JP4554959B2 - Mn-Co-Zn ferrite - Google Patents
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- JP4554959B2 JP4554959B2 JP2004061853A JP2004061853A JP4554959B2 JP 4554959 B2 JP4554959 B2 JP 4554959B2 JP 2004061853 A JP2004061853 A JP 2004061853A JP 2004061853 A JP2004061853 A JP 2004061853A JP 4554959 B2 JP4554959 B2 JP 4554959B2
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- 229910000859 α-Fe Inorganic materials 0.000 title claims description 56
- 229910020521 Co—Zn Inorganic materials 0.000 title claims description 18
- 229910052787 antimony Inorganic materials 0.000 claims description 14
- 229910052785 arsenic Inorganic materials 0.000 claims description 14
- 229910052793 cadmium Inorganic materials 0.000 claims description 14
- 229910052745 lead Inorganic materials 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- 230000002159 abnormal effect Effects 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 238000010304 firing Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910018605 Ni—Zn Inorganic materials 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Compounds Of Iron (AREA)
- Magnetic Ceramics (AREA)
- Soft Magnetic Materials (AREA)
Description
本発明は、比抵抗が高くかつ保磁力の低いMn−Co−Zn系フェライトに関するものである。 The present invention relates to an Mn—Co—Zn ferrite having a high specific resistance and a low coercive force.
軟磁性酸化物磁性材料の代表的な例として、Mn−Znフェライトが挙げられる。従来のMn−Znフェライトでは、正の磁気異方性を持つFe2+を約２mass％以上含み、負の磁気異方性を持つFe3+およびMn2+と相殺させることにより、高透磁率材料や低損失材料が得られている。 A typical example of the soft magnetic oxide magnetic material is Mn-Zn ferrite. Conventional Mn-Zn ferrite contains Fe 2+ with positive magnetic anisotropy of about 2 mass% or more, and cancels it out with Fe 3+ and Mn 2+ with negative magnetic anisotropy. Materials and low-loss materials have been obtained.
しかし、Fe2+量を多くすると、Fe3+−Fe2+間での電子の授受が起こりやすくなる結果、比抵抗が非常に小さな値、具体的には0.1Ω・mのオーダーにまで低下してしまうという欠点がある。そのため、使用する周波数領域が高くなると、フェライト内を流れる渦電流による損失が急増する。そのため高周波領域では、Mn−Znフェライトの初透磁率は大きく低下し、損失も増大する。よって、耐用周波数は数百kHz程度が限界である。 However, increasing the amount of Fe 2+ makes it easier for electrons to be transferred between Fe 3+ and Fe 2+ , resulting in a very low specific resistance, specifically to the order of 0.1 Ω · m. There is a drawback that it will. Therefore, when the frequency region to be used becomes high, the loss due to the eddy current flowing in the ferrite increases rapidly. Therefore, in the high frequency region, the initial permeability of the Mn-Zn ferrite is greatly reduced and the loss is also increased. Therefore, the limit of the useful frequency is about several hundred kHz.
従って、MHzオーダーの周波数領域で使用されるフェライトとしては、Ni−Znフェライトが主流になっている。その理由として、Ni−Znフェライトは、Mn−Znフェライトの約1万倍となる、105（Ω・m）以上の非常に高い比抵抗を持つため、渦電流損失による影響が無視でき、高周波領域でも初透磁率が高くかつ低損失という特性が失われにくい、ことが挙げられる。 Therefore, Ni-Zn ferrite is mainly used as the ferrite used in the frequency range of MHz order. The reason is that Ni-Zn ferrite has a very high specific resistance of 10 5 (Ω · m) or more, which is about 10,000 times that of Mn-Zn ferrite. Even in the region, the characteristics of high initial permeability and low loss are difficult to lose.
ところが、Ni−Znフェライトには大きな問題点がある。すなわち保磁力、軟磁性材料は外部磁場の変化に敏感に反応することが求められるため、Hcは小さい方が好ましいが、Ni−Znフェライトは負の磁気異方性を持つイオンによってのみ構成されているため、この保磁力の値が大きくなることである。なお、保磁力については、JIS C2561に規定されている。 However, Ni-Zn ferrite has a big problem. That is, since coercivity and soft magnetic materials are required to react sensitively to changes in the external magnetic field, it is preferable that Hc be small, but Ni-Zn ferrite is composed only of ions having negative magnetic anisotropy. Therefore, the value of the coercive force is increased. The coercive force is defined in JIS C2561.
また、Ni−Znフェライト以外で比抵抗の大きいフェライトを得る方法として、Mn−Znフェライト中に含まれるFe2+量を減らすことによって比抵抗を上昇させる、というものがある。その一つとして、原料中のFe2O3成分を50mol％未満としてFe2+含有量を減らして比抵抗を高めた、Mn−Znフェライトの開発が行われており、特許文献１、特許文献２および特許文献３等において提案されている。しかし、これらの技術も、正の磁気異方性を持つFe2+の含有量を減らした結果、Ni−Znフェライトと同様に負の磁気異方性を持つイオンのみから構成されることは変わりなく、保磁力の低減という課題は全く解決されていない。 Further, as a method of obtaining a ferrite having a large specific resistance other than Ni-Zn ferrite, there is a method of increasing the specific resistance by reducing the amount of Fe 2+ contained in the Mn-Zn ferrite. As one of them, Mn-Zn ferrite has been developed in which the Fe 2 O 3 component in the raw material is less than 50 mol% and the Fe 2+ content is reduced to increase the specific resistance. 2 and Patent Document 3 and the like. However, as a result of reducing the content of Fe 2+ with positive magnetic anisotropy, these technologies are also composed of only ions with negative magnetic anisotropy like Ni-Zn ferrite. The problem of reducing the coercive force has not been solved at all.
これに対して、特許文献４、特許文献５および特許文献６では、Fe2+以外の正の磁気異方性を持つイオンであるCo2+をさらに添加することが、提案されている。
しかしながら、特許文献４〜６には、保磁力について触れるところがなく、また実際にCo2+の添加によっても保磁力の低減は実現されていなかった。 However, Patent Documents 4 to 6 do not mention the coercive force, and the reduction of the coercive force has not been realized by actually adding Co 2+ .
さらに、実際の製造を鑑みた際に、コスト及び効率の面から劣っているといわざるを得ない。すなわち、特許文献４および５における実施例では、非常に低い酸素濃度雰囲気下で焼成が行われているために、
ａ）焼成炉の厳密なシール及び雰囲気制御
ｂ）（工業用窒素は最低でも１〜20ppmの酸素を含むため）純窒素の使用
が要求される。これらの規制は、工業化を考えた際に、製造効率およびコストの両面において問題となる。
Furthermore, in view of actual manufacturing, it must be said that it is inferior in terms of cost and efficiency. That is, in the examples in Patent Documents 4 and 5, since firing is performed in a very low oxygen concentration atmosphere,
a) Strict sealing of firing furnace and atmosphere control b) Use of pure nitrogen is required (since industrial nitrogen contains at least 1-20 ppm oxygen). These regulations are problematic in terms of both production efficiency and cost when considering industrialization.
また、特許文献６の実施例には、ブリッジマン法による単結晶育成についてのみ記載されている。これは、工業化の際の製造効率やコストにおいて、従来の粉末冶金法でフェライトを製造する場合と比較すると、当然ながら大きく劣ったものとなる。 Moreover, the Example of patent document 6 describes only the single crystal growth by the Bridgman method. This is naturally inferior in terms of production efficiency and cost in industrialization compared to the case where ferrite is produced by a conventional powder metallurgy method.
本発明は、上記の問題を有利に解決するものであり、Fe2+含有量を減らして比抵抗を高める一方、この比抵抗を低下することなしに、保磁力を大幅に低下したMn−Co−Zn系フェライトを提供しようとするものである。 The present invention advantageously solves the above problem, and reduces the Fe 2+ content to increase the specific resistance, while reducing the coercive force without decreasing the specific resistance. -To provide Zn-based ferrite.
さて、フェライト製造の際に課題となるのが、異常粒成長の抑制である。異常粒成長とは、何らかの原因により局部的に粒成長のバランスが崩れた際に起こる、粉末冶金法を用いた製造時にしばしば見られる現象であり、この異常成長粒内には、不純物や格子欠陥等の磁壁の移動を大きく妨げる物質が混入しているために、これが磁壁の移動を妨害する結果、保磁力が上昇することになる。同時に、結晶粒界形成が不十分になることから、比抵抗は低下する。その他の磁気特性および強度についても大きく劣化することから、異常粒成長の抑制はフェライト製造の際の重要なポイントである。 Now, what becomes a problem in the production of ferrite is the suppression of abnormal grain growth. Abnormal grain growth is a phenomenon often seen during the production using powder metallurgy, which occurs when the balance of grain growth is disrupted locally for some reason. As a result, the coercive force increases. As a result, the magnetic wall is prevented from moving. At the same time, since the formation of grain boundaries becomes insufficient, the specific resistance decreases. Since other magnetic characteristics and strength are also greatly deteriorated, suppression of abnormal grain growth is an important point in the production of ferrite.
そこで、この異常粒成長の抑制を達成する手段について鋭意究明したところ、以下の知見を得るに到った。すなわち、Mn−Co−Zn系フェライトの主原料は、Fe2O3，CoO，ZnOおよびMnO等であるが、これらの原料中には、天然鉱石中に含有されたり、または製錬時に混入されたりする等の理由から、Cd，Pb，Sb，As及びSeの各成分がある程度で混入することが不可避である。これらの不純物が適正量を超えて含有されたフェライトは、異常粒成長を誘発し、結果として軟磁性フェライトの磁気特性、比抵抗および強度等の諸特性に対して重大な悪影響を及ばすことが、新たに判明したのである。 Thus, the inventors have earnestly studied the means for achieving the suppression of the abnormal grain growth, and have obtained the following knowledge. That is, the main raw materials of Mn-Co-Zn ferrite are Fe 2 O 3 , CoO, ZnO, MnO, etc., but these raw materials are contained in natural ores or mixed during smelting. For this reason, it is inevitable that Cd, Pb, Sb, As, and Se components are mixed to some extent. Ferrite containing more than the proper amount of these impurities can induce abnormal grain growth, resulting in serious adverse effects on various properties such as magnetic properties, specific resistance and strength of soft magnetic ferrite. It was newly discovered.
上述の特許文献４〜６に記載の技術では、このような不純物についての記載は何ら行われていない。特許文献５では、むしろ反対に、Pbを意図的に添加することが規定されているほどである。そのため、これらの文献に記載された技術をもってしても、望ましい特性、特に高い比抵抗の下に保磁力を低下したMn−Co−Zn系フェライトを得ることは極めて困難であったのである。 In the techniques described in Patent Documents 4 to 6 described above, no description of such impurities is made. On the contrary, in Patent Document 5, it is prescribed that Pb is intentionally added. For this reason, even with the techniques described in these documents, it has been extremely difficult to obtain Mn—Co—Zn-based ferrite having desirable characteristics, particularly a low specific coercive force under a high specific resistance.
本発明は、上記の知見に基づいて成されたものであり、その要旨は次のとおりである。
（１）Fe2O3：45.0 mol％以上50.0mol％未満、
CoO：0.5mol％以上4.0mol％以下、
ZnO：15.5 mol％以上24.0mol％以下および
MnO：残部
を基本成分とし、
フェライト中に含まれるCd，Pb，Sb，AsおよびSeがそれぞれ20massppm未満であることを特徴とするMn−Co−Zn系フェライト。
The present invention has been made based on the above findings, and the gist thereof is as follows.
(1) Fe 2 O 3 : 45.0 mol% or more and less than 50.0 mol%,
CoO: 0.5 mol% or more and 4.0 mol% or less,
ZnO: 15.5 mol% or more and 24.0 mol% or less and
MnO: The balance is the basic component,
An Mn-Co-Zn ferrite characterized in that Cd, Pb, Sb, As and Se contained in the ferrite are each less than 20 massppm.
（２）前記フェライト中に、添加物としてさらに
CaO：0.005〜0.200mass％および
SiO2：0.001〜0.050mass％
のうちから選んだ１種または２種を含有する上記（１）に記載のMn−Co−Zn系フェライト。
(2) In the ferrite, as an additive
CaO: 0.005-0.200 mass% and
SiO 2 : 0.001 to 0.050 mass%
The Mn-Co-Zn ferrite according to (1) above, which contains one or two selected from the above.
（３）前記フェライト中に、添加物としてさらに
ZrO2：0.005〜0.100mass％、
Ta2O5：0.005〜0.100mass％、
HfO2：0.005〜0.100mass％および
Nb2O5：0.005〜0.100mass％
のうちから選んだ１種または２種以上を含有する上記（１）または（２）に記載のMn−Co−Zn系フェライト。
(3) In the ferrite, as an additive
ZrO 2 : 0.005 to 0.100 mass%,
Ta 2 O 5 : 0.005 to 0.100 mass%,
HfO 2 : 0.005 to 0.100 mass% and
Nb 2 O 5 : 0.005 to 0.100 mass%
The Mn-Co-Zn ferrite according to (1) or (2) above, which contains one or more selected from among the above.
本発明のMn−Co−Zn系フェライトは、上記の構成によって、従来実現されなかった、キュリー温度100℃以上、室温（23℃）における比抵抗が30Ω・m以上、かつ保磁力が10.0A／m以下という、優れた特性を有するものとなる。 The Mn—Co—Zn-based ferrite of the present invention has a Curie temperature of 100 ° C. or higher, a specific resistance at room temperature (23 ° C.) of 30 Ω · m or more, and a coercive force of 10.0 A / It has excellent characteristics of m or less.
本発明によれば、キュリー温度を100℃以上に保持したまま、室温（23℃）での比抵抗を上昇し、かつ保磁力を低くした、Mn−Co−Zn系フェライトを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the Mn-Co-Zn type ferrite which raised the specific resistance in room temperature (23 degreeC), and made the coercive force low can be provided, keeping Curie temperature at 100 degreeC or more. .
さらに、このフェライトにCaO，SiO2の１種又は２種を適量添加して、粒界偏析の効果を利用することによって、さらなる比抵抗の上昇を、またZrO2，Ta205，HfO2及びNb205の１種または２種以上を適量添加して結晶粒径を抑えることにより、さらなる保磁力の低下を、それぞれ達成することができる。さらに、これらを組み合わせて添加することにより、上記効果を併せた効果が得られる。 Further, by adding an appropriate amount of one or two of CaO and SiO 2 to the ferrite and utilizing the effect of grain boundary segregation, the resistivity can be further increased, and ZrO 2 , Ta 2 0 5 , HfO 2 Further, a further reduction in coercive force can be achieved by adding an appropriate amount of one or more of Nb 2 0 5 to suppress the crystal grain size. Furthermore, the effect which combined the said effect is acquired by adding combining these.
なお、本発明のフェライトでは、Cd，Pb，Sb，As及びSeの不純物の量を規制し、異常粒成長の発生や雰囲気の変動に伴う特性劣化を抑制している。従って、その製造時に粉末冶金的な手法を用いることができ、さらに焼成の際の冷却時に、例えば酸素を１〜20体積ppm含む工業用の窒素を用いることが可能であるから、従来に比べ大幅な製造コストを削減した、安定した製造を実現できる。 In the ferrite of the present invention, the amount of impurities of Cd, Pb, Sb, As, and Se is regulated to suppress characteristic deterioration caused by abnormal grain growth and atmospheric variation. Therefore, it is possible to use a powder metallurgy method during the production, and furthermore, it is possible to use, for example, industrial nitrogen containing 1 to 20 ppm by volume of oxygen at the time of cooling during firing. Stable manufacturing with reduced manufacturing costs can be realized.
以下、本発明を具体的に説明する。
まず、本発明において、基本成分を上記の範囲に限定した理由を説明する。なお、本発明における基本成分組成は、含まれるFeおよびMnを全てFe203およびMnOとして換算した場合のものである。
The present invention will be specifically described below.
First, the reason why the basic component is limited to the above range in the present invention will be described. The basic component composition of the present invention is for the case where all the Fe and Mn contained in terms as Fe 2 0 3 and MnO.
Fe2O3：45.0 mol％以上50.0mol％未満
主成分組成のうち、Fe203は過剰に含まれた場合Fe2+量が増加し、それによりMn−Znフェライトの比抵抗が低下する。これを避けるために、Fe2O3量は50mol％未満に抑える必要がある。しかし、少なすぎると、今度は室温での保磁力の上昇及びキュリー温度の低下を招くため、最低でも45.0mol％は含有することとした。
Fe 2 O 3 : 45.0 mol% or more and less than 50.0 mol% Among the main component composition, when Fe 2 0 3 is excessively contained, the amount of Fe 2+ increases, thereby reducing the specific resistance of Mn-Zn ferrite. . In order to avoid this, the amount of Fe 2 O 3 needs to be suppressed to less than 50 mol%. However, if the amount is too small, this will cause an increase in coercive force at room temperature and a decrease in Curie temperature. Therefore, the minimum content is 45.0 mol%.
CoO：0.5mol％以上4.0mol％以下
Co2+は、正の磁気異方性エネルギーをもつイオンであるから、CoOの適正量の添加に伴って磁気異方性エネルギーの総和の絶対値が低下する結果、室温での保磁力の低下を実現する。そのためには、CoOを0.5mol％以上で添加する必要がある。しかし、適正量以上の添加は、比抵抗の低下を招き、また磁気異方性エネルギーの総和が過度に正に傾くことから、逆に室温での保磁力の上昇を招くことになる。従って、CoOの添加量は、最大4.0mol％の添加にとどめるものとする。
CoO: 0.5mol% to 4.0mol%
Since Co 2+ is an ion with positive magnetic anisotropy energy, the absolute value of the sum of magnetic anisotropy energy decreases as the appropriate amount of CoO is added, resulting in a decrease in coercivity at room temperature. Is realized. For that purpose, it is necessary to add CoO at 0.5 mol% or more. However, addition of an appropriate amount or more leads to a decrease in specific resistance, and the sum of magnetic anisotropy energy is excessively inclined, and conversely an increase in coercive force at room temperature. Therefore, the amount of CoO added is limited to a maximum of 4.0 mol%.
ZnO：15.5 mol％以上24.0mol％以下
ZnOは、フェライトに軟磁性的な性質を持たせるために不可欠な成分である。その添加に伴い室温での保磁力を低下させる働きがあるため、最低でも15.5mol％は含有するものとする。しかし、含有量が適正な値より多い場合には、キュリー温度の低下を招き、実用上問題がある。そのため、上限を24.0mol％とする。
ZnO: 15.5 mol% to 24.0 mol%
ZnO is an essential component for imparting soft magnetic properties to ferrite. Since the addition has the function of reducing the coercive force at room temperature, it should contain at least 15.5 mol%. However, if the content is higher than the appropriate value, the Curie temperature is lowered, which causes a practical problem. Therefore, the upper limit is 24.0 mol%.
MnO：残部
本発明のMn−Co−Zn系フェライトであり、主成分組成の残部はMnOである。残部をMnOとすることによって、高飽和磁束密度、低損失および高透磁率等の良好な磁気特性が得られる。
MnO: balance The Mn-Co-Zn ferrite of the present invention, and the balance of the main component composition is MnO. By using MnO as the balance, good magnetic properties such as high saturation magnetic flux density, low loss, and high magnetic permeability can be obtained.
Cd，Pb，Sb，AsおよびSe：それぞれ20massppm未満
Cd，Pb，Sb，AsおよびSeの各成分は、主成分原料である酸化鉄、酸化マンガン、酸化コバルトおよび酸化亜鉛中に含まれる成分である。これら成分の含有が極く微量であれば問題はないが、ある一定以上含まれる場合にはフェライトの異常粒成長を誘発し、得られるフェライトの諸特性に重大な悪影響を及ぼす。特に、Fe2O3を50mol％未満しか含まない組成のフェライトは、50mol％以上含むものに比べ結晶の粒成長が進行しやすく、そのため異常粒成長が発生しやすくなる。
Cd, Pb, Sb, As and Se: each less than 20 massppm
Each component of Cd, Pb, Sb, As, and Se is a component contained in iron oxide, manganese oxide, cobalt oxide, and zinc oxide which are main component raw materials. If these components are contained in a very small amount, there is no problem, but if they are contained in a certain amount or more, abnormal grain growth of ferrite is induced, and the various properties of the obtained ferrite are seriously adversely affected. In particular, ferrite having a composition containing less than 50 mol% of Fe 2 O 3 is more likely to cause crystal grain growth than that containing 50 mol% or more, and thus abnormal grain growth is likely to occur.
ここで、CoOについて、前記した理由による保持力の低下を狙い、その添加を行ったものの十分な効果が得られなかったところから、この原因について鋭意調査した結果、前記５成分をすべて抑制することによって、初めてCoOの添加効果が現出することを見出した。すなわち、これら５成分の混入により、異常粒成長が発生する等の弊害が生じてCoOの添加効果が相殺されていたものと考えられる。よって、Cd，Pb，Sb，AsおよびSeの含有量は、それぞれ20ppm未満に制限する必要がある。 Here, about CoO, aiming at a decrease in holding power due to the above-mentioned reason, and adding it, a sufficient effect was not obtained, but as a result of earnest investigation about this cause, all five components are suppressed. As a result, it was found that the addition effect of CoO appears for the first time. That is, it is considered that the effect of adding CoO was offset by the adverse effects such as abnormal grain growth due to the mixing of these five components. Therefore, the contents of Cd, Pb, Sb, As and Se need to be limited to less than 20 ppm, respectively.
CaO：0.005〜0.200mass％およびSiO2：0.001〜0.050mass％のうちから選んだ１種または２種
CaOおよびSiO2はいずれも、結晶粒界に偏析することによりフェライトの電気抵抗を高め、また粒成長時の粒界の移動速度を緩和させることから粒内残留空孔を減らし磁壁移動を容易にし、室温での保磁力を低下させる効果がある。これらの効果を得るには、CaO：0.005mass％以上およびSiO2：0.001mass％以上の添加が必要である。反対に多量に添加し過ぎた場合には、フェライト粒内の異常粒成長を誘発し、比抵抗の低下と保磁力の上昇をまねくことになる。そこで、上限はCaO：0.200mass％およびSiO2：0.050mass％とすることが望ましい。
CaO: 0.005~0.200mass% and SiO 2: chose from among the 0.001~0.050mass% 1 alone or in combination of two or
Both CaO and SiO 2 increase the electrical resistance of ferrite by segregating at the grain boundaries, and also reduce the intra-granular residual vacancies and ease the domain wall movement by reducing the movement speed of the grain boundaries during grain growth. There is an effect of reducing the coercive force at room temperature. In order to obtain these effects, it is necessary to add CaO: 0.005 mass% or more and SiO 2 : 0.001 mass% or more. On the other hand, if too much is added, abnormal grain growth in the ferrite grains is induced, leading to a decrease in specific resistance and an increase in coercive force. Therefore, the upper limit is CaO: 0.200mass% and SiO 2: It is desirable to 0.050 mass%.
ZrO2：0.005〜0.100mass％、Ta2O5：0.005〜0.100mass％、HfO2：0.005〜0.100mass％およびNb2O5：0.005〜0.100mass％のうちから選んだ１種または２種以上
また、添加物として、ZrO2，Ta2O5，HfO2及びNb2O5を１種又は２種以上を添加しても良い。これらの物質はいずれも、高い融点を持つ化合物であり、Mn−Co−Zn系フェライトに添加した場合には結晶粒を小さくする働きを持ち、そのため比抵抗を上昇させる。また、粒内残留空孔を減少させることから、室温での保磁力を低下させる。しかし、添加量が適正な値よりも少ない場合には効果が得られず、また多量の場合には異常粒発生による比抵抗の低下と保磁力の上昇とを招く。そのため、ZrO2：0.005〜0.100mass％、Ta2O5：0.005〜0.100mass％、HfO2：0.005〜0.100mass％およびNb2O5：0.005〜0.100mass％の範囲内に収めることが望ましい。
One or more selected from ZrO 2 : 0.005 to 0.100 mass%, Ta 2 O 5 : 0.005 to 0.100 mass%, HfO 2 : 0.005 to 0.100 mass% and Nb 2 O 5 : 0.005 to 0.100 mass% Further, as an additive, ZrO 2, Ta 2 O 5, the HfO 2 and Nb 2 O 5 may be added alone or in combination. Any of these substances is a compound having a high melting point, and when added to the Mn-Co-Zn ferrite, has a function of reducing crystal grains, and thus increases the specific resistance. In addition, since the intragranular residual vacancies are reduced, the coercivity at room temperature is lowered. However, when the added amount is less than the appropriate value, the effect cannot be obtained, and when the added amount is large, the specific resistance is decreased and the coercive force is increased due to the generation of abnormal grains. Therefore, ZrO 2: 0.005~0.100mass%, Ta 2 O 5: 0.005~0.100mass%, HfO 2: 0.005~0.100mass% and Nb 2 O 5: It is desirable to fall within a range of 0.005~0.100mass%.
なお、上記にて群れ毎に解説した添加物は、その群れ毎の単独添加でも上記のとおり有効であるが、さらに複数の群れの組み合わせにて添加する場合でも、同様に効果を発揮する。その際も、異常粒成長の発生、比抵抗の低下および室温での保磁力の上昇を抑えるため、その添加量は上記の範囲内に抑えることが望ましい。 In addition, although the additive demonstrated for every group above is effective as above-mentioned even if individual addition for every group is carried out, even when it adds by the combination of a some group, it demonstrates an effect similarly. Also in that case, in order to suppress the occurrence of abnormal grain growth, a decrease in specific resistance, and an increase in coercive force at room temperature, it is desirable to suppress the addition amount within the above range.
次に、本発明のMn−Co−Zn系フェライトの好適な製造方法について説明する。
まず、所定の比率となるように、Fe2O3，ZnO，CoO及びMnO粉末を秤量し、これらを十分に混合した後に仮焼を行う。次に、得られた仮焼粉を粉砕する。さらに、上記の添加物を加える際は、それらを所定の比率で加え、仮焼粉と同時に粉砕を行う。この作業で、添加した成分の濃度に偏りがないよう粉末の充分な均質化を行う必要がある。目標組成の粉末をポリビニルアルコール等の有機物バインダーを用いて造粒し、圧力を加えて成形後適宜の焼成条件の下で焼成を行う。
Next, a preferred method for producing the Mn—Co—Zn ferrite of the present invention will be described.
First, Fe 2 O 3 , ZnO, CoO, and MnO powder are weighed so as to have a predetermined ratio, and after sufficiently mixing them, calcining is performed. Next, the obtained calcined powder is pulverized. Furthermore, when adding said additive, they are added by a predetermined | prescribed ratio and it grind | pulverizes simultaneously with calcined powder. In this operation, it is necessary to sufficiently homogenize the powder so that the concentration of the added component is not biased. The powder of the target composition is granulated using an organic binder such as polyvinyl alcohol, and pressure is applied, followed by molding and firing under appropriate firing conditions.
ここで、本発明のMn−Co−Zn系フェライトは、不純物量が制限されているため、粉末冶金的手法を用いた際に問題となる異常粒成長や、焼成時の雰囲気の変動に対しても、保磁力の上昇のような特性劣化を起こしにくい。そのため、上記のように、製造時に粉末冶金的な手法を用いることができ、さらに焼成の際の冷却時に、例えば酸素を１〜20体積ppm含む工業用の窒素を用いることが可能である。 Here, since the amount of impurities in the Mn-Co-Zn ferrite of the present invention is limited, the abnormal grain growth that becomes a problem when using a powder metallurgical technique and the fluctuation of the atmosphere during firing are considered. However, it is difficult to cause characteristic deterioration such as an increase in coercive force. Therefore, as described above, a powder metallurgical technique can be used at the time of production, and industrial nitrogen containing, for example, 1 to 20 ppm by volume of oxygen can be used at the time of cooling during firing.
かくして得られたMn−Co−Zn系フェライトは、Fe2+量が従来のMn−Znフェライトに比べ大きく減少している。そのため、従来のMn−Znフェライトの問題点であった低い比抵抗が、0.1Ω・mオーダーから約300倍の領域にまで上昇する。また、Co添加による磁気異方性エネルギーの制御、並びに不純物量規定により異常粒成長が抑制されたことにより、保磁力が大幅に低下している。 In the Mn—Co—Zn ferrite thus obtained, the amount of Fe 2+ is greatly reduced as compared with the conventional Mn—Zn ferrite. Therefore, the low specific resistance, which has been a problem of the conventional Mn-Zn ferrite, rises from the order of 0.1 Ω · m to about 300 times. In addition, the coercive force is greatly reduced by controlling magnetic anisotropy energy by adding Co and suppressing abnormal grain growth by regulating the amount of impurities.
含まれるFe及びMnをすべてFe2Ｏ3及びMnＯとして換算した場合に、Fe2O3，ZnO，CoO及びMnOが表１に示す比率となるように秤量した各原料粉末を、ボールミルを用いて16時間混合した後、空気中925℃および３時間の仮焼を行った。次に、ボールミルで12時間粉砕を行い、得られた混合粉にポリビニルアルコールを加えて造粒し、1.2ton/cm2の圧力をかけトロイダルコアを成形した。その後、この成形体を焼成炉に装入して、窒素流入により酸素濃度が制御された雰囲気の下、最高温度1350℃で焼成を行い、焼成後の冷却の際には、1100℃から500℃までの温度範囲で酸素分圧10ppmを含む工業用窒素流中で行い、外径25mm、内径15mmおよび高さ５mmの焼結体コアを得た。
このようにして得られた各試料について、室温での比抵抗並びに保磁力を算出した。得られた結果を表１に併記する。
Using a ball mill, each raw material powder weighed so that Fe 2 O 3 , ZnO, CoO and MnO have the ratios shown in Table 1 when all of Fe and Mn contained are converted as Fe 2 O 3 and MnO. After mixing for 16 hours, calcination was performed in air at 925 ° C. for 3 hours. Next, it was pulverized with a ball mill for 12 hours, and polyvinyl alcohol was added to the obtained mixed powder for granulation, and a toroidal core was formed by applying a pressure of 1.2 ton / cm 2 . After that, the compact was charged into a firing furnace and fired at a maximum temperature of 1350 ° C in an atmosphere in which the oxygen concentration was controlled by inflow of nitrogen. During cooling after firing, 1100 ° C to 500 ° C Up to a temperature range of up to 10 ppm in an industrial nitrogen stream containing 10 ppm oxygen partial pressure to obtain a sintered core having an outer diameter of 25 mm, an inner diameter of 15 mm and a height of 5 mm.
For each sample thus obtained, the specific resistance and coercive force at room temperature were calculated. The obtained results are also shown in Table 1.
なお、酸化鉄等の主成分原料に由来する成分であるCd，Pb，Sb，As及びSeの最終的な含有量は全ての試料でそれぞれ３ppmであった。そのため、従来のMn−Co−Zn系フェライトで問題となる異常粒成長については、表１内のすべての発明例および比較例において確認されなかった。 The final contents of Cd, Pb, Sb, As, and Se, which are components derived from main component raw materials such as iron oxide, were 3 ppm for all samples. Therefore, the abnormal grain growth which is a problem in the conventional Mn-Co-Zn ferrite has not been confirmed in all the inventive examples and comparative examples in Table 1.
同表に示したとおり、発明例である試料番号１−３、１−５および１−９では、室温での比抵抗が30Ω・m以上かつ保磁力が10.0A／m以下、という優れた特性を有している。 As shown in the table, Sample Nos. 1-3, 1-5, and 1-9, which are invention examples, have excellent characteristics such as a specific resistance at room temperature of 30 Ω · m or more and a coercive force of 10.0 A / m or less. have.
これに対し、Fe2O3が50.0mol％以上の比較例（試料番号１−１，１−２）はいずれもFe2+を多く含有するため、比抵抗が低く、発明例の300分の1程度にとどまっている。反対に、Fe2O3が不足した比較例（試料番号１−10）では、保磁力の上昇と、キュリー温度の低下が確認される。前記Cd等５成分が低減されていてもCoOを含まない比較例（試料番号１−４）では、負の結晶磁気異方性を持つイオンのみから成るため、室温での保磁力が大きな値をとっている。反対にCoOを多量に含む比較例（試料番号１―６）では、正の結晶磁気異方性が過度に増大し、逆に保磁力が上昇している。ZnOに着目すると、発明範囲より不足した比較例（試料番号１−６）では保磁力の上昇が見られる。反対に、多量に含む比較例（試料番号１−８）では、キュリー温度が100℃未満であり、実用上問題がある。 On the other hand, since the comparative examples (sample numbers 1-1 and 1-2) in which Fe 2 O 3 is 50.0 mol% or more contain a large amount of Fe 2+ , the specific resistance is low, which is 300 minutes of the invention example. It remains at around 1. On the contrary, in the comparative example (sample number 1-10) in which Fe 2 O 3 is insufficient, an increase in coercive force and a decrease in Curie temperature are confirmed. In the comparative example (sample number 1-4) which does not contain CoO even though the five components such as Cd are reduced, the coercive force at room temperature has a large value because it consists only of ions having negative crystal magnetic anisotropy. I'm taking it. On the contrary, in the comparative example (Sample Nos. 1-6) containing a large amount of CoO, the positive magnetocrystalline anisotropy increases excessively, and conversely, the coercive force increases. When attention is focused on ZnO, an increase in coercive force is observed in the comparative example (Sample Nos. 1-6) lacking from the scope of the invention. On the other hand, in the comparative example (sample number 1-8) containing a large amount, the Curie temperature is less than 100 ° C., which is a practical problem.
Cd，Pb，Sb，As及びSeの含有量が異なる種々の酸化鉄、酸化マンガン、酸化コバルト及び酸化亜鉛原料を使用し、試料が最終的にCd，Pb，Sb，As及びSeを表２に示す量だけ含有するように計算した上で、含まれるFe及びMnをすべてFe203及びMnOとして換算した場合に、表１における試料番号１−５と同組成である、Fe203：49.0mol％、ZnO：20.0mol％、CoO：2.0mol％およびMnO：29.0mol％の組成となるように、原料を秤量し、ボールミルを用いて16時間混合した後、空気中925℃で３時間仮焼を行った。次に、ボールミルで12時間粉砕を行い、得た混合粉にポリビニルアルコールを加えて造粒し、1.2ton／cm2の圧力をかけトロイダルコアを成形した。その後、この成形体を焼成炉に入れ、窒素流入により酸素濃度が制御された雰囲気の下、最高温度1350℃で焼成を行い焼成後の冷却の際には、1100℃から500℃までの温度範囲で酸素分圧10ppmを含む工業用窒素流中で行い、外径25mm、内径15mmおよび高さ５mmの焼結体コアを得た。
これらの各試料について、室温での比抵抗および保磁力を測定した。なお、主成分組成により決まるキュリー温度は、全ての試料で130℃であった。
得られた結果を表２に示す。
Various iron oxide, manganese oxide, cobalt oxide and zinc oxide raw materials with different contents of Cd, Pb, Sb, As and Se were used, and the samples finally showed Cd, Pb, Sb, As and Se in Table 2. after having calculated to contain an amount shown, when calculated as all the Fe and Mn Fe 2 0 3 and MnO contained a same composition as sample No. 1-5 in Table 1, Fe 2 0 3: The raw materials were weighed to a composition of 49.0 mol%, ZnO: 20.0 mol%, CoO: 2.0 mol%, and MnO: 29.0 mol%, mixed for 16 hours using a ball mill, and then in air at 925 ° C for 3 hours Calcination was performed. Next, it was pulverized with a ball mill for 12 hours, and polyvinyl alcohol was added to the obtained mixed powder for granulation, and a toroidal core was formed by applying a pressure of 1.2 ton / cm 2 . After that, this molded body is put into a firing furnace, fired at a maximum temperature of 1350 ° C in an atmosphere in which the oxygen concentration is controlled by inflow of nitrogen, and when cooled after firing, a temperature range from 1100 ° C to 500 ° C Was performed in an industrial nitrogen flow containing an oxygen partial pressure of 10 ppm to obtain a sintered body core having an outer diameter of 25 mm, an inner diameter of 15 mm, and a height of 5 mm.
About each of these samples, the specific resistance and coercive force at room temperature were measured. The Curie temperature determined by the main component composition was 130 ° C. for all samples.
The obtained results are shown in Table 2.
同表に示したとおり、Cd，Pb，Sb，AsおよびSe成分がそれぞれ20ppm未満の発明例（試料番号１−５，２−１）はいずれも異常粒成長が見られず、高い比抵抗と低い保磁力とが同時に得られている。
これに対し、５種類のうち１成分でも適正な値より多く含む比較例（試料番号２−２〜２−７）はいずれも異常粒が発生し、比抵抗および保磁力ともに大きく劣化している。
As shown in the table, all of the inventive examples (sample numbers 1-5 and 2-1) in which Cd, Pb, Sb, As and Se components are each less than 20 ppm show no abnormal grain growth, and have high specific resistance. Low coercivity is obtained at the same time.
On the other hand, in all of the comparative examples (sample numbers 2-2 to 2-7) including more than one proper component among the five types, abnormal grains are generated and both the specific resistance and the coercive force are greatly deteriorated. .
実施例２と同組成の混合粉（但し、Cd，Pb，Sb，AsおよびSe：すべて３ppm含有）に、添加物としてCaＯ及びSiO2をそれぞれ最終組成が表３に示す比率となるよう添加し、ボールミルで12時間粉砕を行った。この混合粉にポリビニルアルコールを加えて造粒し、1.2ton／cm2の圧力を加えてトロイダルコアを成形し、その後この成形体を焼成炉に入れて最高温度1350℃で焼成を行い、焼成後の冷却の際には、1100℃から500℃までの温度範囲で酸素分圧10ppmを含む工業用窒素流中で行い、外径25mm、内径15mmおよび高さ５mmの焼結体コアを得た。
これらの各試料について、室温での比抵抗および保磁力を測定した。なお、主成分組成により決まるキュリー温度は、全ての試料で130℃であった。
得られた結果を表３に示す。
Add CaO and SiO 2 as additives to the mixed powder having the same composition as in Example 2 (however, Cd, Pb, Sb, As, and Se: all containing 3 ppm) so that the final composition has the ratio shown in Table 3. Then, the mixture was pulverized with a ball mill for 12 hours. This mixed powder is granulated by adding polyvinyl alcohol, and a toroidal core is formed by applying a pressure of 1.2 ton / cm 2 , and then the formed body is placed in a firing furnace and fired at a maximum temperature of 1350 ° C. Was cooled in an industrial nitrogen flow containing an oxygen partial pressure of 10 ppm in the temperature range from 1100 ° C. to 500 ° C. to obtain a sintered body core having an outer diameter of 25 mm, an inner diameter of 15 mm and a height of 5 mm.
About each of these samples, the specific resistance and coercive force at room temperature were measured. The Curie temperature determined by the main component composition was 130 ° C. for all samples.
The obtained results are shown in Table 3.
表３の結果から、CaＯ及びSiO2を１種または２種添加した発明例（試料番号３−１〜３−３）は、比抵抗が上昇し、また粒内残留空孔の減少から保磁力が低下していることがわかる。しかし、どちらか一方でも適正な値より多く含む比較例（試料番号３−４〜３−６）ではいずれも、異常粒が発生し、粒内に多数の不純物や空孔を含むために比抵抗が低下し、また磁壁の移動が阻害されることから保磁力が上昇している。 From the results shown in Table 3, the invention example (Sample Nos. 3-1 to 3-3) to which one or two of CaO and SiO 2 were added increased the specific resistance, and the coercive force was decreased due to the decrease in residual grains. It can be seen that is decreasing. However, in any of the comparative examples (sample numbers 3-4 to 3-6) including more than the appropriate value in either one of them, abnormal particles are generated and a large number of impurities and vacancies are included in the particles. And the coercive force is increased because the movement of the domain wall is hindered.
実施例２と同組成の混合粉（但し、Cd，Pb，Sb，As及びSe：すべて３ppm含有）に、添加物としてNb205，TaO2，HfO2及びZrO2をそれぞれ最終組成が表４に示す比率となるよう添加し、ボールミルで12時間粉砕を行った。この混合粉にポリビニルアルコールを加えて造粒し、1.2ton／cm2の圧力を加えてトロイダルコアを成形し、その後この成形体を焼成炉に入れ、最高温度1350℃で焼成を行い焼成後の冷却の際には、1100℃から500℃までの温度範囲で酸素分圧10ppmを含む工業用窒素流中で行い、外径25mm、内径15mmおよび高さ５mmの焼結体コアを得た。
これらの各試料について、室温での比抵抗、保磁力を測定した。なお、主成分組成により決まるキュリー温度は、全ての試料で130℃であった。
得られた結果を表４に示す。
The final composition of Nb 2 0 5 , TaO 2 , HfO 2 and ZrO 2 as additives was added to the mixed powder of the same composition as in Example 2 (however, Cd, Pb, Sb, As and Se: all containing 3 ppm). The mixture was added so as to have a ratio shown in FIG. Polyvinyl alcohol is added to this mixed powder and granulated, and a toroidal core is formed by applying a pressure of 1.2 ton / cm 2 , and then the formed body is placed in a firing furnace and fired at a maximum temperature of 1350 ° C. The cooling was performed in an industrial nitrogen flow containing 10 ppm oxygen partial pressure in the temperature range from 1100 ° C. to 500 ° C. to obtain a sintered core having an outer diameter of 25 mm, an inner diameter of 15 mm, and a height of 5 mm.
About each of these samples, the specific resistance and coercive force at room temperature were measured. The Curie temperature determined by the main component composition was 130 ° C. for all samples.
Table 4 shows the obtained results.
表４の結果から、Nb205，TaO2，HfO2およびZrO2を１種または２種以上で適量添加した発明例（試料番号４−１〜４−１５）はいずれも、結晶の成長が抑制された結果、比抵抗が上昇した。また、粒内残留空孔の減少により保磁力も低下している。
しかし、これら４成分のうち１種類でも適正範囲を超えて多量に含有する比較例（試料番号４−16〜４−18）ではいずれも、異常粒が発生し、粒内に多数の不純物や空孔を含むため比抵抗が低下し、また保磁力が上昇している。
From the results shown in Table 4, all of the inventive examples (sample numbers 4-1 to 4-15) to which Nb 2 0 5 , TaO 2 , HfO 2 and ZrO 2 were added in appropriate amounts by one or more types were grown as crystals. As a result, the specific resistance increased. In addition, the coercive force is also reduced due to the reduction of the intragranular residual voids.
However, in any of the comparative examples (Sample Nos. 4-16 to 4-18) containing a large amount of one of these four components exceeding the appropriate range, abnormal grains are generated, and many impurities and vacancies are formed in the grains. Since it includes holes, the specific resistance decreases and the coercive force increases.
実施例２と同組成の混合粉（但し、Cd，Pb，Sb，As及びSe：すべて３ppm含有）に、副成分としてCaＯおよびSiO2と、ZrO2，Ta2O5，HfO2およびNb205とを最終成分が表５に示す比率となるように、それぞれ添加し、ボールミルで12時間粉砕を行った。この混合粉にポリビニルアルコールを加えて造粒し、1.2ton／cm2の圧力を加えてトロイダルコアを成形し、その後この成形体を焼成炉に入れて最高温度1350℃で焼成を行い、焼成後の冷却の際には、1100℃から500℃までの温度範囲で酸素分圧10ppmを含む工業用窒素流中で行い、外径25mm、内径15mmおよび高さ５mmの焼結体コアを得た。
これらの各試料について、室温での比抵抗および保磁力を測定した。なお、主成分組成により決まるキュリー温度は、全ての試料で130℃であった。
得られた結果を表５に示す。
The mixed powder having the same composition as in Example 2 (however, Cd, Pb, Sb, As and Se: all containing 3 ppm), CaO and SiO 2 as accessory components, ZrO 2 , Ta 2 O 5 , HfO 2 and Nb 2 0 and 5 were added so that the final components had the ratios shown in Table 5, and pulverized for 12 hours with a ball mill. This mixed powder is granulated by adding polyvinyl alcohol, and a toroidal core is formed by applying a pressure of 1.2 ton / cm 2 , and then the formed body is placed in a firing furnace and fired at a maximum temperature of 1350 ° C. Was cooled in an industrial nitrogen flow containing an oxygen partial pressure of 10 ppm in the temperature range from 1100 ° C. to 500 ° C. to obtain a sintered body core having an outer diameter of 25 mm, an inner diameter of 15 mm and a height of 5 mm.
About each of these samples, the specific resistance and coercive force at room temperature were measured. The Curie temperature determined by the main component composition was 130 ° C. for all samples.
The results obtained are shown in Table 5.
表５に示したとおり、CaOおよびSiO2と、ZrO2，Ta2O5，HfO2およびNb205とを組み合わせて添加した発明例（試料番号５−１〜５−９）はいずれも、これらが無添加の場合と比べて比抵抗が上昇し、保磁力が低下した。
対して、これら６成分のうちどれか１つでも適正な値より多く含む比較例（試料番号５−10〜５−11）ではいずれも、異常粒が発生し、粒内に多数の不純物や空孔を含むため比抵抗が低下し、保磁力が上昇している。
As shown in Table 5, all of the invention examples (sample numbers 5-1 to 5-9) in which CaO and SiO 2 and ZrO 2 , Ta 2 O 5 , HfO 2 and Nb 2 0 5 were added in combination were added. The specific resistance increased and the coercive force decreased compared to the case where these were not added.
On the other hand, in any of the comparative examples (sample numbers 5-10 to 5-11) in which any one of these six components exceeds the appropriate value, abnormal grains are generated, and a large number of impurities and vacancies are formed in the grains. Since the hole is included, the specific resistance is decreased and the coercive force is increased.
Claims (3)
CoO：0.5mol％以上4.0mol％以下、
ZnO：15.5 mol％以上24.0mol％以下および
MnO：残部
を基本成分とし、
フェライト中に含まれるCd，Pb，Sb，AsおよびSeがそれぞれ20massppm未満であることを特徴とするMn−Co−Zn系フェライト。 Fe 2 O 3 : 45.0 mol% or more and less than 50.0 mol%,
CoO: 0.5 mol% or more and 4.0 mol% or less,
ZnO: 15.5 mol% or more and 24.0 mol% or less and
MnO: The balance is the basic component,
An Mn-Co-Zn ferrite characterized in that Cd, Pb, Sb, As and Se contained in the ferrite are each less than 20 massppm.
CaO：0.005〜0.200mass％および
SiO2：0.001〜0.050mass％
のうちから選んだ１種または２種を含有する請求項１に記載のMn−Co−Zn系フェライト。 In the ferrite, further as an additive
CaO: 0.005-0.200 mass% and
SiO 2 : 0.001 to 0.050 mass%
The Mn-Co-Zn-based ferrite according to claim 1, containing one or two selected from among them.
ZrO2：0.005〜0.100mass％、
Ta2O5：0.005〜0.100mass％、
HfO2：0.005〜0.100mass％および
Nb2O5：0.005〜0.100mass％
のうちから選んだ１種または２種以上を含有する請求項１または２に記載のMn−Co−Zn系フェライト。 In the ferrite, further as an additive
ZrO 2 : 0.005 to 0.100 mass%,
Ta 2 O 5 : 0.005 to 0.100 mass%,
HfO 2 : 0.005 to 0.100 mass% and
Nb 2 O 5 : 0.005 to 0.100 mass%
The Mn—Co—Zn-based ferrite according to claim 1, comprising one or more selected from among the above.
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| JP4554965B2 (en) * | 2004-03-24 | 2010-09-29 | Ｊｆｅケミカル株式会社 | Mn-Co-Zn ferrite |
| JP5742358B2 (en) * | 2011-03-25 | 2015-07-01 | Tdk株式会社 | Ferrite composition for radio wave absorber and ferrite core for radio wave absorber |
| CN102795851B (en) * | 2011-05-23 | 2016-04-13 | Tdk株式会社 | ferrite composition and electronic component |
| JP5733100B2 (en) * | 2011-08-10 | 2015-06-10 | Tdk株式会社 | Ferrite composition and electronic component |
| JP5786454B2 (en) * | 2011-05-23 | 2015-09-30 | Tdk株式会社 | Ferrite core and electronic components |
| JP5488536B2 (en) * | 2011-06-22 | 2014-05-14 | Ｔｄｋ株式会社 | Ferrite core and electronic components |
| JP5742504B2 (en) * | 2011-06-22 | 2015-07-01 | Tdk株式会社 | Ferrite composition and electronic component |
| JP5929119B2 (en) * | 2011-11-21 | 2016-06-01 | Tdk株式会社 | Ferrite composition and electronic component |
| JP5831256B2 (en) * | 2012-01-26 | 2015-12-09 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP5831255B2 (en) * | 2012-01-26 | 2015-12-09 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP5831254B2 (en) * | 2012-01-26 | 2015-12-09 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6064526B2 (en) * | 2012-11-01 | 2017-01-25 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6064525B2 (en) * | 2012-11-01 | 2017-01-25 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6051930B2 (en) * | 2013-01-18 | 2016-12-27 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6311298B2 (en) * | 2013-12-10 | 2018-04-18 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6322987B2 (en) * | 2013-12-10 | 2018-05-16 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6323042B2 (en) * | 2014-02-14 | 2018-05-16 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6323043B2 (en) * | 2014-02-14 | 2018-05-16 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6380729B2 (en) * | 2014-03-13 | 2018-08-29 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6380730B2 (en) * | 2014-03-13 | 2018-08-29 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP2015205787A (en) * | 2014-04-18 | 2015-11-19 | Tdk株式会社 | Ferrite composition, ferrite core and electronic component |
| JP6655381B2 (en) * | 2015-12-21 | 2020-02-26 | Ｎｊコンポーネント株式会社 | Ni-Mn-Zn ferrite material |
| CN110178191B (en) * | 2017-12-20 | 2021-05-11 | 杰富意化学株式会社 | MnCoZn-based ferrite and method for producing same |
| WO2019167393A1 (en) * | 2018-02-28 | 2019-09-06 | Ｊｆｅケミカル株式会社 | Mncozn ferrite and production method for same |
| JP6553833B1 (en) * | 2018-02-28 | 2019-07-31 | Ｊｆｅケミカル株式会社 | MnCoZn-based ferrite and method for producing the same |
| CN112041951B (en) * | 2019-01-31 | 2021-11-23 | 杰富意化学株式会社 | MnCoZn-based ferrite and method for producing same |
| CN111233452B (en) * | 2019-10-18 | 2021-09-17 | 横店集团东磁股份有限公司 | High-frequency high-impedance lean iron manganese zinc ferrite and preparation method thereof |
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