WO2011081397A2 - Procédé de production de ferrite de type y et ferrite de type y obtenue par ce procédé - Google Patents

Procédé de production de ferrite de type y et ferrite de type y obtenue par ce procédé Download PDF

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WO2011081397A2
WO2011081397A2 PCT/KR2010/009398 KR2010009398W WO2011081397A2 WO 2011081397 A2 WO2011081397 A2 WO 2011081397A2 KR 2010009398 W KR2010009398 W KR 2010009398W WO 2011081397 A2 WO2011081397 A2 WO 2011081397A2
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type ferrite
compound
zinc
ferrite
cobalt
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PCT/KR2010/009398
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Korean (ko)
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WO2011081397A3 (fr
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류병훈
성원모
금준식
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주식회사 이엠따블유
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Publication of WO2011081397A2 publication Critical patent/WO2011081397A2/fr
Publication of WO2011081397A3 publication Critical patent/WO2011081397A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • 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
    • C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
    • C04B35/2633—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing barium, strontium or calcium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0063—Mixed oxides or hydroxides containing zinc
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/006—Compounds containing, besides cobalt, 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties
    • 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
    • C04B2235/3215—Barium oxides 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/767—Hexagonal symmetry, e.g. beta-Si3N4, beta-Sialon, alpha-SiC or hexa-ferrites

Definitions

  • the present invention relates to a method for producing a wire type ferrite and a wire type ferrite produced thereby. More particularly, the present invention relates to a method for producing a w-type ferrite having a high permeability value in a high frequency band and a w-type ferrite manufactured thereby.
  • Ferrite is a solid solution in which alloying elements or impurities are dissolved in iron of a body-centered cubic crystal which is stable at 900 ° C. or lower.
  • ferrite is a metallographic term for steel, which is also called silicon ferrite or silicon iron by the name of solid solution or dissolved element based on ⁇ iron.
  • Such a ferrite is a single phase when viewed under a microscope.
  • the ferrite has a characteristic of mixing white portions of ferrite and black portions of perlite, and are used for magnetic heads such as high frequency transformers, pickups, and tape recorders.
  • Y-type ferrite which is a kind of hexagonal ferrite, is known as a material that can be used as an antenna, an electromagnetic wave absorber, etc. in the hundreds of MHz to several GHz.
  • the conventional wire type ferrite has a permeability value of 2 or less in the frequency band of 1 GHz to 3 GHz, that is, the conventional wire type ferrite has a low permeability value in a frequency band of 1 GHz or more, and thus requires a high frequency band of 1 GHz or more.
  • a raw material (antenna, radio wave absorber, etc.) of the device there is a problem that the conventional wire type ferrite is not suitable.
  • a method for producing a type of ferrite having a high permeability in the high frequency band of 1 GHz or more by substituting some of the cobalt ions contained in the type of ferrite with zinc ions and produced by The purpose is to provide a Y type ferrite.
  • the present invention to achieve the above object, Ba 2 Co 2-x Zn x Fe 12 O 22 Wow
  • the x-value range is 0.5 ⁇ x ⁇ 1.5 to provide a w-type ferrite.
  • the molar ratio of the barium compound, the cobalt compound, the iron compound and the zinc compound is 2: 2-x: x: 12, and the range of the x value is preferably 0.5 ⁇ x ⁇ 1.5.
  • the heat treatment step is to perform the first heat treatment at 300 °C to 500 °C and
  • It may include the step of performing a second heat treatment at 1100 °C to 1250 °C.
  • the barium compound may include barium nitrate (Ba (No 3 ) 2 ).
  • the cobalt compound may include cobalt nitrate hexahydrate (Co (No 3 ) 2 .6H 2 O).
  • the iron compound may include ferric nitrate hexahydrate (Fe (No 3 ) 3 .9H 2 0).
  • the zinc compound may include zinc nitrate hexahydrate (Zn (No 3 ) 2 .9H 2 0).
  • a w-type ferrite having a permeability of 2 or more can be produced even at a high frequency band of 1 GHz or more. There is an effect that can be used as a material of a communication device that requires a high frequency band.
  • FIG. 1 is a flow chart showing a manufacturing process of the w-type ferrite according to an embodiment of the present invention
  • FIG. 2 is a graph showing the permeability change of the Y type ferrite according to the molar ratio of zinc nitrate hydrate.
  • FIG. 3 is a view showing a change in the investment loss of the Y-type ferrite according to the molar ratio of zinc nitrate hydrate.
  • FIG. 1 is a flow chart showing a manufacturing method of the w-type ferrite according to an embodiment of the present invention.
  • W type ferrite according to an embodiment of the present invention is Ba 2 Co 2-x Zn x Fe 12 O 22 Wow With the same compositional formula, the x value ranges from 0.5 ⁇ x ⁇ 1.5 to vary the permeability value and the permeability loss value according to the molar ratio of zinc.
  • Initial raw materials for the production of such type ferrites include barium (Ba) compounds, cobalt (Co) compounds, iron (Fe) compounds and zinc (Zn) compounds
  • the barium compounds are barium chloride, barium nitride oxide and barium Any one of the sulfides
  • the cobalt compound is any one of cobalt chloride, cobalt nitrate and cobalt sulfide
  • the iron compound is any one of iron chloride, iron nitrate and iron sulfide
  • the zinc compound is zinc chloride, zinc nitrate and zinc sulfide Which is either.
  • barium may be replaced with strontium (Sr).
  • the barium compound is limited to barium nitrate (Ba (No 3 ) 2 ), which is a barium nitrate, and the cobalt compound is cobalt nitrate hexahydrate (Co (No 3 ) 2 .6H 2 O).
  • the iron compound is limited to ferric nitrate ferric nitrate hexahydrate (Fe (No 3 ) 3 ⁇ 9H 2 0), and the zinc compound is zinc nitrate zinc nitrate hexahydrate (Zn (No 3 ) 2 ⁇ 9H 2 Although limited to 0), it is a matter of course that the present invention is not limited thereto.
  • a portion of the cobalt ion (Co), which is a transition metal ion, is zinc as another transition metal.
  • the coprecipitation method is a method of precipitating the target ion in the mixed solution by adding a precipitant (solution) containing other ions to the mixed solution to precipitate the target ion and the other ions together, in the embodiment of the present invention, sodium hydroxide (NaOH) ) And the initial raw material are co-precipitated using a precipitant mixed with hydrogen peroxide (H 2 O 2 ) dissolved in water.
  • a precipitant solution
  • NaOH sodium hydroxide
  • an initial raw material that is, barium nitrate, cobalt nitrate hexahydrate, ferric nitrate hexahydrate and zinc nitrate hexahydrate are provided (S 110).
  • zinc nitrate hexahydrate is a raw material for substituting some of the cobalt ions contained in the w-type ferrite with zinc ions, barium nitrate, cobalt nitrate hexahydrate, ferric nitrate hexahydrate and zinc nitrate hydrate, ie, barium compound, nitrate
  • the molar ratio of the compound, the iron compound and the zinc compound is 2: 2-x: x: 12, and the range of x values, which is the molar ratio of zinc nitrate hexahydrate, is preferably 0.5 ⁇ x ⁇ 1.5.
  • the range of x values which is the molar ratio of zinc nitrate hexahydrate
  • Barium nitrate, cobalt nitrate hexahydrate, ferric nitrate 9 hydrate, and zinc nitrate hexahydrate are mixed by completely dissolving barium nitrate, cobalt nitrate hexahydrate, ferric nitrate hydrate 9 and zinc nitrate hydrate 9 in water in the air.
  • a mixed solution is prepared, and a precipitant is added to the mixed solution to coprecipitate the mixed solution (S120, S130).
  • the precipitant is preferably a sodium hydroxide-hydrogen peroxide mixed solution in which a hydrogen peroxide solution of 1 to 4 times the stoichiometric amount capable of oxidizing 2 to 4 equivalents of sodium hydroxide and iron divalent ions is mixed.
  • the material precipitated through the step S130 that is, the precipitant is added to the mixed solution to wash and filter the co-precipitated metal hydroxide (S140).
  • This dried metal hydroxide is first heat-treated at a temperature of 300 °C to 500 °C (S150).
  • a primary heat processing temperature is 400 degreeC.
  • the first heat-treated metal hydroxide is second heat treatment at a temperature of 1100 °C to 1250 °C (S160).
  • secondary heat processing temperature is 1200 degreeC.
  • barium nitrate, cobalt nitrate hexahydrate, ferric nitrate hexahydrate and zinc nitrate hexahydrate are synthesized as a w-type ferrite having a compositional formula such as Ba 2 Co 2-x Zn x Fe 12 O 22 .
  • the first heat treatment temperature is limited to 300 ° C. to 500 ° C.
  • the second heat treatment temperature is limited to 1100 ° C. to 1250 ° C. in the step S160.
  • the permeability of the w - type ferrite (formula: Ba 2 Co 2-x Zn x Fe 12 O 22 ) according to the embodiment of the present invention increases when heat-treated at a second heat treatment temperature.
  • the Y according to the change in the molar ratio of zinc nitrate hexahydrate in the initial raw material for the manufacture of the w-type ferrite (Formula: Ba 2 Co 2- xZn x Fe 12 O 22 ) according to an embodiment of the present invention, that is, x value
  • x value Let me explain in detail the change in permeability and loss of type ferrite.
  • FIG. 2 is a view showing a change in permeability of the w-type ferrite according to the change in the molar ratio of zinc nitrate hydrate
  • Figure 3 is a view showing a change in the investment loss of the w-type ferrite according to the change in the molar ratio of zinc nitrate hydrate.
  • a wire type ferrite (Formula: Ba 2 Co 2-x Zn x Fe 12 O 22 ) as an antenna material of a high frequency band (1 GHz to 3 GHz)
  • a wire type ferrite (Formula: Ba 2 Co 2) -x Zn x Fe 12 O 22 ) must maintain a permeability value of 2 or more in the high frequency band and at the same time have a low permeability loss value, the molar ratio (x) of zinc nitrate hexahydrate that satisfies this in FIGS. It can be seen that is 0.5 and 1.0.
  • W-type ferrite (Formula: Ba 2 Co 2-x Zn x Fe 12 O 22 ) as a radio wave absorber that absorbs radio waves in the high frequency band (1GHz to 3GHz)
  • W-type ferrite (Formula: Ba 2 Co 2 -x Zn x Fe 12 O 22 ) has to maintain a high permeability value of at least 2 in the high frequency band and at the same time have a high permeability loss value, the molar ratio (x) of zinc nitrate hexahydrate that satisfies this in Figs. It can be seen that it is 1.5.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Power Engineering (AREA)
  • Compounds Of Iron (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Magnetic Ceramics (AREA)
  • Soft Magnetic Materials (AREA)

Abstract

La présente invention concerne un procédé de production de ferrite de type Y de formule Ba2Co2-xZnxFe12O22, et une ferrite de type Y obtenue par ce procédé. Dans ladite formule, la gamme des valeurs de x est 0,5 ≤ x ≤ 1,5. L'invention offre l'avantage que la ferrite de type Y peut être utilisée comme matière première pour des dispositifs de communications dans lesquels une bande haute fréquence est requise, puisqu'il permet de produire de la ferrite de type Y présentant une perméabilité magnétique d'au moins 2, même dans des bandes haute fréquence de plus de 1 GHz, par remplacement d'une partie des ions de cobalt présents dans la ferrite de type Y par des ions de zinc.
PCT/KR2010/009398 2009-12-29 2010-12-28 Procédé de production de ferrite de type y et ferrite de type y obtenue par ce procédé WO2011081397A2 (fr)

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KR1020090132286A KR20110075745A (ko) 2009-12-29 2009-12-29 와이 타입 페라이트 제조 방법 및 이에 의해 제조된 와이 타입 페라이트
KR10-2009-0132286 2009-12-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130169488A1 (en) * 2011-12-28 2013-07-04 Samsung Electronics Co., Ltd. Magnetic substance and composite material for antennas employing the same
CN115196955A (zh) * 2022-08-01 2022-10-18 苏州银琈玛电子科技有限公司 Y型六角铁氧体材料、其制备方法以及微波器件

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4778734A (en) * 1987-02-03 1988-10-18 Ube Industries, Ltd. Barium ferrite magnetic powder and magnetic recording medium containing the same
KR950008967B1 (ko) * 1992-08-14 1995-08-10 학교법인제철학원 Y-형 육방정 페라이트 분말의 제조방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR950008967A (ko) * 1993-09-03 1995-04-21 단흥덕 조수추력 발전씨스텀의 수압장치

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4778734A (en) * 1987-02-03 1988-10-18 Ube Industries, Ltd. Barium ferrite magnetic powder and magnetic recording medium containing the same
KR950008967B1 (ko) * 1992-08-14 1995-08-10 학교법인제철학원 Y-형 육방정 페라이트 분말의 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LEE, JONG HYEOP ET AL. JOURNAL OF KOREAN MAGNETICS SOCIETY vol. 4, 1994, pages 114 - 121 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130169488A1 (en) * 2011-12-28 2013-07-04 Samsung Electronics Co., Ltd. Magnetic substance and composite material for antennas employing the same
CN115196955A (zh) * 2022-08-01 2022-10-18 苏州银琈玛电子科技有限公司 Y型六角铁氧体材料、其制备方法以及微波器件

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WO2011081397A3 (fr) 2011-11-17

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