EP1246209B1 - Ferromagnetic-metal-based powder, powder core using the same, and manufacturing method for ferromagnetic-metal-based powder - Google Patents

Ferromagnetic-metal-based powder, powder core using the same, and manufacturing method for ferromagnetic-metal-based powder Download PDF

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Publication number
EP1246209B1
EP1246209B1 EP20020006902 EP02006902A EP1246209B1 EP 1246209 B1 EP1246209 B1 EP 1246209B1 EP 20020006902 EP20020006902 EP 20020006902 EP 02006902 A EP02006902 A EP 02006902A EP 1246209 B1 EP1246209 B1 EP 1246209B1
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EP
European Patent Office
Prior art keywords
powder
metal
ferromagnetic
pigment
coating
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EP20020006902
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German (de)
English (en)
French (fr)
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EP1246209A2 (en
EP1246209A3 (en
Inventor
Masateru c/o Technical Research Lab. Ueta
Naomichi c/o Technical Research Lab. Nakamuru
Satoshi c/o Technical Research Lab. Uenosono
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JFE Steel Corp
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JFE Steel Corp
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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
    • H01F41/0206—Manufacturing of magnetic cores by mechanical means
    • H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder
    • 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
    • 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
    • H01F1/26—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 by macromolecular organic substances

Definitions

  • the present invention relates to a ferromagnetic-metal-based powder containing a ferromagnetic metal powder, wherein the surface of said ferromagnetic-metal powder is coated with a coating consisting of silicone resin and fine particle pigments.
  • a powder of this type is known from EP 0 869 517 A1 which discloses a ferromagnetic-metal-based powder of which the powder particles are covered with a thin insulating coating comprising silicone resin and TiO 2 and/or ZrO 2 .
  • Said coating is obtained by adding silicone resin along with TiO 2 sol and/or ZrO 2 sol in the form of micro-particulates uniformly dispersed in a medium to the ferromagnetic metal powder.
  • components using magnetic materials which are used for the switching power supplies (for example, reactors, choke coils, and noise filters), have also been required to deliver performance in high frequency regions of 10 kHz or more and even under conditions in which high current is applied.
  • performances required at this time include reduction of energy loss due to magnetic materials, that is, low core loss, and high saturation magnetic flux density so that magnetic saturation does not occur even when high current is passed.
  • the powder core is a core produced by pressing a powder mixture.
  • a binder for example, a resin
  • a metal powder is appropriately added to a metal powder.
  • metal powders to be used include ferromagnetic metal powders, for example, an iron powder, an iron-based powder, e.g., Fe-Si powder, sendust powder, and Permalloy powder, or an amorphous iron-based alloy powder.
  • the powder core uses a metal powder as a raw material and a resin, having superior insulation property, as a binder, the core loss in high frequencies is lower than that of an iron core using a electrical steel plate. Furthermore, since the raw material is a metal powder, the saturation magnetic flux density becomes higher than that of the soft ferrite core.
  • the powder core has attracted great amounts of attention as a core material instead of the electrical steel plate and soft ferrite.
  • the switching frequency regions of 10 kHz to 100 kHz there is a problem in that the core loss of the powder core is still large. Therefore, because the powder core becomes a new core material instead of the electrical steel plate and soft ferrite, reduction of the core loss of the powder core is indispensable.
  • the core loss of powder core is broadly divided into hysteresis loss and eddy-current loss.
  • various research experiments have been performed in order to reduce the eddy current loss.
  • Japanese Unexamined Patent Application Publication No. 58-147106 discloses a method in which the particle diameter of a metal powder is controlled
  • Japanese Unexamined Patent Application Publication No. 62-71202, 62-29108, 2-153003, etc. disclose methods in which a metal powder and a material having an insulation property, for example, a resin, are mixed.
  • Japanese Unexamined Patent Application Publication No. 61-222207 a manufacturing method for an iron core, in which a magnetic metal powder is contacted with silica sol or alumina sol, is described. An adhesion layer having an electrical insulation property is formed on the surface of a magnetic pure metal powder by drying and, thereafter, compression molding is performed so as to produce the iron core.
  • at least one powder selected from the group consisting of magnesium oxides, chromium oxides, titanium oxides, and aluminum oxides may be added to the silica sol or alumina sol and, thereafter, the magnetic metal powder may be contacted with them.
  • these iron cores may be subjected to annealing at a temperature of 500°C or less.
  • the powder core made by annealing the body also has a low strength.
  • the low strength causes a problem in that winding around the annealed body cannot be performed.
  • Japanese Unexamined Patent Application Publication No. 2-97603 a manufacturing method for a powder core is disclosed, wherein an oblate iron powder, a powder containing silicon, and an inorganic compound powder having inertness toward silicon are mixed and heat-treated so as to produce a silicon-iron alloy powder in which silicon has been diffused into the iron powder, the resulting alloy powder is coated with water glass, etc., so as to form an insulate layer and, thereafter, press and heat treatment are performed.
  • the water glass used in the technique described in Japanese Unexamined Patent Application Publication No. 2-97603 as the material for the insulate layer contains ions of Na, which is an alkali metal element, there is a problem in that the insulation property is inadequate.
  • the present invention was made in consideration of the aforementioned problems in the conventional techniques. Accordingly, it is an object of the present invention to suggest a ferromagnetic-metal-based powder (especially, an iron-based powder) in which insulation is not destroyed during annealing for reducing hysteresis loss, and which is suitable for a powder core having a heat-resistant insulate coating, and to suggest a powder core and a manufacturing method for the ferromagnetic-metal-based powder.
  • tne inventors of the present invention performed research on a means for improving the heat resistance of insulate coating without increase in eddy current loss while insulation was maintained even after annealing for the purpose of reducing hysteresis loss.
  • a silicone resin and at least one selected pigment are added in combination to a ferromagnetic raw metal powder, especially a raw material powder primarily containing iron, superior heat-resistant insulate coating is formed on the powder surface for the first time.
  • a ferromagnetic-metal-based powder having a heat-resistant insulate coating which has remarkably superior insulation property even after annealing, has superior body strength and annealed body strength.
  • a ferromagnetic raw metal powder especially, a raw material powder primarily containing iron
  • a ferromagnetic-metal-based powder (especially, an iron-based powder) is provided, wherein the surface of a ferromagnetic metal powder (especially, a powder primarily containing iron) is coated with a coating either consisting of silicone resin and fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor (especially selected from the group comprising organic bentonite, talc, iron oxide and mica), or containing silicone resin, pigment and sedimentation inhibitor in the form of fine particles having a plate or layer structure.
  • a coating either consisting of silicone resin and fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor (especially selected from the group comprising organic bentonite, talc, iron oxide and mica), or containing silicone resin, pigment and sedimentation inhibitor in the form of fine particles having a plate or layer structure.
  • the ferromagnetic-metal-based powder preferably includes a coating containing at least one material selected from the group consisting of silicon compounds, titanium compounds, zirconium compounds, phosphorus compounds, and chromium compounds as a substrate layer of the coating either consisting of silicone resin and fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or containing silicone resin, pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure.
  • the ratio of the silicone resin content to the pigment content in the coating containing silicone resin and pigment is preferably 0.01 or more, but less than 4.0 on a mass basis.
  • the pigment is at least one selected from the group consisting of metal oxides, metal nitrides, metal carbides, minerals, and glass.
  • the total adhesion amount of the silicone resin and pigment in the coating containing silicone resin and pigment is preferably 0.01% to 25% by mass relative to the total amount of the ferromagnetic-metal-based powder.
  • a powder core is made into a predetermined shape (targeted shape) by pressing any one of the aforementioned iron-based powders, or a powder core made by further annealing of the aforementioned powder core.
  • the density of the powder core is preferably at least 95% or more of the true density. More preferably the powder core, is 98% or more of the true density.
  • a manufacturing method for a ferromagnetic-metal-based powder including the step of forming an insulate coating containing silicone resin and pigment either consisting of silicone resin and fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or containing silicone resin, pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure on the surface of a ferromagnetic raw metal powder is provided.
  • the manufacturing method for a ferromagnetic-metal-based powder includes the step of spraying paint containing silicone resin and pigment either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure on the ferromagnetic raw metal powder (especially, a raw material powder primarily containing iron) in a fluidized state so as to form an insulate coating on the surface of the raw material powder.
  • the manufacturing method for a ferromagnetic-metal-based powder (especially, an iron-based powder) of the present invention includes the steps of adding the paint containing silicone resin and pigment to the ferromagnetic raw metal powder (especially, a raw material powder primarily containing iron), agitating and mixing the resulting mixture, and performing a drying treatment so as to form an insulate coating on the surface of the raw material powder.
  • a coating containing at least one material selected from the group consisting of silicon compounds, titanium compounds, zirconium compounds, phosphorus compounds, and chromium compounds is formed beforehand on the surface of the raw material powder.
  • the total adhesion amount of the silicone resin and pigment in the coating containing silicone resin and pigment is 0.01% to 25% by mass relative to the total amount of the ferromagnetic-metal-based powder, and the ratio of the silicone resin content to the pigment content in the paint is 0.01 or more, but less than 4.0 on a mass basis.
  • an iron-based powder including a heat-resistant insulate coating in which insulation is not destroyed during annealing for reducing hysteresis loss, and a powder core having superior insulation property can be produced. Therefore, the present invention exhibits remarkable industrial effects.
  • Fig. 1 is a diagram showing the relationship between the pressing pressure and the powder core density.
  • Fig. 2 is a diagram showing the relationship between the powder core density and the magnetic flux density.
  • a ferromagnetic-metal-based powder (especially, an iron-based powder) according to the present invention is a powder including an insulate coating having superior heat resistance in which the surface of a ferromagnetic metal powder (especially, a powder primarily containing iron) is coated with a coating containing silicone resin and pigment, either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure.
  • the coating containing silicone resin and pigment can cover the metal particle directly without any intermediate layer.
  • the coating can be used as the only coating layer or can cover with other layers over or under there of.
  • an iron-based powder using a raw material powder composed of a powder primarily containing iron is described as an example, unless otherwise specified.
  • the iron-based powder can be available or can be inexpensively produced and, therefore, the iron-based powder is predicted to become a primary application of the present invention.
  • the present invention can be applied to any ferromagnetic-metal-based powder to exhibit advantageous effects.
  • the paint containing silicone resin and pigment either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure is added to the raw material powder, and agitation and mixing are performed, or, preferably the aforementioned paint is sprayed on the raw material powder primarily containing iron in a fluidized state and, thereafter, a drying treatment is performed so as to remove a solvent. Consequently, a coating containing silicone resin and pigment is formed on the surface of the raw material powder.
  • agitation and mixing refers to mixing substantially accompanied by agitation performed in order to achieve homogeneous mixing. Therefore, the case where materials are mixed and, thereafter, agitation is applied is also included in “agitating and mixing” because homogeneous mixing is achieved by agitation.
  • fluidized state refers to a state in which fluidity of a powder (or mixture of gas and powder) is improved, or fluidization is further effected by introducing a gas into the powder and, in addition to this, by agitating with rotating plates, rotating blades, etc., if necessary.
  • the fluidized state can be realized by the use of an apparatus called a fluidized tank.
  • both may be agitated and mixed at a time, or the raw material powder and a part of the paint may be agitated and mixed, the remainder of the paint may be added during mixing, and further agitation and mixing may be performed.
  • a part of the paint may be agitated, mixed, and dried and, subsequently, the same paint or paint having a changed composition may be agitated and mixed. This operation may be repeated a plurality of times.Thus, a targeted powder can be produced.
  • Atritor, Henschel mixer, ball mill, fluidized granulator, rolling fluidized granulator, etc. can be used for agitation and mixing. Most of all, the fluidized granulator and rolling fluidized granulator can produce powder mixtures having reduced variations in particle diameter because agitation is performed with a fluidized tank and, therefore, coagulation among powder particles is hindered.
  • the paint may be added to the raw material powder by spraying with a spray nozzle.
  • the silicone resin and the pigment are added uniformly and, therefore, the coating which contains the silicone resin, the pigment and is formed on the surface of the raw material powder becomes uniform.
  • an effect of spraying and an effect of using a fluidized tank are synergized and, therefore, further uniform coating is formed on the surface of the raw material powder.
  • spray of the paint when a solvent is promptly and appropriately dried, agglomeration of particles may occur based on a liquid bridge force due to the remaining liquid, and the like.
  • the amount of spray is controlled in order to avoid this phenonenom.
  • a heat treatment may be performed during mixing (or agitation and mixing) or after mixing (or agitation and mixing) in order to accelerate drying of the solvent, to cure the silicone resin, and the like.
  • silicone resin refers to polyorganosiloxane including mono-functional (M unit), difunctional (D unit), tri-functional (T unit), or tetra-functional (Q unit) siloxane units in a molecule.
  • the silicone resin has a crosslinking density higher than that of silicone oil, silicone rubber, etc., When a silicone resin is cured it becomes hard.
  • silicone resin is broadly divided into straight silicone resin in which the only component is silicone alone and silicone modified organic resin, which is a copolymer of a silicone component and an organic resin, any one of them can be used as the silicone resin in the present invention with noadverse affects.
  • the straight silicone resin is broadly divided into MQ resin and DT resin. However, any one of them may be used in the present invention.
  • silicone modified organic resins include, for example, alkyd modified type, epoxy modified type, polyester modified type, acrylic modified type, and phenol modified type. However, any one of them may be used in the present invention. Although modified type resins include those available as intermediates, they can also be used in the present invention.
  • the silicone resin is cured by heating.
  • the resins which cure even in room temperature may be called, a room temperature curing type, and this may be differentiated from the type cured by intentional heating (thermosetting type).
  • the curing mechanism of the thermosetting type silicone resin is broadly divided based on dehydration and condensation reaction, addition reaction, peroxide reaction, etc.
  • the curing mechanism of the room temperature curing type silicone resin includes the resins based on deoxime reaction, dealcohol reaction, etc.
  • resins which are cured by a curing reaction similar to that of an alkyd resin, polyester resin, or epoxy resin are classified into the room temperature curing type, and may be classified into the thermosetting type. Furthermore, photo-curing may occur.
  • any silicone resin can be used suitably regardless of its curing type.
  • a room temperature curing treatment and thermosetting treatment are especially suitable for the method for forming a coating.
  • silicone resin suitable for the present invention examples include, for example, SH805, SH806A, and SH840 (methyl-phenyl silicone: a sort of DT resin-based straight silicone resin / thermosetting type), SH997, SR620, SR2306, SR2309, SR2310, SR2316, and DC 12577 (phenyl-based resin: a sort of DT resin-based straight silicone resin/room temperature curing type, but adhesion between a coating and a substrate is improved by thermosetting), SR2400 (methyl-based resin: a sort of DT resin-based straight silicone resin/thermosetting type), SR2406, SR2410, SR2416, SR2420, and SR2402 (methyl-based resin/dealcohol room temperature curing type), SR2405 and SR2411 (methyl-based resin / deoxime room temperature curing type), SR2404 (methyl-based resin), SR2107 (silicone alkyd modified resin / curing is based on a
  • a fine particle silicone resin which is dispersed in a solvent and becomes a colloidal state may be used.
  • brands of it are R-920, R-925, manufactured by Dow Corning Toray Silicone.
  • a fine particle resins of other than aforementioned brands may be used in the present invention with no problem.
  • silicone resins made by modifying these materials or raw materials thereof may be used. Silicone resins in which at least two kinds of silicone resins having different sorts, molecular weights, and functional groups are combined at a proper ratio may be used.
  • the pigment used together with the silicone resin is not specifically limited as long as it has a high insulation property and heat resistance. However, the pigment is preferably at least one selected from the group consisting of metal oxides, metal nitrides, metal carbides, minerals, and glass. In particular, the metal oxides, metal nitrides, and metal carbides generally have a combination of high insulation property and heat resistance regardless of sorts.
  • metal oxides, metal nitrides and metal carbides have good insulation property and heat resistance, and thus, they are preferable for pigment.
  • preferable metal oxides include oxide powders of, for example, Li, Si, Al, Ti, Th, Zn, Zr, Be, Cu, Mg, K, Ca, Sn, Sb, Mn, Cr, Fe, Ni, and Co.
  • the metal oxide to be added can be chosen from these materials in consideration of insulation property and cost.
  • An oxide powder produced by oxidizing an alloy of at least two metals chosen from these materials may be used.
  • preferable metal carbides include, for example, SiC.
  • preferable metal nitrides include, for example, AlN, Si 3 N 4 , TiN, and BN.
  • preferable minerals having a high insulation property and heat resistance include, for example, mullite, magnesium silicate, bentonite, kaolinite, smectite, talc, natural mica, and artificial mica.
  • preferable glass examples include, for example, quartz glass, phosphoric acid-based glass, alumina-silica glass, boric acid-phosphoric acid-containing glass, and glass for enamel.
  • any other glasses may be used.
  • the pigment used in the present invention contains at least one chosen from these materials.
  • a colloidal oxide for example, colloidal silicon dioxide, colloidal alumina, may be used.
  • magnesium silicate examples include, for example, talc and forsterite.
  • bentonite examples include, for example, Na-montmorillonite, Ca-Mg-montmorillonite, and organic bentonite produced by compounding montmorillonite or hectorite with an organic material.
  • titania examples include, for example, anatase type titania and rutile type titania.
  • alumina examples include, for example, corundum type alumina.
  • the pigment used in the present invention is preferably a powder made of the aforementioned material as a raw material.
  • Examples of probable methods for producing a powder pigment include, for example, a pulverization method in which a raw material having a large particle diameter is pulverized, a sol-gel method or atomization method in which a powder is directly generated from a raw material using a chemical reaction, etc., and a method in which a powder is produced by a gas phase reaction. Any one of these methods may be used. Furthermore, a powder produced by a method other than the aforementioned methods may be used.
  • the powder pigment suitably used for the present invention is a powder having an average particle diameter of 40 ⁇ m or less in order that surface asperities of the coating produced are reduced so as to make the film thickness, etc., uniform, and degradation of heat resistance is prevented.
  • the average particle diameter refers to a 50% separation diameter D 50 .
  • the D 50 indicates a particle diameter at which a volume fraction (partition efficiency) becomes 50% in particle size distribution on a volume basis (hereafter referred to as Tromp curve) determined with a laser diffraction particle size analyzer, etc.
  • the aforementioned silicone resin and pigment either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure are added to a solvent and mixing is performed so as to produce paint.
  • the solvent is not specifically limited as long as the silicone resin is dissolved or dispersed.
  • the solvent is preferably, for example, an alcohol-based solvent typified by ethanol and methanol, ketone-based solvent typified by acetone and methyl ethyl ketone, aromatic-based solvent typified by benzene, toluene, xylene, phenol, and benzoic acid, and petroleum-based solvent, such as ligroin and kerosene.
  • the aromatic-based solvent is especially preferable because the silicone resin is likely to be dissolved.
  • water may be used if the silicone resin can be dissolved or can be dispersed.
  • the concentration of the paint used in the present invention may be determined in consideration of easiness of working (attainment of quantitative addition amount, stability of spraying of the spray, etc.), time required for drying, etc.
  • Additives may be added to the paint suitably used for the present invention in order to control various characteristics of the paint, for example, viscosity, thixotropic property, leveling property, dispersibility of the pigment in the paint, time required until the paint becomes not adhesive to fingers which touch the coated surface (tack time), and strength and hue of the coating.
  • the additives for the paint are preferably metal soaps, such as stearic acid metal salts, surfactants, such as perfluoroalkyl, and the like to control curing of the silicone resin.
  • the pigment sediments due to gravity and, therefore, precipitates on the bottom of container.
  • the mass ratio of the pigment to the silicone resin may locally go out of the preferable range in the paint. Therefore, a sedimentation inhibitor is added to the paint in order to prevent precipitation of the pigment.
  • sedimentation inhibitors include, for example, the following materials; fine particles having a plate or layer structure typified by boron nitride, graphite, molybdenum disulfide, mica, talc, ferrite (iron oxide), vermiculite, kaolin, etc.
  • ceramic and clay minerals for example, boron nitride, mica, talc, ferrite, vermiculite, kaolin, etc., are preferable because they are superior in not only prevention of sedimentation, but also heat resistance and insulation property and, therefore, they can serve as the pigment of the paint used in the present invention as well.
  • mica and talc are preferable because they have a plate structure and, therefore, exhibit high effect of preventing sedimentation.
  • the addition amount of the sedimentation inhibitor required for achieving the effect of preventing sedimentation is different depending on the materials.
  • the ratio thereof on a mass basis relative to the total pigment is specified to be preferably between 10% to 100% by mass, and more preferably, to be between 30% to 100% by mass.
  • the paint in order to further reduce sedimentation, preferably, the paint is used after adequate agitation with a homogenizer, etc., or while being agitated.
  • the paint in which the aforementioned silicone resin and pigment either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure are blended into the solvent is directly dropped or is sprayed using a spray, etc., on the raw material powder primarily containing iron and, therefore, the paint is mixed with the raw material powder. Subsequently, a drying treatment is performed so as to form a coating containing the silicone resin and pigment on the surface of the raw material powder.
  • the blending or spraying amount of the paint relative to the raw material powder is controlled so that the adhesion amount of the coating adhered and formed on the surface of the raw material powder becomes 0.01% to 25% on a percentage by mass basis relative to the total amount of the iron-based powder including the coating. That is, from the viewpoint of ensuring high insulation property after annealing, the adhesion amount of the coating is preferably specified to be 0.01% by mass or more. In order to maintain excellent magnetic flux density and magnetic permeability of the compact and to ensure a high body strength, the adhesion amount of the coating is preferably specified to be 25% by mass or less.
  • the drying treatment in the present invention is specified to be a treatment of standing for 8 hours or more at room temperature or a treatment of heating at 50°C to 300°C for 0.1 to 24 hours from the viewpoint of adequate drying of the solvent.
  • drying of the solvent is inadequate, the powder may become sticky and handling of the powder may become very hard.
  • the coating strength may be reduced due to the solvent remaining in the coating and, therefore, desired heat resistance may not be achieved.
  • this ratio is preferably specified to be 0.01 or more, but less than 2.0, and more preferably, be 0.01 or more, but less than 1.5.
  • the lower limit value is preferably 0.2 or more, and most preferably, is more than 0.25.
  • the R value is specified to be 0.01 or more, and preferably, be 0.2 or more. That is, the silicone resin is preferably contained at a predetermined rate or more relative to the pigment, in order that the performance as the binder for adhering the pigment on the iron powder is adequately exhibited, and that degradation of the insulation property of the compact due to peeling of the coating during handling and pressing of the powder is prevented.
  • the R value is preferably specified to be 4.0 or less, that is, the ratio of the silicone resin relative to the pigment is preferably specified to be a predetermined value or less in order to avoid breakage of the coating due to reduction of fracture strength (because the silicone resin is brittle compared to the pigment) and volume change during annealing (because the silicone resin changes to silica), and to avoid reduction of insulation property of the compact due to the breakage of the coating.
  • the R is preferably less than 4.0, especially, is less than 2.0, and more preferably, is less than 1.5.
  • R (silicone resin content (% by mass)) / (pigment content (% by mass)) in the coating to be within the range of 0.01 or more, but less than 4.0, preferably, the compound ratio of the silicone resin to the pigment in the paint to be blended into or sprayed on the raw material powder is controlled.
  • the paint containing silicone resin and pigment either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure is blended (agitation and mixing) into or sprayed on the raw material powder, and subsequently, drying is performed so as to remove the solvent. Therefore, an iron-based powder, in which a coating composed of silicone resin and pigment is formed on the surface, can be produced. Furthermore, a coating of the same paint or a coating of paint having a different R value or pigment composition, or having a different R value and pigment composition, may be formed over the iron-based powder produced as described above so as to produce an iron-based powder. A plurality of coatings may be overlaid so as to produce an iron-based powder.
  • a powder in which a coating containing at least one material selected from the group consisting of silicon compounds, titanium compounds, zirconium compounds, phosphorus compounds, and chromium compounds is preferably formed beforehand on the surface thereof, is used as the raw material powder.
  • the coating containing at least one material selected from the group consisting of silicon compounds, titanium compounds, zirconium compounds, phosphorus compounds, and chromium compounds is formed beforehand on the surface of the raw material powder
  • the paint containing the aforementioned silicone resin and pigment is blended (agitation and mixing) into or sprayed on the resulting raw material powder and, subsequently, drying is performed so as to remove the solvent, an iron-based powder can be produced, in which a multilayer coating composed of a lower layer coating containing at least one material selected from the group consisting of silicon compounds, titanium compounds, zirconium compounds, phosphorus compounds, and chromium compounds, and an upper layer coating containing the silicone resin and pigment.
  • the insulation property of the iron-based powder after annealing is further improved compared to that in the case where only the coating containing the silicone resin and pigment is included.
  • raw material powder a method for forming the coating containing at least one material selected from the group consisting of silicon compounds, titanium compounds, zirconium compounds, phosphorus compounds, and chromium compounds on the surface of the raw material powder (hereafter may be referred to as raw material powder) will be described.
  • One method includes the step of adding the aforementioned materials to the raw material powder and, thereafter, performing agitating and mixing and finally drying.
  • Another method includes the step of fluidizing or agitating the raw material powder, then spraying a material containg the aforementioned materials or a solution produced by diluting a material containing the aforementioned materials with a colvent on the raw material powder in a fluidized or agitated state, finally drying.
  • Still another method includes the steps of immersing the raw material powder in the resulting solution for a predetermined time, finally drying the raw material powder.
  • the method for forming a coating containing at least two sorts of compounds on the surface of the raw material powder includes the steps of mixing atleast two compounds beforehand, and the resulting mixture is added and treated, a method in which at least two sorts of compounds are prepared separately, and those are added at the same time and treated, a method in which materials containing a compound are added in sequence and treated, or the like is conceivable, although not limited to these methods in the present invention.
  • treatment ways may be different depending on the materials.
  • At least one compound for forming the lower layer coating may be added to the raw material powder by so-called integral blend in which the compound is added into the paint containing silicone resin and pigment.
  • a treatment for forming the lower layer coating is performed and, subsequently, a treatment for forming the upper layer coating is performed, further complete lower layer coating can be produced and insulation property after annealing is improved.
  • the amount of the material containing the aforementioned materials (compounds), concentration of the solution, adding method, mixing method, etc. can be appropriately determined in accordance with the materials to be used and treating methods.
  • the content of silicon compound in the coating is specified to be 0.01% to 4% by mass relative to the total iron-based powder including the coating.
  • the content of titanium compound in the coating is preferably specified to be 0.01% to 4% by mass relative to the total iron-based powder including the coating.
  • the content of zirconium compound in the coating is preferably specified to be 0.01% to 4% by mass relative to the total iron-based powder including the coating.
  • the content of phosphorus compound in the coating is preferably specified to be 0.01% to 4% by mass relative to the total iron-based powder including the coating.
  • the content of chromium compound in the coating is preferably specified to be 0.01% to 4% by mass relative to the total iron-based powder including the coating.
  • silane compounds for example, alkoxysilane and acyloxysilane
  • silanizing agents for example, organohalosilane and derivatives thereof, silicon peroxides, silicate compounds, etc.
  • materials containing silicon compounds although not limited to the silane compounds, silanizing agents, silicon peroxides, and silicate compounds in the present invention.
  • silane compounds include, for example, chlorosilane compounds, e.g., methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and trifluoropropyltrichlorosilane, heptadecafluorodecyltrichlorosilane, alkoxysilane compounds, e.g., tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, hexyttrimethoxys
  • any one of the aforementioned materials is used with no problem. At least two of the aforementioned materials may be mixed and used. Furthermore, silane compounds other than those described above may be used. The silane compounds may be used without any further treatment, or may be used after being diluted with solvents.
  • silicon peroxides include, for example, materials typified by the molecular formula R 4-n Si(OOR') n , e.g., vinyltris(t-butylperoxy)silane, although not limited to this.
  • R represents an organic group
  • n represents an integer of 1 to 4.
  • silicate compounds include, for example, alkyl silicates, e.g., ethyl silicate (tetraethoxysilane), methyl silicate, N-propyl silicate, and N-butyl silicate. These may be used after being hydrolyzed.
  • alkyl silicates e.g., ethyl silicate (tetraethoxysilane), methyl silicate, N-propyl silicate, and N-butyl silicate. These may be used after being hydrolyzed.
  • Silicate compounds other than those described above may be used. The silicate compounds may be used without any further treatment, or may be used after being diluted with solvents.
  • titanium coupling agents are preferably used as materials containing titanium compounds, although not limited to the titanium coupling agents in the present invention.
  • titanium coupling agents include, for example, titanium esters, e.g., tetraisopropyl titanate, tetraisopropyl titanate polymer, tetrabutyl titanate, tetrabutyl titanate polymer, tetrastearyl titanate, and 2-ethylhexyl titanate, titanium acylates, e.g., isopropoxytitanium stearate, titanium chelates, e.g., titanium acetylacetonate and titanium lactate.
  • any one of the aforementioned materials is used with no problem. At least two of the aforementioned materials may be mixed and used.
  • Coupling agents other than the aforementioned titanium coupling agents may be used.
  • the titanium coupling agents may be used without any further treatment, or may be used after being diluted with solvents.
  • zirconium coupling agents are used preferably as materials containing zirconium compounds.
  • zirconium coupling agents include, for example, zirconium alkoxide, although not limited to this.
  • a chromium complex salt in which organic anions are bonded, is used preferably as a material containing a chromium compound, although not limited to this.
  • a solution in which phosphoric acid is diluted with a solvent for example, water and organic solvents, a solution in which phosphate is dissolved into water, organic solvents, or a mixed solvent thereof, or phosphoric acid ester or phosphoric acid ester solution, etc.
  • a solvent for example, water and organic solvents
  • phosphoric acid diluted with a solvent is used, the degree of reaction becomes likely to be controlled, the addition amount of phosphoric acid is reduced, and excessive generation of phosphorus compounds can be inhibited.
  • at least two sorts of compounds include, for example, some kinds of phosphate compounds, although not limited to this.
  • a solution in which phosphate and chromate, preferably and surfactants, such as oxyethylen-oxypropylene block polymer, and boric acid are dissolved into water is used preferably as a material containing a phosphate compounds, although not limited to this.
  • the content of compound in cluding two or more sorts of aforementioned compounds in the coating is preferably specified to be 0.01% to 4% by mass relative to the total iron-based powder including the coating.
  • the sort of the raw material powder primarily containing iron used in the present invention is not specifically limited as long as it is a powder which exhibits ferromagnetism and has a high saturation magnetic flux density.
  • iron, steel, and iron alloys exhibit ferromagnetism and have high saturation magnetic flux densities.
  • Examples of the raw material powder primarily containing iron suitably used for the present invention include those descried below (composition is shown on a % by mass basis); iron powder (Fe content is 90% or more, and the remainder is impurities, for example, about 0.2% or less of carbon): especially, so-called pure iron powder containing 98% or more of Fe is preferable, Fe-Si alloy powder: especially preferably, Si content is on the order of 0 to 6.5%, and the remainder is impurities as typified by, for example, Fe-3%Si alloy powder, Fe-4%Si alloy powder, and Fe-6.5%Si alloy powder, Fe-Al alloy powder (preferably, Al content is on the order of 10 to 20%, and the remainder is iron and impurities), Fe-Ni alloy powder (preferably, Ni content is on the order of 20% to 50%, and the remainder is iron and impurities), sendust powder (preferably, Al content is on the order of 4% to 6%, Si content is on the order of 9% to 11%, and the remainder is iron and im
  • Thermoperm (Fe-30%Ni: the remainder is preferably impurities).
  • the aforementioned powders primarily contain iron, and iron content is 50% or more, and preferably, is 70% or more, although not limited to these, any metal powder which exhibits ferromagnetism can be used in the present invention.
  • the present invention can be applied to a Permalloy primarily containing iron and nickel, and the like.
  • Permalloys examples include, for example, 45Permalloy (Fe-45%Ni), 68Permalloy (Fe-68%Ni), 78Permalloy (Fe-78.5%Ni), 4-79Permalloy (Fe-4%Mo-79%Ni), and 2-81Permalloy (Fe-2%Mo-81%Ni), wherein the remainder is impurities, although not limited to these.
  • ferromagnetic-metal-based powders are produced instead of iron-based powders.
  • At least one powder selected from these ferromagnetic metal powders, especially from the powders primarily containing iron is used preferably as a raw material powder. Even when small amounts of (preferably 10% or less) additives and impurities, which are not ferromagnetic materials, are present in the raw material powder, there is no problem as long as the powder exhibits ferromagnetism.
  • the shape of the powder is not specifically limited.
  • oblate iron-based powder processed to be oblate by some manufacturing methods or mechanical processing (for example, crushing) may be used as the aforementioned raw material powder.
  • pure iron powders typified by atomized iron powders, electrolytic iron powders, etc.
  • Examples of pure iron powders include, for example, KIP(R)-MG270H, KIP(R)-304A, and KIP(R)-304AS manufactured by Kawasaki Steel Corporation.
  • the particle diameter of the raw material powder used in the present invention is not specifically limited, although it is desirable that the particle diameter is appropriately determined in accordance with uses and required properties of the powder core. For example, when particles having a large particle diameter are taken out by classification and are used, compressibility is improved. Furthermore, magnetic gaps generated among particles are reduced by a large degree. As a result, a powder core having a high permeability, high magnetic flux density, and remarkably reduced hysteresis loss due to reduction of magnetic gaps can be produced. Such a powder core is suitable for the use in which usable frequencies are on the order of 1 kHz or less, and a high magnetic flux density is required. In this case, the particle diameter is preferably 75 ⁇ m or more, and more preferably, is 100 ⁇ m or more.
  • the particle diameter of the iron-based powder is reduced, eddy current loss is reduced because the amount of eddy current passing through the particle is reduced. Consequently, when particles having small particle diameters are taken out of the raw material powder in advance by classification and are used, reduction of core loss due to eddy current loss can be realized. This is very effective for reduction of iron loss in high frequency regions in which the eddy current loss makes up a large proportion of the total core loss compared to that in low frequency regions (for example, 1 kHz or less).
  • the powder core produced using such an iron-based powder is suitable for the use where usable frequencies are on the order of 10 kHz to 500 kHz, and reduced loss is required. In this case, the particle diameter is preferably 75 ⁇ m or less.
  • a powder having a small particle diameter exhibits a somewhat reduced compact density and magnetic flux density compared to those of a powder having a large particle diameter when pressed under the same conditions.
  • the compact density can be improved by, for example, increasing the pressing pressure.
  • the ferromagnetic raw metal powder especially the raw material powder, may be used after the elements contained therein are adjusted within the range in which compressibility and magnetic characteristics of the powder core are not adversely affected.
  • the ferromagnetic-metal-based powder produced by the aforementioned method, especially the iron-based powder sometimes contains small amounts of impurities, for example, a sedimentation inhibitor which do not function as pigment, other than the raw material powder, silicone resin, pigment including pigment that functions as a sedimentation inhibitor, lower layer coating materials (silicon compound, and the like).
  • impurities for example, a sedimentation inhibitor which do not function as pigment, other than the raw material powder, silicone resin, pigment including pigment that functions as a sedimentation inhibitor, lower layer coating materials (silicon compound, and the like).
  • the iron-based powder produced by the aforementioned method can be pressed using a die, etc., after addition of a lubricant, etc., if necessary, and therefore, made to be a compact (powder core).
  • this pressing by applying, for example, a high-pressure pressing method in which the pressing pressure is 980 MPa or more; a so-called powder forging method in which the powder is made to be a preliminary body in advance and is subjected to cold forging; a so-called warm pressing method in which the powder and a dieare heated, and the pressing is performed at a predetermined temperature; a die lubrication method in which even a powder containing no lubricant can be pressed without causing galling of a die, and the like by coating the surface of the die, instead of the powder, with a lubricant; and a warm die lubrication pressing method which is a combination of the die lubrication method and the warm pressing method, a high density powder core (powder core density is 7.47
  • a hole In general, a hole, a so-called pore, is present in the inside of a powder core. It is known that the pore becomes a cause of reduction of the powder core strength. The pore also becomes a cause of degradation of the magnetic characteristics so as to reduce the magnetic flux density, and the like. This is because when the pore is present, a demagnetizing field is generated so as to reduce the magnetic flux density in the powder core. In order to prevent generation of the demagnetizing field and to improve the magnetic characteristics, for example, improvement of magnetic flux density, it is very effective to minimize the size of the pore.
  • the pore is present between particles in the powder core, and when the powder core density, relative to the true density, is less than 95%, a plurality of pores between adjacent particles form in a continuously connected state, that is, the pores become a so-called open hole.
  • the powder core density becomes 95% or more relative to the true density
  • the pore present between particles remains in an isolated state, that is, the pore becomes a so-called closed hole.
  • the powder core density is specified to be preferably 95% or more relative to the true density, and more preferably, be 98% or more.
  • lubricants include, for example, metal soap, e.g., lithium stearate, zinc stearate, and calcium stearate, or wax, e.g., aliphatic amide. Addition of the lubricant may be omitted depending on the use of the powder core.
  • the lubricant may melt and separate from the powder portion, that is, so-called melt-off of lubricant may occur and, therefore, an effect of the lubricant may be reduced. Consequently, preferably, at least one lubricant having a melting point higher than the pressing temperature is used.
  • a plurality of lubricants may be mixed beforehand, and may be used as a lubricant.
  • a powder core can be used without annealing.
  • the body after pressing, in order to relieve strain applied to the iron-based powder during pressing and to reduce hysteresis loss, the body is preferably subjected to a heat treatment for relieving strain (annealing).
  • the time, temperature and atmosphere of the heat treatment after pressing may be appropriately determined in accordance with the uses.
  • an annealing atmosphere may be any one of an inert gas atmosphere of Ar gas, N 2 gas, etc., a reducing gas atmosphere of hydrogen gas, etc., and vacuum.
  • the dew point of the atmospheric gas may be appropriately determined in accordance with the uses, etc.
  • the temperature raising rate and temperature lowering rate during annealing may be appropriately determined in accordance with the working environment and uses.
  • a step for keeping a constant temperature during the annealing process may be provided.
  • a typical range of the annealing temperature is on the order of 400°C to 1000°C, and a typical range of the annealing time is on the order of 10 minutes to 300 minutes.
  • the aforementioned powder core produced by pressing using the iron-based powder exhibits high insulation property even when annealed at a high temperature at which most organic materials are decomposed.
  • the paint containing silicone resin and pigment either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure is added to the raw material powder and these are mixed, the silicon resin and said pigment in the paint integrally coat the raw material powder, and after drying, the silicone resin is cured. Consequently, the silicone resin forms a strong coating containing the pigment as a reinforcement filler. Since the surface of the iron-based powder is covered with a coating which is composed of the silicone resin and pigment, and which has a high insulation property, the insulation property of the powder core is improved by a large degree.
  • the silicone resin on the surface of the iron-based powder is thermally decomposed and changed into silica and, at the same time, is sintered together with the pigment and iron-based powder so as to form a ceramic-like or vitreous material having a high insulation property and high strength. Therefore, high insulation property and practical strength can be realized even after annealing.
  • the pigment used in the present invention preferably improves the strength and insulation property of the aforementioned sintered structure.
  • a method, in which alumina, silica, etc., are combined, or materials functioning as fillers in the inside of the sintered structure because of a plate structure like mica and talc and of a high insulation property are combined, and the like is effective.
  • the powder in which the coating containing at least one material selected from the group consisting of silicon compounds, titanium compounds, zirconium compounds, phosphorus compounds, and chromium compounds is formed on the surface, is used as the raw material powder, the insulation property after annealing is further improved.
  • reaction products are densely generated on the surface of the raw material powder and, therefore, insulation property among the raw material powder is remarkably improved. Furthermore, the wettability and adhesion between the raw material powder and the coating composed of the silicone resin and pigment either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure are remarkably improved due to the reaction products (coating) formed on the surface. Said coating becomes further uniform due to improvement of the wettability.
  • a paint in which a silicone resin and pigment either fine particle pigments selected from ceramic and clay minerals having a plate or layer structure and also functioning as sedimentation inhibitor, or pigment and a sedimentation inhibitor in the form of fine particles having a plate or layer structure were added to a solvent in order that the content thereof became as shown in Tables 2-1, 2-2 and 2-3, was added to a raw material powder primarily containing iron, and agitation and mixing were performed. The resulting powder was subjected to a drying treatment.
  • silicone resin SR-2410, SR-2400, SH805, SH2115 and R-925 manufactured by Dow Corning Toray Silicone Co., Ltd., were used.
  • the powder to be used was chosen from powders of silica (silicon oxide), alumina(corundum type), zirconia(zirconium oxide), titania(rutile type), mullite, forsterite, silicon nitride, aluminum nitride, silicon carbide, talc, organic bentonite, iron oxide, chromium oxide, copper oxide, frit glass for enamel (01-4102P manufacrured by FERRO ENAMELS (JAPAN) LIMITED), and mica.
  • a colloidal silica which was dispersed in methyl-ethyl ketone solvent (the concentration of the silica in the solution was 20% by mass.) was used as a silica.
  • a collidal silica which was dispersed in water solvent (the concentration of the silica in the solution was 20% by mass.) was used as a silica.
  • a collidal alumina-silica in which 90% by mass of a colloidal silica and 10% by mass of a colloidal alumina with 3% of an acetic acid were dispersed in water solvent (the concentration of the silica in the solution was 20% by mass) was used as a silica.
  • a Henschel mixer or rolling fluidized granulator was used for agitation and mixing of the pigment, raw material powder primarily containing iron, and paint.
  • the whole paint was added to the raw material powder and thereafter, agitation and mixing were performed.
  • the mixing time was specified to be 400 seconds.
  • the adhesion amount of the coating was adjusted to the value shown in Tables 3-1, 3-2 and 3-3 by changing the addition amount of the paint.
  • the raw material powder was fluidized in a fluidized tank and, thereafter, the paint was added to the raw material powder through a spray nozzle.
  • the paint was added at a rate of 20 g per minute. After addition of the paint was completed, fluidization was performed for 1,200 seconds for the drying treatment.
  • the adhesion amount of the coating was adjusted at the value shown in Tables 3-1 to 3-3 by changing the spraying amount of the paint.
  • drying treatment after agitation and mixing, standing was performed at room temperature for 10 hours, and heating and drying were performed at 250°C for 120 minutes (this also serves as curing treatment of the thermosetting type silicone resin, and as a treatment for ensuring curing and adhesion of the room temperature curing type silicone resin).
  • a lubricant was added to the iron-based powder including a coating on the surface produced as described above, and mixing was performed. Zinc stearate was used as the lubricant. The addition amount of the lubricant was specified to be 0.25 parts by weight relative to 100 parts by weight of the iron-based powder.
  • Addition and mixing of the lubricant was performed according to the following steps.
  • the iron-based powder was put in a bag.
  • a predetermined amount of lubricant was added into the bag.
  • the inlet of the bag was closed tightly, and the whole bag was vibrated in order that the lubricant was uniformly mixed with the whole iron-based powder.
  • the resulting powder mixture was pressed at a pressing pressure shown in Tables 3-1 to 3-3.
  • compacts of a ring test piece (outer diameter of 38 mm, inner diameter of 25 mm, and height of 6.2 mm) for magnetic measurement and a rectangular parallelepiped test piece (width of 10 mm, length of 35 mm, and height of 6.2 mm) for resistivity measurement were produced.
  • the resulting compacts were subjected to annealing at 800°C for 1 hour in a nitrogen atmosphere. Regarding Example 1-19, annealing was not performed.
  • the powder core density was determined by calculation based on the measured values of mass and volume of the test piece.
  • the resistivity was measured by a four-terminal method using the rectangular parallelepiped test piece.
  • inductance was performed with a LCR meter (HP4284A) manufactured by Agilent Technologies using a coil made from 11 turns of formal covered wire 0.6 mm in diameter wound on the ring test piece.
  • AC relative initial permeability ⁇ iAC was determined by calculation based on the obtained inductance value.
  • the core loss was measured with a B-H Analyzer (E5060A) manufactured by Agilent Technologies using a coil made from 40 turns at each of primary side and secondary side of formal covered wire 0.6 mm in diameter wound on the ring test piece.
  • E5060A B-H Analyzer
  • the manual bending test is a test in which the test piece for resistivity measurement is manually bended, and test pieces manually broken were evaluated to be not usable for the powder core.
  • Example 1-10 in which alumina, talc, titania, organic bentonite, iron oxide, chromium oxide, and copper oxide were used as pigment shows a high resistivity and reduced core loss compared to those of the third and sixth comparative examples in Tables 2-1 and 3-1, in which the same amount of pigment was added.
  • Example 1-18 in which the paint was added by a spraying method using a rolling fluidized granulator shows a high resistivity and reduced core loss compared to those of Example 1-10 in which the same amount of the same paint was added and, therefore, it is clear that the spraying method is effective.
  • Example 1-19 in which annealing was not performed shows a remarkably high resistivity but high core loss compared to those of Example 1-11 in which annealing was performed.
  • Example 1-28 and Example 1-29 test pieces were produced under the same condition except for the composition of the paint for the use.
  • Example 1-29 in which the ratio of talc is larger, shows a higher resistivity and lower core loss. Consequently, it is clear that when the ratio of talc in the paint composition is increased, the resistivity is increased and the core loss is reduced.
  • each of Comparative examples which is outside of the scope of the present invention shows remarkably reduced resistivity.
  • the resistivity of iron is on the order of 0.1 ⁇ m.
  • Comparative example 1-1 in which only silicone resin was added
  • Comparative example 1-2 in which only pigment was added
  • Comparative example 1-2 showed remarkably reduced resistivity. Furthermore, core loss was increased by a large degree and, therefore, could not be measured.
  • Comparative example 1-3 in which an epoxy resin was used instead of the silicone resin
  • Comparative example 1-6 in which a phenol resin was used instead of the silicone resin
  • the resistivity after annealing was reduced by a large degree, and the core loss was remarkably increased and, therefore, could not be measured.
  • Comparative examples 1-4 and 1-5 in which silica sol was used
  • the test piece was brittle, and could be manually bended. The ring was also brittle and winding could not be performed. Consequently, the magnetic characteristics could not be examined.
  • an iron powder "KIP(R)-304A" manufactured by Kawasaki Steel Corporation, shown in Table 1 (No. b) was used as the raw material powder primarily containing iron.
  • This raw material powder was subjected to a surface treatment so as to form beforehand a coating containing the compound (material) shown in Table 4-1 and 4-2 as a lower layer coating, and was made to be a raw material powder for the succeeding step.
  • the surface treatment for forming the lower layer coating was performed by the steps of adding or spraying a solution containing respective compounds shown in Table 4-1 and 4-2 to the raw material powder, agitating and mixing, standing for 24 hours in a draft, and drying.
  • Example 2-36 37, 38, after addition of the solution was completed, the treament was perfomed by the steps of curing at 350°C for 10min in ambient atmosphere and drying at 100°C for 60min.
  • the concentration of the compound in the solution was specified to be 5% by mass.
  • the solution was added or sprayed in order that the addition amount of the compound to the raw material powder became the value shown in Table 4-1 and 4-2.
  • the amount of the compound added to the raw material powder becomes 1% by mass.
  • Example 2-32 dilution was not performed, and a silane compound was added to the raw material powder with no solvent and mixing was performed.
  • the whole solution containing various compounds was added to the raw material powder and, thereafter, agitation and mixing were performed.
  • the mixing time was specified to be 400 seconds.
  • the adhesion amount of the coating was adjusted at the value shown in Table 6 by changing the amount of the solution added.
  • the raw material powder was fluidized in a fluidized tank and, thereafter, the solution was added to the raw material powder through a spray nozzle. After addition of the solution was completed, fluidization was performed for 1,200 seconds in order to dry. The adhesion amount of the coating was adjusted at the value shown in Table 6 by changing the spraying amount of the solution.
  • a coating (upper layer coating) containing silicone resin and pigment was formed on the aforementioned lower layer coating as the upper layer coating and, therefore, an iron-based powder including the lower layer coating and upper layer coating was produced.
  • An iron-based powder including only a lower layer coating was taken as a comparative example, in which a coating (upper layer coating) containing silicone resin and pigment was not formed.
  • a lubricant was added to the iron-based powder including the coating on the surface produced as described above, and mixing was performed. Zinc stearate was used as the lubricant. The amount of the lubricant added was specified to be 0.25 parts by weight relative to 100 parts by weight of the iron-based powder.
  • Example 1 Regarding these compacts (powder core) after annealing, similarly to Example 1, the powder core density, resistivity, inductance at 10 kHz, and core loss at 10 kHz and 0.1 T were measured. Furthermore, a manual bending test was performed. The measuring method and the testing method were similar to those in Example 1.
  • This insulating layer forming solution is prepared by mixing 10pts.wt. of phosphoric acid (as 100% concentration.), 20pts.wt. potassium bichromate, 5pts.wt. of ammonium bichromate, 5% of as boric acid, and 0.5wt% of oxyethylen-oxypropylene, based on 100pts.wt. of phosphates of Al and water. The concentation of the solution is 5% by mass. *****) This insulating layer forming solution is prepared by mixing 10pts.wt. of phosphoric acid (as 100% concentration.), 20pts.wt. potassium bichromate, 5pts.wt. of ammonium bichromate.
  • This insulating layer forming solution is prepared by mixing 10pts.wt. of phosphoric acid (as 100% concentration.), 20pts.wt. potassium bichromate, 5pts.wt. of ammonium bichromate, 5% of as boric acid, and 0.5wt% of oxyethylen-oxyoropylene, based on 100pts.wt. of phosphates of Zn and water. The concentration of the solution is 5% by mass.
  • Example CE Comparative example [Table 5-2] Category Raw material powder No. *** Paint** Remark Silicone resin* Pigment Total Sort Content Alumina Organic bentonite Talc Titania iron oxide Chromium oxide Copper oxide content* EX 2-17 M SR2410 20 40 40 80 EX 2-18 N SR2410 20 40 40 80 EX 2-19 O SR2410 20 40 40 80 EX 2-20 O SR2410 20 40 40 80 EX 2-21 P SR2410 20 40 40 80 EX 2-22 Q SR2410 20 40 40 80 EX 2-23 R SR2410 20 40 40 80 EX 2-24 S SR2410 20 40 40 80 EX 2-25 T SR2410 20 40 40 80 EX 2-26 U SR2410 20 40 40 80 EX 2-27 L SR2410 20 40 80 $1 : 0.5***** EX 2-28 L SR2410 20 40 40 80 $2: 1.0***** EX 2-29 V SR2410 20 40 40 80 EX 2-30 W SR2410 20 40 40 80 EX 2-31
  • Example 2-10 shows improved insulation property compared to that in the case where only the coating containing silicone resin and pigment including pigment which functions as sedimentation inhibitor was formed on the surface (Example 1-23). Furthermore, the insulation property is excellent and the core loss is reduced compared to comparative examples 2-1 and 2-2 in which a coating containing silicone resin and pigment was not formed on the surface.
  • Example 2-11 in which a rolling fluidized granulator was used for mixing during formation of the lower layer coating, shows an improved insulation property and reduced core loss compared to those of Example 2-7, in which a Henschel mixer was used.
  • a lubricant was added to the iron-based powder including the coating on the surface produced as described above, and mixing was performed. Zinc stearate was used as the lubricant. The addition amount of the lubricant was specified to be 0.25 parts by weight relative to 100 parts by weight of the iron-based powder.
  • the resulting powder mixture was pressed at a pressure shown in Table 9 and, therefore, compacts of a ring test piece (outer diameter of 38 mm, inner diameter of 25 mm, and height of 6.2 mm) for magnetic measurement and a rectangular parallelepiped test piece (width of 10 mm, length of 35 mm, and height of 6.2 mm) for resistivity measurement were produced.
  • the resulting compacts were subjected to annealing at 800°C for 1 hour in nitrogen atmosphere.
  • Example 3-11 to 3-14 in which a raw material powder having a particle diameter smaller than that in Example 1-23 was used, shows a reduced core loss at 5 kHz and 0.2 T and a reduced core loss at 10 kHz and 0.1 T.
  • Fig. 1 is a diagram showing the relationship between the pressing pressure and the powder core density.
  • the powder core density increases with increases in pressing pressure, and regarding the iron-based powder shown in this example, when the pressing pressure is 980 MPa or more, a powder core having a density of 95% or more relative to the true density is produced.
  • Fig. 2 is a diagram showing the relationship between the powder core density and the magnetic flux density. Increases in the magnetic flux density are observed as the powder core density increases. Furthermore, when the powder core density is 7.47 Mg/m 3 or more, the degree of improvement of the magnetic flux density becomes remarkably large relative to the increase in the powder core density. Since when the powder core density shows the value of 95% or more relative to the true density, the magnetic characteristics, for example, a magnetic flux density, are improved remarkably, it is clear that the powder core density is preferably specified to be 95% or more of the true density.
  • the magnetic flux density B 10000 becomes 1.70 T or more and, therefore, the magnetic flux density equivalent to that in the case where an electrical steel plate is used is realized. This indicates that the present invention can be applied to the uses in which high torque output is required, such as motors.
  • Example 5-1 to 5-7 powder core test pieces were produced from an iron-based powder produced in a manner similar to those in Example 1 and Example 2.
  • the producing conditions were as shown in Table 12.
  • pressing was performed at a pressing pressure of 1,470 MPa, and the condition of subsequent annealing was changed as shown in Table 12.
  • Methyltrimethoxysilane was used as the silicon compound for the lower layer coating.
  • the paint for the upper layer coating the same paint as that in Example 1-47 was used (refer to Table 2-3).
  • characteristics were evaluated in a manner similar to those in Example 1. The results thereof are shown in Table 12.
  • the core loss is reduced with increases in annealing temperature, and especially, when the annealing temperature is raised to 400°C or more, remarkable reduction of core loss is observed.
  • the initial permeability is increased as the annealing temperature is increased. Consequently, it is clear that the magnetic characteristics of the powder core produced according to the present invention are improved by annealing, and in particular, remarkable effect of improving magnetic characteristics can be achieved by annealing at a temperature of 400°C or more.
  • Examples 6-1 to 6-8 powder core test pieces were produced from an iron-based powder produced in a manner similar to those in Example 1 and Example 2.
  • the producing conditions were as shown in Table 13.
  • pressing was performed at 686 MPa and, thereafter, cold core forging was performed so as to control the density to be as shown in Table 13.
  • Annealing was performed at a temperature shown in Table 13.
  • Methyltrimethoxysilane was used as the silicon compound for the lower layer coating.
  • the paint for the upper layer coating the same paint as that in Example 1-47 was used (refer to Table 2-2).
  • Table 13 As the powder core according to the present invention exhibits superior magnetic characteristics similarto those in the case where common pressing is performed even when the powder core is produced by cold forging.
  • Example 7 an iron-based powder was produced in a manner similar to those in Example 1 and Example 2. Subsequently, powder core test pieces were produced under the conditions shown in Table 14-1. Pressing temperatures and lubricating conditions are shown in Table 14-1. After pressing, annealing was performed at a temperature shown in Table 14-2. Methyltrimethoxysilane or hydrolized ethyl silicate were used as the silicon compound for the lower layer coating. Paint used for the upper layer coating are shown in Table 15. Regarding a warm pressing method or warm die lubrication pressing method in which pressing was performed at a pressing temperature of 130°C, a die for pressing was pre-heated, so that the die surface temperature was made to be at the pressing temperature.
  • the iron-based powder heated to the same temperature as the pressing temperature was put into the die and, thereafter, pressing was performed.
  • a so-called fluid die lubrication method in which the concentration of a lubricant in an ethanol solvent was adjusted to be 5% by mass so as to prepare a lubricant solution, the resulting lubricant solution was applied by coating, and after the solvent was dried, pressing was performed, and a so-called powder die lubrication method, in which a lubricant electricaly charged in a lubrication apparatus was introduced in a die by spraying using a die lubrication apparatus (manufactured by Gasbarre Products, Inc.), and the lubricant was adhered on the die surface due to charge, were used.
  • the adhesion amount of the labricant to the die was specified to be 10 g/m 2 in each method. Regarding these test pieces, characteristics were evaluated in a manner similar to those in Example 1. The results thereof are shown in Table 14-2. It is clear that the powder core according to the present invention exhibits superior magnetic characteristics similar to those in the case where common pressing is performed even when the powder core is produced using a so-called warm pressing, die lubrication pressing, or warm die lubrication pressing.
EP20020006902 2001-03-27 2002-03-26 Ferromagnetic-metal-based powder, powder core using the same, and manufacturing method for ferromagnetic-metal-based powder Expired - Fee Related EP1246209B1 (en)

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WO2012136758A2 (en) 2011-04-07 2012-10-11 Höganäs Ab (Publ) New composition and method
WO2015092002A1 (en) 2013-12-20 2015-06-25 Höganäs Ab (Publ) Soft magnetic powder mix
WO2015091762A1 (en) 2013-12-20 2015-06-25 Höganäs Ab (Publ) Soft magnetic composite powder and component
EP3199264A1 (en) 2016-02-01 2017-08-02 Höganäs Ab (publ) New composition and method
EP3576110A1 (en) 2018-05-30 2019-12-04 Höganäs AB (publ) Ferromagnetic powder composition

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JP4507663B2 (ja) * 2004-03-30 2010-07-21 住友電気工業株式会社 軟磁性材料の製造方法、軟磁性粉末および圧粉磁心
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JP4802182B2 (ja) * 2007-12-14 2011-10-26 Ｊｆｅスチール株式会社 圧粉磁心用鉄粉
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CN104392836B (zh) * 2014-09-25 2017-02-15 中钢集团安徽天源科技股份有限公司 高性能各向异性干压烧结铁氧体多极磁环制造方法
CN106563801A (zh) * 2016-11-09 2017-04-19 安徽孺子牛轴承有限公司 一种耐高温耐腐蚀轴承材料及其制备方法
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WO2012136758A2 (en) 2011-04-07 2012-10-11 Höganäs Ab (Publ) New composition and method
WO2015092002A1 (en) 2013-12-20 2015-06-25 Höganäs Ab (Publ) Soft magnetic powder mix
WO2015091762A1 (en) 2013-12-20 2015-06-25 Höganäs Ab (Publ) Soft magnetic composite powder and component
EP3199264A1 (en) 2016-02-01 2017-08-02 Höganäs Ab (publ) New composition and method
WO2017134039A1 (en) 2016-02-01 2017-08-10 Höganäs Ab (Publ) New composition and method
US11285533B2 (en) 2016-02-01 2022-03-29 Höganäs Ab (Publ) Composition and method
EP3576110A1 (en) 2018-05-30 2019-12-04 Höganäs AB (publ) Ferromagnetic powder composition

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