WO2013015074A1 - フェライト焼結体およびこれを備えるフェライトコア - Google Patents

フェライト焼結体およびこれを備えるフェライトコア Download PDF

Info

Publication number
WO2013015074A1
WO2013015074A1 PCT/JP2012/066755 JP2012066755W WO2013015074A1 WO 2013015074 A1 WO2013015074 A1 WO 2013015074A1 JP 2012066755 W JP2012066755 W JP 2012066755W WO 2013015074 A1 WO2013015074 A1 WO 2013015074A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
ferrite
mass
zno
ferrite sintered
Prior art date
Application number
PCT/JP2012/066755
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
憲一 古舘
竹之下　英博
ひとみ 落合
Original Assignee
京セラ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 京セラ株式会社 filed Critical 京セラ株式会社
Priority to CN201280037364.6A priority Critical patent/CN103717551B/zh
Priority to JP2013525642A priority patent/JP5693725B2/ja
Publication of WO2013015074A1 publication Critical patent/WO2013015074A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/265—Compositions containing one or more ferrites of the group comprising manganese or zinc and one or more ferrites of the group comprising nickel, copper or cobalt
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
    • 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
    • H01F1/34—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 non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/24—Magnetic cores
    • H01F27/255—Magnetic cores made from particles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C04B2235/85—Intergranular or grain boundary phases

Definitions

  • the present invention relates to a ferrite sintered body and a ferrite core formed by winding a metal wire around the ferrite sintered body.
  • the core part is an inductor, transformer, ballast, electromagnet, noise filter. Similar to the above, a ferrite sintered body is used. Such a core is required to have a high magnetic permeability. For this reason, among ferrite sintered bodies, Mn—Zn ferrite sintered bodies having high magnetic permeability have been widely used. However, Mn—Zn ferrite has a problem of low specific resistance (electric resistance).
  • Ni—Zn ferrite is known as a ferrite having a specific resistance approximately two orders of magnitude higher than that of Mn—Zn ferrite.
  • Patent Document 1 discloses that 45.0 to 50.0 mol% of Fe converted to Fe 2 O 3 , 5.0 to 10.0 mol% of Ni converted to NiO, 5.0 to 15.0 mol% converted to CuO, When Zn is converted to ZnO, 25.0 to 35.0 mol%, at least one metal selected from Mo, W, V, Cr, Mg, Ca, Sr and Ba and Mn are respectively added to MoO 3 , WO and V 2 O 5. , Cr 2 O 3 , MgO, CaO, SrO, BaO, and Mn 3 O 4 in total 0.1 to 3.0 mol%, and an oxide magnetic material containing Li in Li 2 O 0.01 to 3.0 mol% Proposed.
  • Patent Document 1 Although the oxide magnetic material of Patent Document 1 has a high specific resistance, there is a problem that the magnetic permeability shown in the examples is only 2000 at the highest, and the magnetic permeability is low.
  • the ferrite sintered body needs to have no characteristic change when the use environment temperature changes due to heat generated from mounted parts such as various IT-related devices, the specific resistance, In addition to high magnetic permeability and Curie temperature, there is a demand for a low temperature change rate of magnetic permeability at room temperature (25 ° C.) to 100 ° C.
  • the present invention relates to a ferrite sintered body having a high specific resistance, magnetic permeability, and Curie temperature and a small temperature change rate of magnetic permeability from room temperature (25 ° C.) to 100 ° C., and a pulse formed by winding a metal wire around the ferrite sintered body.
  • the object is to provide a transformer core.
  • the ferrite sintered body of the present invention comprises Fe of 49 mol% or more and 50 mol% or less in terms of Fe 2 O 3 , Zn of 32 mol% or more and 34.5 mol% or less in terms of ZnO, among 100 mol% of the main component composition, Ni That the content of ZnO is 6.5 mol% to 12.5 mol% in terms of NiO and Cu is 5 mol% to 9 mol% in terms of CuO, and that ZnO is present at the grain boundaries of the ferrite crystal composed of the main component. It is a feature.
  • the ferrite core of the present invention is characterized in that a metal wire is wound around the ferrite sintered body having the above configuration.
  • ferrite sintered body of the present invention a ferrite sintered body having a high specific resistance, magnetic permeability and Curie temperature and a small temperature change rate of magnetic permeability from room temperature (25 ° C.) to 100 ° C. can be obtained.
  • ferrite core of the present invention a ferrite core having stable and good performance in a wide temperature range from a low temperature range to a high temperature range can be obtained.
  • FIG. 1 An example of the ferrite sintered compact of this embodiment is shown, (a) is a perspective view of a toroidal core, (b) is a perspective view of a bobbin core. It is a schematic diagram which shows an example of the crystal structure of the ferrite sintered compact of this embodiment.
  • the ferrite sintered body of the present embodiment has an inductor, a transformer, a ballast, an electromagnet, a noise filter, and recently, a personal computer, a digital TV, an AV, by winding a metal wire around the ferrite sintered body as a core. It is used for a pulse transformer for the purpose of insulation, noise removal, etc., which is mounted on a LAN interface unit equipped in equipment.
  • the ferrite sintered body of the present embodiment constituting such a ferrite core has a high specific resistance, magnetic permeability ( ⁇ ), and Curie temperature (Tc), in addition to various IT-related devices, for example. Since it is necessary that the characteristics do not change when the operating environment temperature changes due to the heat generated from the mounted components, the temperature change rate of the magnetic permeability at 25 ° C. to 100 ° C. is required to be small.
  • the ferrite sintered body of the present embodiment satisfy this requirement, among the main component composition 100 mol%, the Fe Fe 2 O 3 50 mol% 49 mol% or more in terms of less, and Zn in terms of ZnO Grain boundaries of ferrite crystals comprising 32 mol% to 34.5 mol%, Ni containing 6.5 mol% to 12.5 mol% in terms of NiO and Cu containing 5 mol% to 9 mol% in terms of CuO It is characterized in that ZnO is present in (hereinafter also simply referred to as a crystal grain boundary).
  • the reason why the main component is in the composition range described above is that a ferrite sintered body having a high specific resistance, magnetic permeability, and Curie temperature can be obtained.
  • the Fe is less than 49 mol% calculated as Fe 2 O 3, there is a tendency for permeability is low, tends to decrease the specific resistance exceeds 50 mol%.
  • Zn is less than 32 mol% in terms of ZnO
  • the magnetic permeability tends to be low, and when it exceeds 34.5 mol%, the Curie temperature tends to decrease.
  • Ni is less than 6.5 mol% in terms of NiO
  • the Curie temperature tends to decrease, and when it exceeds 12.5 mol%, the magnetic permeability tends to decrease.
  • Cu is less than 5 mol% in terms of CuO, the magnetic permeability tends to be low, and if it exceeds 9 mol%, the Curie temperature tends to be low.
  • the mass in terms of oxides of Fe, Zn, Ni, and Cu constituting the main component should occupy 95% by mass or more when all the components constituting the ferrite sintered body are 100% by mass.
  • content of Fe, Zn, Ni, and Cu using an ICP (Inductively Coupled Plasma) emission spectroscopic analyzer or a fluorescent X-ray analyzer May be converted into Fe 2 O 3 , ZnO, NiO, and CuO, the molar value may be calculated from each molecular weight, and the occupation ratio of each molar value in the total of the calculated molar values may be calculated.
  • ICP Inductively Coupled Plasma
  • a hexagonal shape shown in FIG. 2 is a ferrite crystal 2 composed of the above-described main components, and a boundary between the ferrite crystals 2 is a crystal grain boundary 3.
  • the presence of ZnO indicated by reference numeral 1 at the grain boundary 3 suppresses the interaction of magnetic force between the ferrite crystals 2, so that the temperature change of the magnetic permeability The rate can be reduced.
  • the ferrite sintered body is cut and the cross section is mirror finished. Then, a mirror-processed cross section is observed with a transmission electron microscope (TEM) to confirm the presence or absence of the compound at the crystal grain boundary, and the crystal structure of the compound is confirmed using the attached energy dispersive X-ray diffractometer. Thus, it can be confirmed whether or not ZnO exists in the crystal grain boundaries 3.
  • TEM transmission electron microscope
  • a method for measuring specific resistance, magnetic permeability, Curie temperature, and magnetic permeability temperature change rate will be described.
  • specific resistance for example, a plate-shaped sample having a diameter of 10 to 20 mm and a thickness of 0.5 to 2 mm is prepared, and an applied voltage of 1000 V and a temperature of 26 are measured using a super insulation resistance meter (DSM-8103 manufactured by TOA). What is necessary is just to measure by 3 terminal method (JIS K6271; double ring electrode method) in the measurement environment of °C and humidity 36%.
  • the sample may be measured under the condition of a frequency of 100 kHz using an LCR meter.
  • a sample for example, a ring-shaped toroidal core 10 made of a ferrite sintered body shown in FIG. 1A having an outer diameter of 13 mm, an inner diameter of 7 mm, and a thickness of 3 mm is used.
  • a wire with a wire diameter of 0.2 mm wound around the entire circumference is used 10 times.
  • the Curie temperature can be obtained by a bridge circuit method using an LCR meter using a sample similar to that at the time of permeability measurement.
  • the temperature change rate of the magnetic permeability may be measured by using a similar sample and connecting it to a measurement jig in a thermostatic bath.
  • the measurement jig is connected to an LCR meter, measured at a frequency of 100 kHz, the magnetic permeability at 25 ° C. is ⁇ 25 , and the highest magnetic permeability when the temperature is raised from 25 ° C. to 100 ° C. is ⁇ 100 , ( ⁇ 100 ⁇ 25 ) / ⁇ 25 ⁇ 100.
  • the ferrite sintered body of the present embodiment has a high specific resistance, magnetic permeability, and Curie temperature, and has a small temperature change rate of magnetic permeability.
  • the specific resistance is 10 7 ⁇ ⁇ m or more
  • the permeability is 2700 or more
  • the Curie temperature is 75 ° C. or more
  • the temperature change rate of the permeability at 25 ° C. to 100 ° C. can be 30% or less.
  • the area occupation ratio of ZnO is 0.1% or more and 3.0% or less.
  • the area occupancy of ZnO is one field when measuring a mirror-finished cross section of a ferrite sintered body using a wavelength dispersive X-ray microanalyzer (JXA-8100 manufactured by JEOL), for example, 70 ⁇ m. It is an area ratio occupied by ZnO in an area of 4900 ⁇ m 2 of ⁇ 70 ⁇ m.
  • the method for calculating the occupation area ratio is as follows. First, Zn is measured using a wavelength dispersive X-ray microanalyzer (JXA-8100 manufactured by JEOL). A mapping is used in which the intensity of characteristic X-rays detected at each analysis point in one field of view is recorded in the XY coordinates. When ZnO is present at the grain boundary, the mapping shows a high value of the characteristic X-ray intensity of Zn. Therefore, a portion showing a value 20% or more higher than the average value of the characteristic X-ray intensity of Zn in this mapping is regarded as a portion where ZnO is present at the crystal grain boundary, and the area of this portion is the viewing area. By dividing by 4900 ⁇ m 2 and expressing as a percentage, the area occupation ratio of ZnO can be obtained.
  • the magnetic permeability can be improved and the temperature change of the magnetic permeability can be suppressed by suppressing the interaction of magnetic force between ferrite crystals. The rate can be further reduced.
  • the ferrite sintered compact of this embodiment contains 0.05 mass% or more and 0.3 mass% or less in terms of MnO 2 with respect to 100 mass% of the main component having the above composition range. Since Mn can have a plurality of valences, MnO 2 and Mn 3 O 4 existing as oxides are changed in valence to MnO by heating, and the excess oxygen component accompanying the change is the crystal of the main component. By filling oxygen defects, the magnetic permeability can be improved.
  • the ferrite sintered compact of this embodiment contains 0.01 mass% or more and 0.3 mass% or less of Mo in conversion of MoO 3 with respect to 100 mass% of the main component having the composition range described above.
  • Mo can promote the crystal grain growth of the main component, and the magnetic permeability can be improved by setting the content within the above-described range.
  • Si and Ca oxides may be included.
  • the specific resistance can also be improved by including this Si or Ca oxide.
  • the oxide of Si or Ca it is preferable that it is 0.4 mass% or less in total in which Si is converted into SiO 2 and Ca is converted into CaO with respect to 100 mass% of the main component.
  • the contents of Mo and Mn are obtained using an ICP emission spectroscopic analyzer or a fluorescent X-ray analyzer, and converted to MoO 3 and MnO 2 , respectively.
  • the value for can be calculated.
  • Si and Ca are the same applies to Si and Ca.
  • the ferrite core formed by winding a metal wire around the ferrite sintered body of the present embodiment uses a ferrite sintered body having a high specific resistance, magnetic permeability, and Curie temperature, and a low rate of change in the temperature of the magnetic permeability.
  • a ferrite core that has stable and good performance, and can be suitably used for inductors, transformers, ballasts, electromagnets, noise filters, personal computers, digital TVs, It can also be suitably used for a pulse transformer mounted on a LAN interface unit equipped in an AV device.
  • an oxide of Fe, Zn, Ni, Cu or a metal salt such as carbonate or nitrate that generates an oxide by firing is prepared.
  • the average particle size at this time is, for example, 0.5 ⁇ m when Fe is iron oxide (Fe 2 O 3 ), Zn is zinc oxide (ZnO), Ni is nickel oxide (NiO), and Cu is copper oxide (CuO). It is 5 ⁇ m or less.
  • the ferrite sintered body has 32 mol% or more and 34.5 mol% in terms of ZnO. Since it is contained below, the starting material is weighed by subtracting the amount added after calcination.
  • Fe, Ni, and Cu Fe is 49 mol% or more and 50 mol% or less in terms of Fe 2 O 3
  • Ni is 6.5 mol% or more and 12.5 mol% or less in terms of NiO
  • Cu is 5 mol% or more in terms of CuO. Weigh so that the composition range is 9 mol% or less.
  • each powder constituting the main component weighed as a starting material is pulverized and mixed with a ball mill or a vibration mill, and then calcined at a temperature of 700 ° C. or higher and 750 ° C. or lower for 2 hours or longer to obtain a calcined body synthesized into ferrite Get.
  • a predetermined amount of zinc oxide serving as a ZnO source to be present at the crystal grain boundaries is weighed, and put into a ball mill, a vibration mill or the like together with the calcined body and a solvent and pulverized and mixed.
  • the addition amount of a zinc oxide is 0.001 mol% or more and 0.02 mol% or less in conversion of ZnO.
  • the average particle diameter of the zinc oxide added here is 2 micrometers or more and 4 micrometers or less. The reason why the average particle diameter of zinc oxide is 2 ⁇ m or more and 4 ⁇ m or less is that the zinc oxide to be added does not easily dissolve in the ferrite crystal but is dispersed in the crystal grain boundaries of the ferrite sintered body.
  • a predetermined amount of binder is added and it is set as a slurry, It granulates using a spray granulator (spray dryer), and obtains a spherical granule.
  • this spherical granule is press-molded to obtain a molded body having a predetermined shape.
  • the molded body is degreased in a degreasing oven in the range of 400 to 800 ° C. to obtain a degreased body, and then this is fired in a firing furnace in the range of 1000 to 1200 ° C. for 2 to 5 hours.
  • firing is preferably performed with the degreased body completely covered with a refractory material in order to prevent evaporation of the Fe and Zn components.
  • molybdenum oxide (MoO 3 ) or manganese oxide (MnO 2 ) may be prepared and added during pulverization after calcination.
  • MoO 3 molybdenum oxide
  • MnO 2 manganese oxide
  • Si and Ca silicon oxide (SiO 2 ) and calcium oxide (CaO) may be prepared and added during pulverization after calcination.
  • Mn since it is preferable that Mn is contained in an amount of 0.05% by mass or more and 0.3% by mass or less in terms of MnO 2 with respect to 100% by mass of the main component of the ferrite sintered body, is taken as 100 mass% of the mass of the main components plus the zinc oxide to be added later, contrary, is preferably 0.05 mass% or more and 0.3 mass% or less with MnO 2 basis.
  • Mo since it is preferable to include Mo in an amount of 0.01% by mass or more and 0.3% by mass or less in terms of MoO 3 with respect to 100% by mass of the main component of the ferrite sintered body, when the mass of the main component added with zinc oxide to be added later is 100% by mass, it is preferably in the range of 0.01% by mass to 0.3% by mass in terms of MoO 3 .
  • Ca and Si it is preferable that the total mass converted to CaO and SiO 2 is set to 0.4% by mass or less with respect to 100% by mass.
  • Samples No. 1 and No. 18 with no zinc oxide added after calcining 1 to 17 and sintered bodies were produced, and the presence or absence of ZnO at the grain boundaries, magnetic permeability, Curie temperature, and room temperature (25 ° C.) to 100 ° C.
  • a test was conducted to measure the rate of change in permeability with temperature.
  • powders of iron oxide, zinc oxide, nickel oxide and copper oxide having an average particle diameter of 1 ⁇ m were prepared and weighed so as to have the ratio shown in Table 1.
  • zinc oxide the quantity except the addition amount after calcination was used for the starting material.
  • Each powder constituting the main component weighed as a starting material was pulverized and mixed with a vibration mill, and calcined at 750 ° C. for 2 hours to obtain a calcined body.
  • the amount of zinc oxide powder shown in Table 1 is weighed, put into a ball mill with a calcined body and a solvent and pulverized, and then a binder is added to form a slurry, which is prepared using a spray granulator (spray dryer). Granulated to give spherical granules.
  • the zinc oxide powder added after calcination had an average particle size of 3 ⁇ m.
  • this spherical granule was press-molded to obtain a molded body that becomes a toroidal core 10 having the shape shown in FIG.
  • the compact was subjected to a degreasing process at 600 ° C. in a degreasing furnace to obtain a degreased body.
  • the degreased bodies are arranged on a fired shelf made of a refractory material, and the degreased body is completely covered with a block-shaped refractory material, and then in an atmospheric firing furnace at 1000 to 1200 ° C. for 2 hours. Hold and fired.
  • grinding was performed, and sample No. 1 consisting of a toroidal core 10 having the shape shown in FIG. 1 to 17 ferrite sintered bodies were obtained.
  • Sample No. No. 18 was obtained by the same production method as described above except that zinc oxide powder was not added after calcination.
  • a coated copper wire having a wire diameter of 0.2 mm was wound 10 times around the entire circumference of the winding portion 10a of each sample, and the magnetic permeability at a frequency of 100 kHz was measured using an LCR meter.
  • the Curie temperature was determined by the bridge circuit method.
  • the sample similar to the measurement of magnetic permeability it connected to the measurement jig
  • This measuring jig is connected to an LCR meter, and measured at a frequency of 100 kHz.
  • the magnetic permeability at 25 ° C. is ⁇ 25
  • the highest magnetic permeability when the temperature is raised from 25 ° C. to 100 ° C. is ⁇ 10
  • the temperature change rate of the magnetic permeability from 25 ° C. to 100 ° C. was determined by the calculation formula of ( ⁇ 100 ⁇ 25 ) / ⁇ 25 ⁇ 100.
  • the sample was cut and the cross section was mirror-finished, and the mirror-processed cross section was observed with a transmission electron microscope to confirm the presence of the compound at the crystal grain boundary.
  • the crystal structure of the compound was confirmed using a dispersive X-ray diffractometer.
  • the main component composition was as shown in Table 1.
  • ZnO it confirmed that it was the mol% which added ZnO which is a main component in Table 1, and ZnO added after calcination. The results are shown in Table 1.
  • 2, 3, 6, 7, 10, 11, 14, 15, and 17 have a permeability of 2700 or more, a Curie temperature of 75 ° C or more, and a temperature change rate of permeability of 25 ° C to 100 ° C of 30% The following were confirmed to have good characteristics.
  • FIG. 1A shows an outer diameter of 13 mm, an inner diameter of 7 mm, and a thickness of 3 mm according to the same production method as in Example 1 except that the amount and particle size of zinc oxide added after calcination were changed.
  • Sample No. comprising the toroidal core 10 having the shape shown in FIG. 19-30 ferrite sintered bodies were obtained.
  • the magnetic permeability and the temperature change rate of the magnetic permeability were measured by the same method as in Example 1.
  • the sample was cut and the cross section was mirror-finished, Zn was measured using a wavelength dispersive X-ray microanalyzer (JXA-8100, manufactured by JEOL Ltd.), and each analysis point within one field of view (70 ⁇ m ⁇ 70 ⁇ m)
  • JXA-8100 manufactured by JEOL Ltd.
  • a mapping was obtained in which the intensity of the characteristic X-ray detected in step 1 was recorded in the XY coordinates.
  • ZnO is present at the crystal grain boundary, the intensity of the characteristic X-ray of Zn is high in this mapping, so that it is 20% or more than the average value of the characteristic X-ray intensity of Zn in this mapping.
  • the area occupied by ZnO present at the grain boundary is expressed by expressing the high part as ZnO at the grain boundary and dividing the area of this part by the viewing area of 4900 ⁇ m 2 as a percentage. Asked. The results are shown in Table 2. In addition, about the main component composition of each sample, it confirmed that it was as having described in Table 2 by the method similar to Example 1.
  • FIG. 1 The area occupied by ZnO present at the grain boundary is expressed by expressing the high part as ZnO at the grain boundary and dividing the area of this part by the viewing area of 4900 ⁇ m 2 as a percentage. Asked. The results are shown in Table 2. In addition, about the main component composition of each sample, it confirmed that it was as having described in Table 2 by the method similar to Example 1. FIG.
  • sample Nos. With an area occupancy of ZnO existing at the grain boundaries of 0.1% or more and 3% or less. Samples Nos. 20 to 24 and 26 to 30 have sample numbers of less than 0.1% or more than 3.0% of the occupied area of ZnO existing at the grain boundaries. It was confirmed that the magnetic permeability or the temperature change rate of the magnetic permeability was better than 19 and 25.
  • sample No. Sample No. 28 is the same as sample No. 28, but the content in terms of MnO 2 is varied. 31 to 38 were prepared, and the permeability was measured by the same method as in Example 1. The addition of MnO 2 was performed during pulverization after calcination.
  • the main component composition was calculated by the same method as in Example 1 and confirmed to be as shown in Table 3.
  • Mn using a fluorescent X-ray analyzer, in terms of MnO 2 in search of metallic element content was calculated mass for the main component of 100% by mass. The results are shown in Table 3.
  • the magnetic permeability can be improved by containing Mn in an amount of 0.05% by mass or more and 0.3% by mass or less in terms of MnO 2 with respect to 100% by mass of the main component.
  • sample No. Sample No. 33 was the same as Sample No. 33, but the content in terms of MoO 3 was varied. 39 to 46 were prepared, and the permeability was measured by the same method as in Example 1. The addition of MoO 3 was carried out in the same manner as MnO 2 during pulverization after calcination.
  • the main component composition was calculated by the same method as in Example 1 and confirmed to be as shown in Table 4. Further, Mn, for Mo, using a fluorescent X-ray analyzer, respectively seeking metal element content in terms of MnO 2, MoO 3, was calculated mass for the main component of 100% by mass. The results are shown in Table 4.
  • the permeability can be improved by containing Mo in an amount of 0.01% by mass to 0.3% by mass in terms of MoO 3 with respect to 100% by mass of the main component.
  • sample no. Nos. 41 to 43 obtained high magnetic permeability, and it was found that it is more preferable to contain Mo in an amount of 0.05% by mass or more and 0.2% by mass or less in terms of MoO 3 with respect to 100% by mass of the main component.
  • ZnO (zinc oxide) 2 Ferrite crystal 3: Grain boundary 10: Toroidal core 10a: Winding part 20: Bobbin core

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Magnetic Ceramics (AREA)
  • Soft Magnetic Materials (AREA)
  • Compounds Of Iron (AREA)
PCT/JP2012/066755 2011-07-28 2012-06-29 フェライト焼結体およびこれを備えるフェライトコア WO2013015074A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201280037364.6A CN103717551B (zh) 2011-07-28 2012-06-29 铁氧体烧结体及具备它的铁氧体磁芯
JP2013525642A JP5693725B2 (ja) 2011-07-28 2012-06-29 フェライト焼結体およびこれを備えるフェライトコア

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-165653 2011-07-28
JP2011165653 2011-07-28
JP2011234069 2011-10-25
JP2011-234069 2011-10-25

Publications (1)

Publication Number Publication Date
WO2013015074A1 true WO2013015074A1 (ja) 2013-01-31

Family

ID=47600929

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/066755 WO2013015074A1 (ja) 2011-07-28 2012-06-29 フェライト焼結体およびこれを備えるフェライトコア

Country Status (3)

Country Link
JP (1) JP5693725B2 (zh)
CN (1) CN103717551B (zh)
WO (1) WO2013015074A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2550376B (en) * 2016-05-17 2018-07-11 Thales Holdings Uk Plc Magnetic phase transition exploitation for enhancement of electromagnets
CN112430102A (zh) * 2020-12-08 2021-03-02 江门安磁电子有限公司 一种铁氧体颗粒料及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104078186A (zh) * 2014-06-27 2014-10-01 霍山东磁电子有限公司 一种锌基铁氧体磁芯材料
JP2023042387A (ja) * 2021-09-14 2023-03-27 株式会社村田製作所 磁器組成物および巻線型コイル部品

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06295811A (ja) * 1993-02-10 1994-10-21 Kawasaki Steel Corp 酸化物軟質磁性材料
JPH09270313A (ja) * 1996-03-29 1997-10-14 Taiyo Yuden Co Ltd フエライト材料及びフェライト及びその製造方法
JP2001284117A (ja) * 2000-03-30 2001-10-12 Tdk Corp コモンモードチョークコイル、コモンモードチョークコイル用フェライト焼結体
JP2004107158A (ja) * 2002-09-19 2004-04-08 Kyocera Corp 低損失フェライト材料及びこれを用いたフェライトコア
JP2004323283A (ja) * 2003-04-23 2004-11-18 Tdk Corp フェライト焼結体、フェライト焼結体の製造方法
WO2008132834A1 (ja) * 2007-04-24 2008-11-06 Toda Kogyo Corporation Ｎｉ－Ｚｎ－Ｃｕ系フェライトの粉末、グリーンシート及び焼結体
WO2012018052A1 (ja) * 2010-08-03 2012-02-09 京セラ株式会社 フェライト焼結体およびこれを備えるノイズフィルタ

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7195717B2 (en) * 2003-07-28 2007-03-27 Kyocera Corporation Ferrite core for RFID application, method of manufacturing the same, and ferrite coil using the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06295811A (ja) * 1993-02-10 1994-10-21 Kawasaki Steel Corp 酸化物軟質磁性材料
JPH09270313A (ja) * 1996-03-29 1997-10-14 Taiyo Yuden Co Ltd フエライト材料及びフェライト及びその製造方法
JP2001284117A (ja) * 2000-03-30 2001-10-12 Tdk Corp コモンモードチョークコイル、コモンモードチョークコイル用フェライト焼結体
JP2004107158A (ja) * 2002-09-19 2004-04-08 Kyocera Corp 低損失フェライト材料及びこれを用いたフェライトコア
JP2004323283A (ja) * 2003-04-23 2004-11-18 Tdk Corp フェライト焼結体、フェライト焼結体の製造方法
WO2008132834A1 (ja) * 2007-04-24 2008-11-06 Toda Kogyo Corporation Ｎｉ－Ｚｎ－Ｃｕ系フェライトの粉末、グリーンシート及び焼結体
WO2012018052A1 (ja) * 2010-08-03 2012-02-09 京セラ株式会社 フェライト焼結体およびこれを備えるノイズフィルタ

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2550376B (en) * 2016-05-17 2018-07-11 Thales Holdings Uk Plc Magnetic phase transition exploitation for enhancement of electromagnets
AU2017203188B2 (en) * 2016-05-17 2018-09-13 Thales Holdings Uk Plc Magnetic phase transition exploitation for enhancement of electromagnets
US10894588B2 (en) 2016-05-17 2021-01-19 Thales Holdings Uk Plc Magnetic phase transition exploitation for enhancement of electromagnets
CN112430102A (zh) * 2020-12-08 2021-03-02 江门安磁电子有限公司 一种铁氧体颗粒料及其制备方法

Also Published As

Publication number Publication date
JPWO2013015074A1 (ja) 2015-02-23
CN103717551A (zh) 2014-04-09
CN103717551B (zh) 2016-02-17
JP5693725B2 (ja) 2015-04-01

Similar Documents

Publication Publication Date Title
JP5960904B2 (ja) フェライト焼結体およびフェライトコアならびにコイル部品
JP5752125B2 (ja) フェライト焼結体およびこれを備えるノイズフィルタ
TWI712575B (zh) 鐵氧體組合物和層疊電子部件
US10839995B2 (en) Ferrite composition and multilayer electronic component
JP5898313B2 (ja) フェライト焼結体およびフェライトコアならびにコイル部品
JP5693725B2 (ja) フェライト焼結体およびこれを備えるフェライトコア
JP4826093B2 (ja) フェライト、電子部品及びそれらの製造方法
US11373789B2 (en) Ferrite sintered body and electronic component using thereof
JP5734078B2 (ja) フェライト焼結体およびこれを備えるノイズフィルタ
JP5871017B2 (ja) 磁性体材料およびそれを用いて形成したコアを備える巻線型コイル部品
JP5836887B2 (ja) フェライト焼結体およびこれを備えるノイズフィルタ
JP5733995B2 (ja) フェライト焼結体およびこれを備えるノイズフィルタ
JP5882811B2 (ja) フェライト焼結体およびこれを備えるパルストランス用コア
JP5952123B2 (ja) フェライト焼結体およびこれを備えるノイズフィルタ
JP2022059859A (ja) ＭｎＺｎ系フェライト、及びその製造方法
JP2016094321A (ja) フェライト焼結体およびノイズフィルタ
JP6408323B2 (ja) フェライト焼結体およびフェライトコアならびにコイル部品
JP2015113247A (ja) フェライト組成物、フェライトコアおよび電子部品
JP2023097903A (ja) ジルコニア質セッタおよびＭｎＺｎ系フェライトの製造方法
JP2006143530A (ja) Ｎｉ−Ｚｎ系フェライト組成物および磁性素子
JP2023162551A (ja) Ｍｎ－Ｚｎ系フェライト、及びその製造方法
JP2012096952A (ja) フェライト焼結体および電子部品

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201280037364.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12818355

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013525642

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12818355

Country of ref document: EP

Kind code of ref document: A1