JP6827584B1 - MnZn-based ferrite and its manufacturing method - Google Patents
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 230000005291 magnetic effect Effects 0.000 claims abstract description 76
- 230000035699 permeability Effects 0.000 claims abstract description 66
- 230000004907 flux Effects 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910007541 Zn O Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000010586 diagram Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000011162 core material Substances 0.000 description 17
- 239000008187 granular material Substances 0.000 description 11
- 238000004804 winding Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910007564 Zn—Co Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002907 paramagnetic material Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
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Abstract
【課題】広い温度域及び広い周波数帯に対して高い比初透磁率を有し、且つ、キュリー温度及び飽和磁束密度が高いＭｎＺｎ系フェライト及びその製造方法を提供する。【解決手段】Ｆｅ２Ｏ３とＺｎＯとＭｎＯを主成分とし、前記主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部がＭｎＯであり、前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有する、ＭｎＺｎ系フェライトである。【選択図】なしPROBLEM TO BE SOLVED: To provide an MnZn-based ferrite having a high relative initial magnetic permeability for a wide temperature range and a wide frequency band, and having a high Curie temperature and a high saturation magnetic flux density, and a method for producing the same. SOLUTION: Fe2O3, ZnO and MnO are the main components, and Fe2O3 is 51.3 to 54.5 mol%, ZnO is 9.0 to 14.3 mol%, and the balance is MnO in 100 mol% of the main components. Based on 100% by mass of the main component, 0.001 to 0.015% by mass of SiO2, 0.02 to 0.06% by mass of CaO, 0.03 to 0.07% by mass of ZrO2, and TiO2 as subcomponents. It is a MnZn-based ferrite containing 0.01 to 2.5% by mass and 0.15 to 0.45% by mass of Co2O3. [Selection diagram] None
Description
本発明は、ＭｎＺｎ系フェライト及びその製造方法に関する。 The present invention relates to MnZn-based ferrite and a method for producing the same.
テレビやエアコンなど家電機器等の電源ラインから発生するノイズを抑制するため、ＡＣラインフィルタなどコモンモードチョークコイルの開発が行われてきた。ＭｎＺｎ系フェライトは当該チョークコイルのコア材などとして用いられている。当該コア材は、ノイズを除去したい周波数においてノイズ電流に対する大きなインピーダンスが求められている。
特に近年では、１５０ｋＨｚから数ＭＨｚの領域におけるノイズ減衰能力（インピーダンス）を高めるため、コアとなるＭｎＺｎフェライトの透磁率の向上及び透磁率の周波数に対する安定性を高める開発が行われてきた。
Common mode choke coils such as AC line filters have been developed in order to suppress noise generated from power lines of home appliances such as televisions and air conditioners. MnZn-based ferrite is used as a core material for the choke coil. The core material is required to have a large impedance with respect to a noise current at a frequency at which noise is desired to be removed.
In particular, in recent years, in order to increase the noise attenuation capability (impedance) in the region of 150 kHz to several MHz, development has been made to improve the magnetic permeability of MnZn ferrite as a core and to improve the stability of the magnetic permeability with respect to the frequency.
例えば特許文献１及び２には、幅広い温度範囲で高い比初透磁率を有するＭｎ−Ｚｎ−Ｃｏ系フェライトとして、特定量のＦｅ２Ｏ３、ＺｎＯ、ＣｏＯ及びＭｎＯを基本成分とし、特定量のＳｉＯ２、ＣａＯ、及びＮｂ２Ｏ５を副成分として含み、炭素の含有量を０．００５０質量％以下に抑制したＭｎ−Ｚｎ−Ｃｏ系フェライトが開示されている。 For example, Patent Documents 1 and 2, as Mn-Zn-Co ferrite having a high specific initial permeability in a wide temperature range, a certain amount of Fe 2 O 3, ZnO, CoO, and MnO as basic components, a specific amount of Mn—Zn—Co-based ferrite containing SiO 2 , CaO, and Nb 2 O 5 as subcomponents and suppressing the carbon content to 0.0050% by mass or less is disclosed.
また、特許文献３には、温度依存性が小さく、直流磁場印加下でも広い温度範囲において高い実効透磁率を維持することができるＭｎＣｏＺｎフェライトとして、特定量のＦｅ２Ｏ３、ＺｎＯ、ＣｏＯ及びＭｎＯを基本成分とし、特定量のＳｉＯ２、ＣａＯ、及びＴｉＯ２を副成分として含み、Ｐ及びＢの含有量が３質量ｐｐｍ未満であるＭｎＣｏＺｎフェライトが開示されている。 Further, Patent Document 3 states that as MnCoZn ferrite, which has a small temperature dependence and can maintain a high effective magnetic permeability in a wide temperature range even when a DC magnetic field is applied, a specific amount of Fe 2 O 3 , ZnO, CoO and MnO. MnCoZn ferrite is disclosed, which contains a specific amount of SiO 2 , CaO, and TiO 2 as a sub-component, and has a P and B content of less than 3% by mass ppm.
また近年では、ＣＯ２排出削減や省エネルギーのニーズが高まり、ハイブリット車や電気自動車など車載の電装化が進んでおり、車載に関するノイズ規制をクリアするための検討が進められている。
中でも、電動コンプレッサにおけるインバータとモータからは、コモンモードノイズが発生することが明らかとなっており、ＡＣラインフィルタ等を用いたノイズ対策の必要性が増している。
Further, in recent years, the needs for CO 2 emission reduction and energy saving have been increasing, and the electrification of vehicles such as hybrid vehicles and electric vehicles is progressing, and studies for clearing noise regulations related to vehicles are being promoted.
Above all, it has been clarified that common mode noise is generated from the inverter and the motor in the electric compressor, and the need for noise countermeasures using an AC line filter or the like is increasing.
特許文献１及び２では、炭素の含有量を０．００５０質量％以下に抑制することで、−２０〜１５０℃の広い温度域において１０ｋＨｚにおける初透磁率が高められるとされている。
一方、車載用の電子部品などにおいては、高い温度環境に加えて、巻線に大電流を印加すること求められてきている。このような用途において、コア材となるＭｎＺｎ系フェライトには、比初透磁率のみだけはなく、キュリー温度及び飽和磁束密度が高いものが求められている。
According to Patent Documents 1 and 2, the initial magnetic permeability at 10 kHz can be increased in a wide temperature range of -20 to 150 ° C. by suppressing the carbon content to 0.0050% by mass or less.
On the other hand, in electronic components for automobiles and the like, it has been required to apply a large current to the winding in addition to a high temperature environment. In such applications, the MnZn-based ferrite used as the core material is required to have not only the relative initial magnetic permeability but also the Curie temperature and the saturation magnetic flux density.
本発明は上記の課題を解決するものであり、広い温度域及び広い周波数帯に対して高い比初透磁率を有し、且つ、キュリー温度及び飽和磁束密度が高いＭｎＺｎ系フェライト及びその製造方法を提供する。 The present invention solves the above-mentioned problems, and provides MnZn-based ferrite having a high relative initial magnetic permeability over a wide temperature range and a wide frequency band, and having a high Curie temperature and saturation magnetic flux density, and a method for producing the same. provide.
本発明に係るＭｎＺｎ系フェライトは、
Ｆｅ２Ｏ３とＺｎＯとＭｎＯを主成分とし、
前記主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部がＭｎＯであり、
前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有する。
The MnZn-based ferrite according to the present invention is
Fe 2 O 3 and ZnO and MnO are the main components
Of the 100 mol% of the main component, Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 9.0 to 14.3 mol%, and the balance is MnO.
The relative main component of 100% by mass, as an auxiliary component, the SiO 2 0.001 to 0.015 mass%, 0.02-0.06 mass% of CaO, a ZrO 2 0.03 to 0.07 wt% , TiO 2 in an amount of 0.01 to 2.5% by mass and Co 2 O 3 in an amount of 0.15 to 0.45% by mass.
上記ＭｎＺｎ系フェライトの一実施形態は、前記ＴｉＯ２の含有量が前記主成分１００質量％に対し、０．５〜２．５質量％である。 In one embodiment of the MnZn-based ferrite, the content of TiO 2 is 0.5 to 2.5% by mass with respect to 100% by mass of the main component.
上記ＭｎＺｎ系フェライトの一実施形態は、キュリー温度が２００℃以上、２３℃における飽和磁束密度が５００ｍＴ以上、２３℃における１０ｋＨｚ〜７００ｋＨｚの比初透磁率μ（２３℃）が４５００以上である。 In one embodiment of the MnZn-based ferrite, the Curie temperature is 200 ° C. or higher, the saturation magnetic flux density at 23 ° C. is 500 mT or higher, and the relative initial magnetic permeability μ (23 ° C.) at 23 ° C. of 10 kHz to 700 kHz is 4500 or higher.
上記ＭｎＺｎ系フェライトの一実施形態は、２３℃における１０ｋＨｚの比初透磁率μ（２３℃）に対する、１５０℃における１０ｋＨｚの比初透磁率μ（１５０℃）の比（μ（１５０℃）／μ（２３℃））が０．７５〜１．２５である。 In one embodiment of the MnZn-based ferrite, the ratio of the specific initial magnetic permeability μ (150 ° C.) of 10 kHz at 150 ° C. to the specific initial magnetic permeability μ (23 ° C.) of 10 kHz at 23 ° C. (μ (150 ° C.) / μ). (23 ° C.)) is 0.75 to 1.25.
上記ＭｎＺｎ系フェライトの一実施形態は、密度が４．９〜５．０５ｇ／ｃｃである。 One embodiment of the MnZn-based ferrite has a density of 4.9 to 5.05 g / cc.
上記ＭｎＺｎ系フェライトの一実施形態は、比抵抗が、５０〜５００Ω・ｃｍである。 One embodiment of the MnZn-based ferrite has a specific resistance of 50 to 500 Ω · cm.
本発明に係るＭｎＺｎ系フェライトの製造方法は、
前記本発明に係るＭｎＺｎ系フェライトの製造方法であって、
焼結後に、主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部がＭｎＯとなるように、各主成分を含む原料を混合する工程と、
得られた混合物に、焼結後に前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有するように、各副成分を含む原料を添加する工程を有する。
The method for producing MnZn-based ferrite according to the present invention is
The method for producing an MnZn-based ferrite according to the present invention.
After sintering, the raw material containing each main component is prepared so that Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 9.0 to 14.3 mol%, and the balance is MnO in 100 mol% of the main components. The process of mixing and
After sintering, the obtained mixture contains 0.001 to 0.015% by mass of SiO 2 , 0.02 to 0.06% by mass of CaO, and ZrO 2 as subcomponents with respect to 100% by mass of the main component. A raw material containing each subcomponent is added so as to contain 0.03 to 0.07% by mass, 0.01 to 2.5% by mass of TiO 2 , and 0.15 to 0.45% by mass of Co 2 O 3. Has a step to do.
上記ＭｎＺｎ系フェライトの製造方法の一実施形態は、前記ＳｉＯ２、ＺｒＯ２、ＴｉＯ２及びＣｏ２Ｏ３を含む原料が、平均粒子径が０．１μｍ以上の粒子である。 In one embodiment of the method for producing MnZn-based ferrite, the raw material containing the SiO 2 , ZrO 2 , TiO 2 and Co 2 O 3 is particles having an average particle diameter of 0.1 μm or more.
本発明により、広い温度域及び広い周波数帯に対して高い比初透磁率を有し、且つ、キュリー温度及び飽和磁束密度が高いＭｎＺｎ系フェライト及びその製造方法が提供される。 INDUSTRIAL APPLICABILITY The present invention provides an MnZn-based ferrite having a high relative initial magnetic permeability over a wide temperature range and a wide frequency band, and having a high Curie temperature and a high saturation magnetic flux density, and a method for producing the same.
以下、本発明に係るＭｎＺｎ系フェライト及びその製造法について説明する。
なお、数値範囲を示す「〜」は特に断りがない限り、その下限値及び上限値を含むものとする。
Hereinafter, the MnZn-based ferrite according to the present invention and a method for producing the same will be described.
Unless otherwise specified, "~" indicating the numerical range shall include the lower limit value and the upper limit value.
［ＭｎＺｎ系フェライト］
本発明に係るＭｎＺｎ系フェライト（以下、本ＭｎＺｎ系フェライトとも記す）は、Ｆｅ２Ｏ３とＺｎＯとＭｎＯを主成分とし、
前記主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部がＭｎＯであり、前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有する。
[MnZn-based ferrite]
MnZn ferrite according to the present invention (hereinafter, also referred to as the MnZn ferrite) is mainly composed of Fe 2 O 3 and ZnO and MnO,
Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 9.0 to 14.3 mol%, and the balance is MnO in 100 mol% of the main component. As a sub component with respect to 100 mass% of the main component. , SiO 2 0.001 to 0.015 mass%, CaO 0.02 to 0.06 mass%, ZrO 2 0.03 to 0.07 mass%, TiO 2 0.01 to 2.5 mass%. %, Co 2 O 3 is contained in an amount of 0.15 to 0.45% by mass.
上記本ＭｎＺｎ系フェライトは上記のように各金属酸化物を上記特定の割合で含むことにより、広い温度域及び広い周波数帯に対して高い比初透磁率を有し、且つ、キュリー温度及び飽和磁束密度が高いものとなる。具体的には、本ＭｎＺｎ系フェライトは、例えば、キュリー温度が２００℃以上、２３℃における飽和磁束密度が５００ｍＴ以上、２３℃における１０ｋＨｚ〜７００ｋＨｚの比初透磁率μ（２３℃）が４５００以上を達成する。更に本ＭｎＺｎ系フェライトは、例えば、１５０℃における１０ｋＨｚの比初透磁率μ（１５０℃）が４５００以上を達成することもできる。
一方で本ＭｎＺｎ系フェライトは、例えば、２３℃における１０ｋＨｚの比初透磁率μ（２３℃）に対する、１５０℃における１０ｋＨｚの比初透磁率μ（１５０℃）の比（μ（１５０℃）／μ（２３℃））を０．７５〜１．２５の範囲とすることもできる。本ＭｎＺｎ系フェライト１５０℃における比初透磁率が、２３℃における比初透磁率に対して高すぎないことで、高温環境下において大電流が印可された場合にも、飽和しにくいフェライトコア材として好適に用いることができる。
また、２３℃における周波数１０ｋＨｚの比初透磁率μ（１０ｋＨｚ）に対する、周波数７００ｋＨｚの比初透磁率μ（７００ｋＨｚ）の比（μ（７００ｋＨｚ）／μ（１０ｋＨｚ））を０．７５〜１．２とすることもできる。
このように本ＭｎＺｎ系フェライトは広い温度域及び広い周波数帯に対して高く安定した比初透磁率を有し、且つ、キュリー温度及び飽和磁束密度が高いという特徴を有する。そのため、本ＭｎＺｎ系フェライトを、例えば、コモンモードチョークコイルのコア材として使用することで、高温環境下において大電流が印可された場合にもノイズ減衰効果に優れたコモンモードチョークコイルを製造することができる。
By containing each metal oxide in the above-mentioned specific ratio as described above, the present MnZn-based ferrite has a high relative initial magnetic permeability in a wide temperature range and a wide frequency band, and has a Curie temperature and a saturation magnetic flux. The density will be high. Specifically, this MnZn-based ferrite has, for example, a Curie temperature of 200 ° C. or higher, a saturation magnetic flux density of 500 mT or higher at 23 ° C., and a relative initial magnetic permeability μ (23 ° C.) of 4500 or higher at 10 kHz to 700 kHz at 23 ° C. Achieve. Further, the MnZn-based ferrite can achieve, for example, a relative initial magnetic permeability μ (150 ° C.) of 10 kHz at 150 ° C. of 4500 or more.
On the other hand, in this MnZn-based ferrite, for example, the ratio of the specific initial magnetic permeability μ (150 ° C.) of 10 kHz at 150 ° C. to the specific initial magnetic permeability μ (23 ° C.) of 10 kHz at 23 ° C. (μ (150 ° C.) / μ (23 ° C.)) can also be in the range of 0.75 to 1.25. This MnZn-based ferrite as a ferrite core material that does not easily saturate even when a large current is applied in a high temperature environment because the relative initial magnetic permeability at 150 ° C. is not too high with respect to the specific initial magnetic permeability at 23 ° C. It can be preferably used.
Further, the ratio of the specific initial magnetic permeability μ (700 kHz) at a frequency of 700 kHz to the specific initial magnetic permeability μ (10 kHz) at a frequency of 10 kHz at 23 ° C. (μ (700 kHz) / μ (10 kHz)) is 0.75 to 1.2. It can also be.
As described above, this MnZn-based ferrite has a feature that it has a high and stable relative initial magnetic permeability in a wide temperature range and a wide frequency band, and also has a high Curie temperature and a high saturation magnetic flux density. Therefore, by using this MnZn-based ferrite as, for example, the core material of a common mode choke coil, it is possible to manufacture a common mode choke coil having an excellent noise attenuation effect even when a large current is applied in a high temperature environment. Can be done.
本ＭｎＺｎ系フェライトの、２３℃における１０ｋＨｚの比初透磁率μ（２３℃）；２３℃における７００ｋＨｚの比初透磁率μ（７００ｋＨｚ）；及び１５０℃における１０ｋＨｚの比初透磁率μ（１５０℃）は、各々独立に４５００以上であることが好ましい。いずれの比初透磁率も４５００以上であることで、広い温度域、広い周波数域において、安定して高い比初透磁率が維持される。 10 kHz specific initial permeability μ (23 ° C) at 23 ° C; 700 kHz specific initial permeability μ (700 kHz) at 23 ° C; and 10 kHz specific initial permeability μ (150 ° C) of this MnZn-based ferrite. Is preferably 4500 or more independently. When the relative initial magnetic permeability is 4500 or more, a high specific initial magnetic permeability can be stably maintained in a wide temperature range and a wide frequency range.
本ＭｎＺｎ系フェライトのキュリー温度は、高温環境下での長時間連続使用に好適に用いることができる点から、２００〜２５０℃が好ましい。なお、キュリー温度とは、強磁性体が常磁性体に変わる温度である。 The Curie temperature of the MnZn-based ferrite is preferably 200 to 250 ° C. from the viewpoint that it can be suitably used for long-term continuous use in a high temperature environment. The Curie temperature is a temperature at which a ferromagnet changes to a paramagnetic material.
本ＭｎＺｎ系フェライトの２３℃における飽和磁束密度は、巻線に大電流が印加された場合においても飽和しにくくノイズ減衰能力を維持できる点から、５００ｍＴ以上が好ましい。 The saturation magnetic flux density of the MnZn-based ferrite at 23 ° C. is preferably 500 mT or more because it is difficult to saturate even when a large current is applied to the winding and the noise attenuation capability can be maintained.
本ＭｎＺｎ系フェライトの密度は特に限定されないが、機械強度の点から密度が４．９〜５．０５ｇ／ｃｃが好ましい。後述する製造方法によれば比較的高密度のＭｎＺｎ系フェライトを製造することができる。 The density of the MnZn-based ferrite is not particularly limited, but the density is preferably 4.9 to 5.05 g / cc from the viewpoint of mechanical strength. According to the production method described later, a relatively high-density MnZn-based ferrite can be produced.
また、本ＭｎＺｎ系フェライトの比抵抗は、渦電流損失を抑制する点から、５０〜５００Ω・ｃｍが好ましい。 The specific resistance of the MnZn-based ferrite is preferably 50 to 500 Ω · cm from the viewpoint of suppressing eddy current loss.
上記の各物性は本ＭｎＺｎ系フェライトに含まれる金属酸化物の組成により調整できる。
本ＭｎＺｎ系フェライトはＦｅ２Ｏ３とＺｎＯとＭｎＯを主成分とする。当該主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３は５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部（３１．２〜３９．７ｍｏｌ％）がＭｎＯである。
Each of the above physical properties can be adjusted by the composition of the metal oxide contained in the MnZn-based ferrite.
This MnZn-based ferrite contains Fe 2 O 3 , ZnO, and MnO as main components. Of the 100 mol% of the main component, Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 9.0 to 14.3 mol%, and the balance (31.2 to 39.7 mol%) is MnO.
Ｆｅ２Ｏ３を５１．３ｍｏｌ％以上とすることで、他の主成分との組み合わせにより２００℃以上のキュリー温度を達成しやすくなる。キュリー温度を上昇する点からは、Ｆｅ２Ｏ３は５２．１ｍｏｌ％以上が好ましい。一方、Ｆｅ２Ｏ３を５４．５ｍｏｌ％以下とすることで副成分との組み合わせにより２３℃〜１５０℃における１０ｋＨｚの比初透磁率μが４５００以上を達成しやすくなる。高い比初透磁率を得る点からは、Ｆｅ２Ｏ３は５４．１ｍｏｌ％以下が好ましい。 By setting Fe 2 O 3 to 51.3 mol% or more, it becomes easy to achieve a Curie temperature of 200 ° C. or higher by combining with other main components. From the viewpoint of raising the Curie temperature, Fe 2 O 3 is preferably 52.1 mol% or more. On the other hand, by setting Fe 2 O 3 to 54.5 mol% or less, it becomes easy to achieve a relative initial magnetic permeability μ of 10 kHz at 23 ° C. to 150 ° C. of 4500 or more in combination with a subcomponent. From the viewpoint of obtaining a high relative initial magnetic permeability, Fe 2 O 3 is preferably 54.1 mol% or less.
また、ＺｎＯを１４．３ｍｏｌ％以下とすることで、他の主成分との組み合わせにより２００℃以上のキュリー温度を達成しやすくなる。キュリー温度を上昇する点からは、ＺｎＯは１２．５０ｍｏｌ％以下が好ましい。一方、ＺｎＯを９．０ｍｏｌ％以上とすることで副成分との組み合わせにより２３℃〜１５０℃における１０ｋＨｚの比初透磁率μが４５００以上を達成しやすくなる。高い比初透磁率を得る点からは、ＺｎＯは１０．５０ｍｏｌ％以上が好ましい。 Further, by setting ZnO to 14.3 mol% or less, it becomes easy to achieve a Curie temperature of 200 ° C. or higher by combining with other main components. From the viewpoint of raising the Curie temperature, ZnO is preferably 12.50 mol% or less. On the other hand, when ZnO is set to 9.0 mol% or more, it becomes easy to achieve a relative initial magnetic permeability μ of 10 kHz at 23 ° C. to 150 ° C. of 4500 or more in combination with a subcomponent. From the viewpoint of obtaining a high relative initial magnetic permeability, ZnO is preferably 10.50 mol% or more.
また本ＭｎＺｎ系フェライトは前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有する。 Further, this MnZn-based ferrite contains 0.001 to 0.015% by mass of SiO 2 , 0.02 to 0.06% by mass of CaO, and 0.03 of ZrO 2 as subcomponents with respect to 100% by mass of the main component. It contains ~ 0.07% by mass, TiO 2 0.01 to 2.5% by mass, and Co 2 O 3 0.15 to 0.45% by mass.
ＳｉＯ２を０．００１質量％以上とすることで、高い比抵抗を有する結晶粒界を形成することができ、その結果、高周波領域における渦電流の発生を抑制して高周波数領域における比初透磁率が向上する。高周波領域における比初透磁率を向上する点から、ＳｉＯ２は０．００２質量％以上が好ましい。一方、ＳｉＯ２を０．０１５質量％以下とすることで、１０ｋＨｚにおける比初透磁率が向上する。１０ｋＨｚにおける比初透磁率が向上する点から、ＳｉＯ２は０．０１２質量％以下が好ましい。 By setting SiO 2 to 0.001% by mass or more, a grain boundary having a high specific resistance can be formed, and as a result, the generation of eddy current in the high frequency region is suppressed and the relative initial permeability in the high frequency region is suppressed. The magnetic coefficient is improved. From the viewpoint of improving the relative initial magnetic permeability in the high frequency region, SiO 2 is preferably 0.002% by mass or more. On the other hand, by setting SiO 2 to 0.015% by mass or less, the relative initial magnetic permeability at 10 kHz is improved. The SiO 2 is preferably 0.012% by mass or less from the viewpoint of improving the relative initial magnetic permeability at 10 kHz.
ＣａＯを０．０２質量％以上とすることで、高い比抵抗を有する結晶粒界を形成することができ、高周波数領域における比初透磁率が向上する。高周波領域における比初透磁率を向上する点から、ＣａＯは０．０３質量％以上が好ましい。一方、ＣａＯを０．０６質量％以下とすることで、１０ｋＨｚにおける比初透磁率が向上する。１０ｋＨｚにおける比初透磁率が向上する点から、ＣａＯは０．０５質量％以下が好ましい。 By setting CaO to 0.02% by mass or more, a grain boundary having a high specific resistance can be formed, and the specific initial magnetic permeability in a high frequency region is improved. CaO is preferably 0.03% by mass or more from the viewpoint of improving the relative initial magnetic permeability in the high frequency region. On the other hand, by setting CaO to 0.06% by mass or less, the relative initial magnetic permeability at 10 kHz is improved. CaO is preferably 0.05% by mass or less from the viewpoint of improving the relative initial magnetic permeability at 10 kHz.
ＺｒＯ２を０．０３質量％以上とすることで、高い比抵抗を有する結晶粒界を形成することができ、高周波数領域における比初透磁率が向上する。高周波領域における比初透磁率を向上する点から、ＺｒＯ２は０．０４質量％以上が好ましい。一方、ＺｒＯ２を０．０７質量％以下とすることで、１０ｋＨｚにおける比初透磁率が向上する。１０ｋＨｚにおける比初透磁率が向上する点から、ＺｒＯ２は０．０６質量％以下が好ましい。 By setting ZrO 2 to 0.03% by mass or more, a crystal grain boundary having a high specific resistance can be formed, and the specific initial magnetic permeability in a high frequency region is improved. ZrO 2 is preferably 0.04% by mass or more from the viewpoint of improving the relative initial magnetic permeability in the high frequency region. On the other hand, by setting ZrO 2 to 0.07% by mass or less, the relative initial magnetic permeability at 10 kHz is improved. ZrO 2 is preferably 0.06% by mass or less from the viewpoint of improving the relative initial magnetic permeability at 10 kHz.
ＴｉＯ２を０．０１質量％以上とすることで、結晶粒内の抵抗を高めることができ、高周波数領域における比初透磁率が向上する。高周波領域における比初透磁率を向上する点から、ＴｉＯ２は０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．５質量％以上が更に好ましい。一方、ＴｉＯ２を２．５質量％以下とすることで、１０ｋＨｚにおける比初透磁率が向上する。１０ｋＨｚにおける比初透磁率が向上する点から、ＴｉＯ２は１．０質量％以下が好ましい。 By setting TiO 2 to 0.01% by mass or more, the resistance in the crystal grains can be increased, and the relative initial magnetic permeability in the high frequency region is improved. From the viewpoint of improving the relative initial magnetic permeability in the high frequency region, TiO 2 is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more. On the other hand, by setting TiO 2 to 2.5% by mass or less, the relative initial magnetic permeability at 10 kHz is improved. TiO 2 is preferably 1.0% by mass or less from the viewpoint of improving the relative initial magnetic permeability at 10 kHz.
また、Ｃｏ２Ｏ３を０．１５〜０．４５質量％とすることで、結晶磁気異方性定数を広い温度範囲において小さく抑制し、比初透磁率の温度依存性を抑えることができる。その結果、２３℃〜１５０℃の広い温度域における１０ｋＨｚの比初透磁率を高く維持することができる。また、Ｃｏ２Ｏ３を０．４５質量％以下とすることで、２３℃における比初透磁率を向上することができる。このような点からＣｏ２Ｏ３は０．２５〜０．３５質量％が好ましい。 Further, by setting Co 2 O 3 to 0.15 to 0.45% by mass, the magnetocrystalline anisotropy constant can be suppressed small in a wide temperature range, and the temperature dependence of the relative initial magnetic permeability can be suppressed. As a result, the relative initial magnetic permeability of 10 kHz can be maintained high in a wide temperature range of 23 ° C to 150 ° C. Further, by setting Co 2 O 3 to 0.45% by mass or less, the relative initial magnetic permeability at 23 ° C. can be improved. From this point of view, Co 2 O 3 is preferably 0.25 to 0.35% by mass.
本ＭｎＺｎ系フェライトは、本発明の効果を奏する範囲で更に他の成分を含有してもよい。他の成分としては、必要に応じて添加される他の金属酸化物や、不可避的に含まれる元素などが挙げられる。
他の金属酸化物としては、例えば、Ｔａ２Ｏ５、Ｎｂ２Ｏ５、Ｂｉ２Ｏ３、ＭｏＯ３などが挙げられる。また、不可避的に含まれる元素としては、Ｃ（炭素原子）、Ｐ（リン原子）、Ｂ（ホウ素原子）などが挙げられる。
他の成分の合計の含有量は、主成分１００質量％に対して０．１質量％以下が好ましく、０．０１質量％以下が更に好ましい。
The MnZn-based ferrite may further contain other components as long as the effects of the present invention are exhibited. Examples of other components include other metal oxides added as needed and elements inevitably contained.
Examples of other metal oxides include Ta 2 O 5 , Nb 2 O 5 , Bi 2 O 3 , and MoO 3 . Moreover, as an element unavoidably contained, C (carbon atom), P (phosphorus atom), B (boron atom) and the like can be mentioned.
The total content of the other components is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, based on 100% by mass of the main component.
本ＭｎＺｎ系フェライトは、例えば、車載など高温環境下で使用可能なＡＣラインフィルタ等の電磁気ノイズ対策部品のコア材として好適に用いることができる。また、本ＭｎＺｎ系フェライトのコアに巻線を施した電磁気ノイズ対策部品は、ラインフィルタの磁心として使用する際、特に重要と考えられる周波数帯域（１５０ｋＨｚから１ＭＨｚ近傍）において、大きなノイズ減衰能力（インピーダンス）を有する。 This MnZn-based ferrite can be suitably used as a core material for electromagnetic noise countermeasure components such as AC line filters that can be used in a high temperature environment such as in a vehicle. In addition, the electromagnetic noise countermeasure component with windings on the MnZn-based ferrite core has a large noise attenuation capability (impedance) in the frequency band (from 150 kHz to around 1 MHz), which is considered to be particularly important when used as the magnetic core of a line filter. ).
［ＭｎＺｎ系フェライトの製造方法］
次に、ＭｎＺｎフェライトの製造方法（以下、本製造方法とも記す）の一実施形態について説明する。
本製造方法は、少なくとも、
焼結後に、主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部がＭｎＯとなるように、各主成分を含む原料を混合する工程（混合工程）と、
得られた混合物に、焼結後に前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有するように、各副成分を含む原料を添加する工程（添加工程）を有するものであればよく、通常、更に、乾燥・造粒工程、仮焼工程、解砕工程、乾燥・造粒工程、成型工程、焼結工程などＭｎＺｎフェライトの製造工程として公知の工程を含んでいる。
[Manufacturing method of MnZn-based ferrite]
Next, an embodiment of a method for producing MnZn ferrite (hereinafter, also referred to as this production method) will be described.
This manufacturing method is at least
After sintering, the raw material containing each main component is used so that Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 9.0 to 14.3 mol%, and the balance is MnO in 100 mol% of the main components. Mixing process (mixing process) and
After sintering, the obtained mixture contains 0.001 to 0.015% by mass of SiO 2 , 0.02 to 0.06% by mass of CaO, and ZrO 2 as subcomponents with respect to 100% by mass of the main component. A raw material containing each subcomponent is added so as to contain 0.03 to 0.07% by mass, 0.01 to 2.5% by mass of TiO 2 , and 0.15 to 0.45% by mass of Co 2 O 3. It suffices as long as it has a step (addition step), and usually, a manufacturing step of MnZn ferrite such as a drying / granulating step, a calcining step, a crushing step, a drying / granulating step, a molding step, and a sintering step. It includes a known step as.
上記混合工程では、焼結後の主成分が前記本ＭｎＺｎフェライトの組成となるように主成分を混合する。主成分の混合前の形態は特に限定されないが、取り扱いが容易で均一に混合できる点から、粉末状であることが好ましい。主成分の原料粉末は混合して、必要に応じて解砕することで混合粉末とする。混合及び解砕方法は、公知の方法の中から適宜選択すればよい。具体的には例えば、アトライタやビーズミルなどが挙げられる。混合粉末の粒子径は、特に限定されないが、均一性などの点から、メジアン径Ｄ５０が０．５μｍ〜１．５μｍとなるように調整することが好ましい。なお、混合粉末の粒度分布は粒度分布測定装置で測定することができる。 In the mixing step, the main components are mixed so that the main component after sintering has the composition of the present MnZn ferrite. The form of the main component before mixing is not particularly limited, but it is preferably in the form of powder from the viewpoint of easy handling and uniform mixing. The raw material powder of the main component is mixed and crushed as necessary to obtain a mixed powder. The mixing and crushing method may be appropriately selected from known methods. Specific examples thereof include an attritor and a bead mill. The particle size of the mixed powder is not particularly limited, but it is preferable to adjust the median diameter D50 to 0.5 μm to 1.5 μm from the viewpoint of uniformity and the like. The particle size distribution of the mixed powder can be measured with a particle size distribution measuring device.
上記主成分の混合粉末に対し、乾燥・造粒工程を実施してもよい。乾燥・造粒工程では、例えば、混合工程で得られた混合粉末に、混合粉末の全質量を１００質量部としたときに０．５〜１質量部のポリビニルアルコールなどのバインダーを加え、スプレードライヤーなどを用いて噴霧することで顆粒を得ることができる。
得られた顆粒は、次いで、例えば空気雰囲気下７５０℃で１時間程度仮焼して仮焼物としてもよい（仮焼工程）。
A drying / granulating step may be carried out on the mixed powder of the above main components. In the drying / granulating step, for example, 0.5 to 1 part by mass of a binder such as polyvinyl alcohol is added to the mixed powder obtained in the mixing step when the total mass of the mixed powder is 100 parts by mass, and a spray dryer is used. Granules can be obtained by spraying with or the like.
The obtained granules may then be calcined at 750 ° C. for about 1 hour in an air atmosphere to obtain a calcined product (temporary firing step).
次いで、焼結後の副成分が前記本ＭｎＺｎフェライトの組成となるように仮焼物に副成分を添加する。副成分の添加前の形態は特に限定されないが、取り扱いが容易で均一に混合できる点から、粒子状であることが好ましい。中でも、ＳｉＯ２、ＺｒＯ２、ＴｉＯ２及びＣｏ２Ｏ３を含む原料は、各々平均粒子径が０．１μｍ以上の粒子であることが好ましい。平均粒子径が０．１μｍ以上の原料を用いることで比初透磁率を向上することができる、また、特に後述する解砕工程においてアトライタを用いる場合には分散性に優れ、得られるＭｎＺｎフェライトの製造安定性に優れている。 Next, the sub-component is added to the calcined product so that the sub-component after sintering has the composition of the present MnZn ferrite. The form before the addition of the sub-ingredient is not particularly limited, but it is preferably in the form of particles from the viewpoint of easy handling and uniform mixing. Among them, the raw materials containing SiO 2 , ZrO 2 , TiO 2 and Co 2 O 3 are preferably particles having an average particle diameter of 0.1 μm or more. The relative initial magnetic permeability can be improved by using a raw material having an average particle size of 0.1 μm or more, and the dispersibility is excellent especially when an attritor is used in the crushing step described later, and the obtained MnZn ferrite can be obtained. Excellent manufacturing stability.
副成分を添加した後、得られた混合粉末を解砕して解砕粉末を得る。具体的には、解砕工程において、解砕後の粒径のメジアン径Ｄ５０が０．５μｍ以上、且つ１．０μｍ以下になるまで仮焼物を解砕して解砕粉末を得る。 After adding the auxiliary component, the obtained mixed powder is crushed to obtain a crushed powder. Specifically, in the crushing step, the calcined product is crushed until the median diameter D50 of the particle size after crushing becomes 0.5 μm or more and 1.0 μm or less to obtain a crushed powder.
乾燥・造粒工程では、解砕工程において得られた解砕粉末に解砕粉末の全質量を１００質量部としたときに、０．５〜１．０質量部のポリビニルアルコールなどのバインダーを加え、スプレードライヤーなどで噴霧することで顆粒を得る。このとき、顆粒のメジアン径Ｄ５０は４０μｍ以上、２００μｍ以下となることが望ましい。 In the drying / granulating step, 0.5 to 1.0 part by mass of a binder such as polyvinyl alcohol is added to the crushed powder obtained in the crushing step when the total mass of the crushed powder is 100 parts by mass. , Granules are obtained by spraying with a spray dryer or the like. At this time, it is desirable that the median diameter D50 of the granules is 40 μm or more and 200 μm or less.
成型工程においては、乾燥・造粒工程で得られた顆粒を所定の形状に成形する。所定の形状とは用途等に応じて設計すればよい。例えば、外径が１９ｍｍ、内径が１３ｍｍ、高さが１１ｍｍのトロイダル型のコアに成形する。 In the molding step, the granules obtained in the drying / granulating step are molded into a predetermined shape. The predetermined shape may be designed according to the application and the like. For example, it is formed into a toroidal core having an outer diameter of 19 mm, an inner diameter of 13 mm, and a height of 11 mm.
成形後の顆粒は熱処理することで、焼結体（本ＭｎＺｎフェライト）とする。熱処理（焼結）条件は特に限定されないが、例えば、１３００℃程度で数時間加熱することで焼結することができる。 The granules after molding are heat-treated to obtain a sintered body (this MnZn ferrite). The heat treatment (sintering) conditions are not particularly limited, but for example, sintering can be performed by heating at about 1300 ° C. for several hours.
上記の製造方法によれば、広い温度域及び広い周波数帯に対して高い比初透磁率を有し、且つ、キュリー温度及び飽和磁束密度が高いＭｎＺｎ系フェライトを好適に製造することができる。 According to the above manufacturing method, MnZn-based ferrite having a high relative initial magnetic permeability in a wide temperature range and a wide frequency band, and having a high Curie temperature and a high saturation magnetic flux density can be preferably manufactured.
以下、実施例および比較例を挙げて本発明を具体的に説明する。なお、これらの記載により本発明を制限するものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. It should be noted that these descriptions do not limit the present invention.
［実施例１］
焼結後のＦｅ２Ｏ３含有量が５１．３ｍｏｌ％、ＺｎＯ含有量が１１．５ｍｏｌ％、ＭｎＯ含有量が３７．２ｍｏｌ％として合計１００ｍｏｌ％となるように、Ｆｅ２Ｏ３を５０．１ｍｏｌ％、ＺｎＯを１２．１ｍｏｌ％、Ｍｎ３Ｏ４を３７．８ｍｏｌ％として各原料粉末を秤量して混合した。混合工程では、混合物のメジアン径Ｄ５０が０．５μｍ以上、１．５μｍ以下となるまで混合物をアトライタで解砕した。次に、上記混合物の全質量１００質量部に対して０．５質量部相当のポリビニルアルコールを加え、スプレードライヤーで噴霧することで顆粒を得た。次に、当該顆粒を空気雰囲気中で７５０℃で１時間仮焼して仮焼物を得た。次いで焼結後の副成分の含有量が表１に示す通りとなるように、当該仮焼物の全質量１００質量部に対し、０．００７質量部のＳｉＯ２と、０．０５１質量部のＣａ（ＯＨ）２と、０．０５０質量部のＺｒＯ２、０．２０質量部のＴｉＯ２と、０．２７質量部のＣｏ３Ｏ４をそれぞれ添加した。なお、ＳｉＯ２、ＺｒＯ２、ＴｉＯ２及びＣｏ２Ｏ３は、各々平均粒子径が０．１μｍ以上の粒子を用いた。
次に、解砕工程として仮焼物と添加物の混合物を、解砕後の粒径のメジアン径Ｄ５０が０．５μｍ以上、１．０μｍ以下になるように解砕機で解砕して解砕粉末を得た。次に乾燥・造粒工程としてこの解砕物に、解砕物の全質量を１００質量部としたときに、１質量部のポリビニルアルコールを加え、スプレードライヤーで噴霧することで顆粒を得た。このときの顆粒のメジアン径Ｄ５０は１１０μｍであった。次に成型工程、および焼結工程としてこの顆粒を外径が２５ｍｍ、内径が１５ｍｍ、高さが１０ｍｍのトロイダル型のコアに成形し、１３００℃で焼結して焼結体（ＭｎＺｎ系フェライト）を得た。
[Example 1]
Fe 2 O 3 content 51.3Mol% after sintering, ZnO content of 11.5 mol%, as MnO content is the total 100 mol% as 37.2mol%, the Fe 2 O 3 50.1mol %, ZnO was 12.1 mol%, and Mn 3 O 4 was 37.8 mol%, and each raw material powder was weighed and mixed. In the mixing step, the mixture was crushed with an attritor until the median diameter D50 of the mixture was 0.5 μm or more and 1.5 μm or less. Next, 0.5 parts by mass of polyvinyl alcohol was added to 100 parts by mass of the total mass of the mixture, and the mixture was sprayed with a spray dryer to obtain granules. Next, the granules were calcined at 750 ° C. for 1 hour in an air atmosphere to obtain a calcined product. Next, 0.007 parts by mass of SiO 2 and 0.051 parts by mass of Ca with respect to 100 parts by mass of the total mass of the calcined product so that the content of the sub-components after sintering is as shown in Table 1. (OH) 2 , 0.050 parts by mass of ZrO 2 , 0.20 parts by mass of TiO 2 and 0.27 parts by mass of Co 3 O 4 were added, respectively. For SiO 2 , ZrO 2 , TiO 2 and Co 2 O 3 , particles having an average particle diameter of 0.1 μm or more were used.
Next, as a crushing step, the mixture of the calcined product and the additive is crushed by a crusher so that the median diameter D50 of the particle size after crushing is 0.5 μm or more and 1.0 μm or less, and crushed powder. Got Next, as a drying / granulating step, when the total mass of the crushed material was 100 parts by mass, 1 part by mass of polyvinyl alcohol was added to the crushed material and sprayed with a spray dryer to obtain granules. The median diameter D50 of the granules at this time was 110 μm. Next, as a molding step and a sintering step, the granules are molded into a toroidal core having an outer diameter of 25 mm, an inner diameter of 15 mm, and a height of 10 mm, and sintered at 1300 ° C. to obtain a sintered body (MnZn-based ferrite). Got
［実施例２〜１７］
実施例１において、焼結後の主成分及び副成分の含有割合が表１の通りとなるように原料を混合及び添加した以外は、実施例１と同様にして、実施例２〜１７のＭｎＺｎ系フェライトを得た。
[Examples 2 to 17]
In Example 1, MnZn of Examples 2 to 17 is the same as in Example 1 except that the raw materials are mixed and added so that the content ratios of the main component and the sub-component after sintering are as shown in Table 1. A system ferrite was obtained.
［比較例１〜１４］
実施例１において、焼結後の主成分及び副成分の含有割合が表１の通りとなるように原料を混合及び添加した以外は、実施例１と同様にして、比較例１〜１４のＭｎＺｎ系フェライトを得た。
[Comparative Examples 1 to 14]
MnZn of Comparative Examples 1 to 14 in the same manner as in Example 1 except that the raw materials were mixed and added so that the content ratios of the main component and the sub-component after sintering were as shown in Table 1. A system ferrite was obtained.
＜評価＞
上記実施例及び比較例で得られたＭｎＺｎ系フェライトについて、下記（１）〜（３）の方法により、２３℃における１０ｋＨｚの比初透磁率μ（２３℃）；２３℃における７００ｋＨｚの比初透磁率μ（７００ｋＨｚ）；及び１５０℃における１０ｋＨｚの比初透磁率μ（１５０℃）、キュリー温度、及び２３℃における飽和磁束密度を測定した。結果を表１に示す。
<Evaluation>
With respect to the MnZn-based ferrites obtained in the above Examples and Comparative Examples, the specific initial magnetic flux density of 10 kHz at 23 ° C. μ (23 ° C.); the specific initial permeability of 700 kHz at 23 ° C. by the following methods (1) to (3). Magnetic permeability μ (700 kHz); and specific initial permeability μ (150 ° C) at 10 kHz at 150 ° C, Curie temperature, and saturation magnetic flux density at 23 ° C were measured. The results are shown in Table 1.
（１）比初透磁率
実施例及び比較例のＭｎＺｎ系フェライトをリングコアとし、当該リングコアに巻き線を１０回巻き付け、インピーダンスアナライザーにより、各温度及び各周波数におけるインダクタンスを測定し、比初透磁率を算出した。
（２）キュリー温度
実施例及び比較例のＭｎＺｎ系フェライトをリングコアとし、当該リングコアに巻き線を１０回巻き付け、恒温槽を用いて１８０℃から２５０℃の温度範囲においてインダクタンスを測定し、各温度における比初透磁率を算出した。次いで、得られた温度と比初透磁率の関係より、比初透磁率が１となる温度をキュリー温度とした。
（３）飽和磁束密度
実施例及び比較例のＭｎＺｎ系フェライトをリングコアとし、当該リングコアに１次巻き線を５０回、２次巻き線を２０回巻き付け、直流磁界１１９６Ａ／ｍを印可したときの飽和磁束密度を測定した。
(1) Specific initial magnetic permeability Using MnZn-based ferrite of Examples and Comparative Examples as a ring core, winding a winding around the ring core 10 times, measuring the inductance at each temperature and each frequency with an impedance analyzer, and determining the specific initial magnetic permeability. Calculated.
(2) Curie temperature Using MnZn-based ferrite of Examples and Comparative Examples as a ring core, winding a winding around the ring core 10 times, measuring the inductance in the temperature range of 180 ° C to 250 ° C using a constant temperature bath, and measuring the inductance at each temperature. The relative initial permeability was calculated. Next, based on the relationship between the obtained temperature and the specific initial magnetic permeability, the temperature at which the specific initial magnetic permeability was 1 was defined as the Curie temperature.
(3) Saturation magnetic flux density Saturation when the MnZn-based ferrite of Examples and Comparative Examples is used as a ring core, the primary winding is wound 50 times and the secondary winding is wound 20 times around the ring core, and a DC magnetic field of 1196 A / m is applied. The magnetic flux density was measured.
［結果のまとめ］
主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部がＭｎＯであり、前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有する、実施例１〜１７のＭｎＺｎ系フェライトは、いずれも、２３℃における１０ｋＨｚの比初透磁率μ（２３℃）；２３℃における７００ｋＨｚの比初透磁率μ（７００ｋＨｚ）；及び１５０℃における１０ｋＨｚの比初透磁率μ（１５０℃）が４５００以上であり、キュリー温度が２００℃以上であり、且つ、２３℃における飽和磁束密度が５００ｍＴ以上であることが示された。
[Summary of results]
Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 9.0 to 14.3 mol%, and the balance is MnO in 100 mol% of the main component. SiO 2 is 0.001 to 0.015% by mass, CaO is 0.02 to 0.06% by mass, ZrO 2 is 0.03 to 0.07% by mass, and TiO 2 is 0.01 to 2.5% by mass. , Co 2 O 3 in an amount of 0.15 to 0.45% by mass, all of the MnZn-based ferrites of Examples 1 to 17 have a relative initial magnetic permeability of μ (23 ° C.) of 10 kHz at 23 ° C.; 700 kHz relative initial permeability μ (700 kHz); and 10 kHz relative initial permeability μ (150 ° C) at 150 ° C is 4500 or higher, Curie temperature is 200 ° C or higher, and saturation magnetic flux density at 23 ° C is It was shown to be above 500 mT.
Claims (10)
前記主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが１０．５０〜１４．３ｍｏｌ％、残部がＭｎＯであり、
前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．３質量％含有する、ＭｎＺｎ系フェライト。 Fe 2 O 3 and ZnO and MnO are the main components
During the main component 100mol%, Fe 2 O 3 is 51.3~54.5mol%, ZnO is 10.50~14.3mol%, balance being MnO,
The relative main component of 100% by mass, as an auxiliary component, the SiO 2 0.001 to 0.015 mass%, 0.02-0.06 mass% of CaO, a ZrO 2 0.03 to 0.07 wt% , MnZn-based ferrite containing 0.01 to 2.5% by mass of TiO 2 and 0.15 to 0.3 % by mass of Co 2 O 3 .
前記主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部がＭｎＯであり、
前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．５〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有する、ＭｎＺｎ系フェライト。 Fe 2 O 3 and ZnO and MnO are the main components
Of the 100 mol% of the main component, Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 9.0 to 14.3 mol%, and the balance is MnO.
The relative main component of 100% by mass, as an auxiliary component, the SiO 2 0.001 to 0.015 mass%, 0.02-0.06 mass% of CaO, a ZrO 2 0.03 to 0.07 wt% , MnZn-based ferrite containing 0.5 to 2.5% by mass of TiO 2 and 0.15 to 0.45% by mass of Co 2 O 3 .
焼結後に、主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが１０．５０〜１４．３ｍｏｌ％、残部がＭｎＯとなるように、各主成分を含む原料を混合する工程と、
得られた混合物に、焼結後に前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．０１〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．３質量％含有するように、各副成分を含む原料を添加する工程を有する、ＭｎＺｎ系フェライトの製造方法。 The method for producing an MnZn-based ferrite according to claim 1 .
After sintering, the raw material containing each main component is prepared so that Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 10.50 to 14.3 mol%, and the balance is MnO in 100 mol% of the main components. The process of mixing and
After sintering, the obtained mixture contains 0.001 to 0.015% by mass of SiO 2 , 0.02 to 0.06% by mass of CaO, and ZrO 2 as subcomponents with respect to 100% by mass of the main component. A raw material containing each subcomponent is added so as to contain 0.03 to 0.07% by mass, 0.01 to 2.5% by mass of TiO 2 , and 0.15 to 0.3 % by mass of Co 2 O 3. A method for producing MnZn-based ferrite, which comprises a step of:
焼結後に、主成分１００ｍｏｌ％中、Ｆｅ２Ｏ３が５１．３〜５４．５ｍｏｌ％、ＺｎＯが９．０〜１４．３ｍｏｌ％、残部がＭｎＯとなるように、各主成分を含む原料を混合する工程と、
得られた混合物に、焼結後に前記主成分１００質量％に対し、副成分として、ＳｉＯ２を０．００１〜０．０１５質量％、ＣａＯを０．０２〜０．０６質量％、ＺｒＯ２を０．０３〜０．０７質量％、ＴｉＯ２を０．５〜２．５質量％、Ｃｏ２Ｏ３を０．１５〜０．４５質量％含有するように、各副成分を含む原料を添加する工程を有する、ＭｎＺｎ系フェライトの製造方法。 The method for producing an MnZn-based ferrite according to claim 2 .
After sintering, the raw material containing each main component is prepared so that Fe 2 O 3 is 51.3 to 54.5 mol%, Zn O is 9.0 to 14.3 mol%, and the balance is MnO in 100 mol% of the main components. The process of mixing and
After sintering, the obtained mixture contains 0.001 to 0.015% by mass of SiO 2 , 0.02 to 0.06% by mass of CaO, and ZrO 2 as subcomponents with respect to 100% by mass of the main component. Raw materials containing each subcomponent are added so as to contain 0.03 to 0.07% by mass, TiO 2 by 0.5 to 2.5% by mass, and Co 2 O 3 by 0.15 to 0.45% by mass. A method for producing MnZn-based ferrite, which comprises a step of:
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| CN117125970A (en) * | 2023-08-24 | 2023-11-28 | 山东凯通电子有限公司 | Wide-temperature high-DC low-power-consumption manganese-zinc ferrite core and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05267040A (en) * | 1992-03-19 | 1993-10-15 | Kawasaki Steel Corp | Low-loss mn-zn ferrite |
| JPH06283320A (en) * | 1993-03-30 | 1994-10-07 | Nippon Steel Corp | Oxide magnetic material having high saturation flux density and its manufacture |
| JP3654303B2 (en) * | 1993-05-18 | 2005-06-02 | Ｎｅｃトーキン株式会社 | Low loss magnetic material |
| JP3471896B2 (en) * | 1994-04-27 | 2003-12-02 | Ｔｄｋ株式会社 | Ferrite and ferrite core for power supply |
| JPH097813A (en) * | 1995-06-26 | 1997-01-10 | Tdk Corp | Method of manufacturing mn-zn-based oxide magnetic material |
| JP2000173841A (en) * | 1998-12-09 | 2000-06-23 | Tdk Corp | Transformer and drive method thereof |
| JP2003217920A (en) * | 2002-01-22 | 2003-07-31 | Fdk Corp | MANUFACTURING METHOD OF Mn-Zn FERRITE MATERIAL |
| JP2005119892A (en) * | 2003-10-14 | 2005-05-12 | Fdk Corp | Low-loss ferrite |
| JP2007103677A (en) * | 2005-10-04 | 2007-04-19 | Tdk Corp | Method for manufacturing ferrite material, ferrite core, and baking furnace system |
| JP5332254B2 (en) * | 2008-03-25 | 2013-11-06 | Ｔｄｋ株式会社 | Ferrite sintered body |
| JP5786322B2 (en) * | 2010-11-30 | 2015-09-30 | Tdk株式会社 | Ferrite core |
| JP6472674B2 (en) * | 2015-02-03 | 2019-02-20 | Fdk株式会社 | NiMnZn ferrite |
| EP3441995A4 (en) * | 2016-03-25 | 2019-08-14 | Hitachi Metals, Ltd. | METHOD FOR PRODUCING MnZn-BASED FERRITE, AND MnZn-BASED FERRITE |
| JP7278787B2 (en) * | 2019-01-28 | 2023-05-22 | Ｎｊコンポーネント株式会社 | magnetic material |
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| CN111116188A (en) * | 2019-12-30 | 2020-05-08 | 江门安磁电子有限公司 | Manganese-zinc high-magnetic-permeability high-Curie-temperature high-frequency high-magnetic-flux material and preparation method thereof |
| CN111116188B (en) * | 2019-12-30 | 2022-08-19 | 江门安磁电子有限公司 | Manganese-zinc high-magnetic-permeability high-Curie-temperature high-frequency high-magnetic-flux material and preparation method thereof |
| CN117125970A (en) * | 2023-08-24 | 2023-11-28 | 山东凯通电子有限公司 | Wide-temperature high-DC low-power-consumption manganese-zinc ferrite core and preparation method thereof |
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