown as a confirmed example there is a spherical portion that appears dark at the center of the substantially spherical particle, and a portion that appears thin and substantially transparent appears in the periphery.
  • the soft magnetic metal powder obtained by the present invention is formed of a core portion made of metal and a shell portion made of an oxide film.
  • composition analysis of the core / shell particles examples include ICP emission analysis, ESCA, TEM-EDX, XPS, SIMS, and the like.
  • ESCA a change in composition from the particle surface in the depth direction can be confirmed, and a core portion formed of metal and a shell portion formed of oxide can be distinguished.
  • TEM-EDX the particle is focused to irradiate EDX and semi-quantitatively to confirm the rough composition of the particle.
  • the core part formed of metal and the shell formed of oxide The part can be discriminated (for example, refer to paragraph [0078] of JP-A-2006-128535).
  • Example 9 to 10 For Examples 9 to 10, 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. Various physical properties and bulk characteristics of the obtained soft magnetic metal powder are shown in Table 2, and high frequency characteristics of a molded body using the soft magnetic metal powder are shown in Table 3.
  • Example 11 In Example 2, the same procedure as in Example 2 was repeated except that the reduction temperature with hydrogen gas in the through-type reduction furnace was changed to 600 ° C. Various physical properties and bulk characteristics of the obtained soft magnetic metal powder are shown in Table 2, and high frequency characteristics of a molded body using the soft magnetic metal powder are shown in Table 3.
  • Table 2 Various physical properties and bulk characteristics of the obtained soft magnetic metal powder are shown in Table 2, high frequency characteristics of a molded body using the soft magnetic metal powder are shown in Table 3, and a TEM photograph of the obtained powder is shown in FIG. Also from this photograph, it can be seen that the soft magnetic metal powder obtained in the present invention is formed of a core portion formed of metal and a shell portion formed of an oxide film.
  • Comparative Example 1 As the soft magnetic metal powder of Comparative Example 1, a commercially available Mn—Zn ferrite powder was used. Table 2 shows various physical properties and bulk characteristics of the soft magnetic metal powder, and Table 3 shows high-frequency characteristics of a molded body using the soft magnetic metal powder.
  • Comparative Example 2 As the soft magnetic metal powder of Comparative Example 2, a commercially available Fe—Cr—Si powder was used. Table 2 shows various physical properties and bulk characteristics of the soft magnetic metal powder, and Table 3 shows high-frequency characteristics of a molded body using the soft magnetic metal powder.
  • the soft magnetic metal powder of the present invention is used not only for inductors and antennas but also for soft magnetic applications such as magnetic heads, lower layers of magnetic recording media, iron cores of electromagnets, transformer cores, antennas, electromagnetic shielding materials, and radio wave absorbers. be able to.

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

Abstract

La présente invention concerne un composant magnétique d'un inducteur, antenne ou assimilé, utilisant une poudre magnétique de métal et ayant un plus grand composant complexe de perméabilité magnétique, qui est une perte dans la bande GHz. Il est possible de supprimer le coefficient de perte dans la bande GHz à un niveau bas au moyen du composant magnétique, qui est formé à partir d'une poudre magnétique de métal doux qui a du fer comme composant principal et qui est caractérisé comme ayant une taille de particules moyenne de pas plus de 300 nm, une coercivité (Hc) de 16-119 kA/m (200-1500 Oe), une magnétisation à saturation d'au moins 90 Am2/kg, et une résistivité en volume mesurée au moyen d'un procédé de sonde à quatre points d'un corps moulé formé par compression verticale de 1,0 g de la poudre métallique à 64 MPa (20 kN) d'au moins 1,0x101Ω·cm.
PCT/JP2013/001638 2012-01-20 2013-03-13 Composant magnétique, poudre de métal magnétique doux utilisée dans celui-ci, et son procédé de production WO2014141318A1 (fr)

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KR1020147008494A KR101496626B1 (ko) 2013-03-13 2013-03-13 자성 부품과 그것에 이용되는 연자성 금속 분말 및 그 제조 방법
CN201380003390.1A CN103999170B (zh) 2013-03-13 2013-03-13 磁性部件和磁性部件所使用的软磁性金属粉末及其制造方法
EP13848104.9A EP2801424B1 (fr) 2013-03-13 2013-03-13 Composant magnétique, poudre de métal magnétique doux utilisée dans celui-ci, et son procédé de production
US14/372,342 US20150104664A1 (en) 2012-01-20 2013-03-13 Magnetic component, and soft magnetic metal powder used therein and manufacturing method thereof
PCT/JP2013/001638 WO2014141318A1 (fr) 2013-03-13 2013-03-13 Composant magnétique, poudre de métal magnétique doux utilisée dans celui-ci, et son procédé de production
TW102112474A TWI471876B (zh) 2013-03-13 2013-04-09 A magnetic part, a soft magnetic metal powder for use, and a method for manufacturing the same
US14/850,109 US20160001371A1 (en) 2012-01-20 2015-09-10 Magnetic component, and soft magnetic metal powder used therein and manufacturing method thereof

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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
CN110181036A (zh) * 2019-05-14 2019-08-30 合肥博微田村电气有限公司 一种复合软磁金属粉末、制备方法及一体成型电感
CN116825468B (zh) * 2023-08-04 2024-01-12 广东泛瑞新材料有限公司 一种铁钴磁芯及其制备方法和应用

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KR20140121810A (ko) 2014-10-16
TW201426773A (zh) 2014-07-01
KR101496626B1 (ko) 2015-02-26
EP2801424A1 (fr) 2014-11-12
CN103999170A (zh) 2014-08-20
EP2801424B1 (fr) 2017-03-08
EP2801424A4 (fr) 2015-03-25
CN103999170B (zh) 2016-06-15

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