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JP3590941B2 - Low-loss oxide magnetic material and method for producing the same - Google Patents
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JP3590941B2 - Low-loss oxide magnetic material and method for producing the same - Google Patents

Low-loss oxide magnetic material and method for producing the same Download PDF

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JP3590941B2
JP3590941B2 JP22047795A JP22047795A JP3590941B2 JP 3590941 B2 JP3590941 B2 JP 3590941B2 JP 22047795 A JP22047795 A JP 22047795A JP 22047795 A JP22047795 A JP 22047795A JP 3590941 B2 JP3590941 B2 JP 3590941B2
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loss
low
less
magnetic material
oxide magnetic
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JPH0963824A (en
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吉孝 安田
努 大塚
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Tokin Corp
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NEC Tokin Corp
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/342Oxides
    • H01F1/344Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4

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  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Compounds Of Iron (AREA)
  • Magnetic Ceramics (AREA)
  • Soft Magnetic Materials (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、主に電気・通信機器等のスイッチング電源材料(トランス材料)として使用されると共に、主成分及び副成分を含むスピネル型結晶構造のMn−Zn系フェライトから成り、詳しくは副成分にP(五酸化リン)を含む低損失酸化物磁性材料及びその製造方法に関する。
【0002】
【従来の技術】
従来、この種の低損失酸化物磁性材料としては主にMn−Zn系フェライトが用いられている。このMn−Zn系フェライトがスイッチング電源材料として用いられる場合、駆動周波数帯域が数十〜200(kHz)程度の範囲とされるのが一般的である。Mn−Zn系フェライト自体はこうした使用周波数帯域で高性能であると共に、安価に製造可能であることが要求されるが、このような周波数帯域では一般に渦電流損失やヒステリシス損失を生じ易くなっているため、この両者を如何に低減するかが極めて重要な問題となっている。
【0003】
そこで、渦電流損失を低減するためには、スピネル相の電気抵抗や焼結体の粒界相の電気抵抗を向上させることが不可欠となっている。
【0004】
スピネル相自体の電気抵抗を向上させる場合、Fe2+及びFe3+間の電子によるホッピング現象を如何に抑制するかが重要となっており、こうした見地に立って製造過程では焼結条件の酸素分圧を高めることによってFe2+の減少化を計るか、或いはTi4+,Sn4+を含有させてFe3+と置換することによってホッピング現象の発生を抑制している。
【0005】
しかしながら、前者の手法の場合、Fe2+の極端な減少により透磁率μiが著しく劣化すると共に、保磁力Hcが増大して磁気特性の劣化を招いてしまう。又、後者の手法の場合、Ti4+,Sn4+等を添加していることで電力損失の温度特性において電力損失値が最小となる温度(ミニマムポイントと呼ばれる)が低温側へ著しく移動してしまい、これによって温度特性が劣化してしまう。更に、両者の何れの手法においても、スピネル相自体の電気抵抗を向上させても、焼結体の電気抵抗の方はさほど大きくならないという根本的な欠点がある。
【0006】
一方、粒界相の電気抵抗を向上させる場合、SiO,CaOを添加することにより高抵抗な粒界相を形成している。この手法はフェライト焼結体の抵抗を向上させるものとして最も効果的であり、それ故、最も頻度高く使用されている。この手法では適量のSiO,CaOを添加することによって結晶粒成長を制御できると共に、均一な結晶粒組織が得られる上、ヒステリシス損失(P)を低減化できる。
【0007】
【発明が解決しようとする課題】
上述した低損失酸化物磁性材料の場合、一般にMn−Zn系フェライトにPが含有されているとその製造過程で結晶粒径が不均一になり易く、これによってヒステリシス損失(P)が増大するばかりか、渦電流損失(P)の方も著しく劣化してしまう。
【0008】
特に、このようにMn−Zn系フェライトにPが含有されていると、粒界相の電気抵抗を向上させるためにSiO,CaOを添加してもその製造過程で結晶粒径が一層不均一になり易く、これによってヒステリシス損失(P)及び渦電流損失(P)の双方が著しく劣化してしまう。
【0009】
一般に、Pは主として酸化鉄原料中に多量に含有される場合が多く、こうした酸化鉄原料は含有しないものに比べて価格が安価になっている。ところが、このようにPを含有する酸化鉄原料を使用した場合には結晶粒径を均一にして充分に粒界相の電気抵抗を向上させることができない。この結果、Pを含むMn−Zn系フェライトをスイッチング電源材料とすると電力損失の増大を招いて発熱量を抑制し難くなるため、低損失が要求される各種OA機器等では適用不可能となっている。このように、Pを含むMn−Znフェライトは、均一な結晶粒径を有する優れた磁気特性を示すもの,即ち、良質な磁気特性を有する低損失酸化物磁性材料になり得ていないのが現状である。
【0010】
本発明は、このような問題点を解決すべくなされたもので、その技術的課題は、Pを含む酸化鉄原料を用いても使用周波数帯域において電力損失が小さく優れた磁気特性を有する低損失酸化物磁性材料及びその製造方法を提供することにある。
【0011】
【課題を解決するための手段】
本発明によれば、主成分及び副成分を含むスピネル型結晶構造のMn−Zn系フェライトから成る低損失酸化物磁性材料において、主成分は、52〜54(mol%)のFe,33〜37(mol%)のMnO,及び残部ZnOから成り、副成分は、0.007〜0.07(wt%)のP,0.12(wt%)以下(但し、0を含まず)のNaO,0.004〜0.020(wt%)のSiO,及び0.03〜0.12(wt%)のCaOを必須要素とすると共に、他要素として異なるナトリウム複合酸化物原料であるNaCOとNaNbO及びNaTaOのうちの少なくとも1種とをPを含む酸化鉄原料に対して同時に添加して生成される0.020wt%以下(但し、0を含まず)のNb並びに0.060(wt%)以下(但し、0を含まず)のTaのうちの少なくとも1種を含んで成り、且つ該Nb並びに該Taによる2種は総量で0.060(wt%)以下(但し、0を含まず)である低損失酸化物磁性材料が得られる。
【0012】
一方、本発明によれば、上記低損失酸化物磁性材料を製造するための方法において、Pを0.01〜0.1(wt%)含有する酸化鉄原料に対し、Nb並びにTaのうちの少なくとも1種を得るためにNaCOとNaNbO及びNaTaOのうちの少なくとも1種とによる異なるナトリウム複合酸化物原料を混合する混合工程と、混合工程で得られる混合体を予焼,解砕,造粒して成形プレスすることにより得られるプレス成形体を酸素分圧10.0%以下,温度条件1200〜1400(℃)において焼成する焼成工程とを含む低損失酸化物磁性材料の製造方法が得られる。
【0013】
【作用】
本発明の低損失酸化物磁性材料においては、主成分及び副成分を含むスピネル型結晶構造のMn−Zn系フェライトにおける副成分にPが含有される場合、その製造過程において安価な酸化鉄原料(Fe原料)におけるPの含有量が0.01〜0.01(wt%)の範囲であれば、副成分の必須要素として0.12wt%以下(但し、0を含まず)のNaO,0.004〜0.020(wt%)のSiO及び0.03〜0.12(wt%)のCaOが含有されることにより、電気抵抗が高く、優れた磁気特性を有するMn−Zn系フェライト(低損失酸化物磁性材料)が得られることを基本とし、更に、副成分の他要素として異なるナトリウム複合酸化物原料であるNaCOとNaNbO及びNaTaOのうちの少なくとも1種とをPを含む酸化鉄原料に対して同時に添加して生成される0.020(wt%)以下のNb並びに0.060(wt%)以下のTaのうちの少なくとも1種 が含有され、これらの2種が含有される場合には総量で0.060(wt%)以下(0を含まず)であるという条件を満たせば、一層電気抵抗が高く、優れた磁気特性を有するMn−Zn系フェライトが得られることを見い出したものである。
【0014】
【発明の実施の形態】
以下に実施例を挙げ、本発明の低損失酸化物磁性材料について、図面を参照して詳細に説明する。
【0015】
最初に、本発明の低損失酸化物磁性材料の概要を簡単に説明する。この低損失酸化物磁性材料は、主成分及び副成分を含むスピネル型結晶構造のMn−Zn系フェライトから成るもので、主成分は52〜54(mol%)のFeと、33〜37(mol%)のMnOと、残部ZnOとから成る。又、副成分は0.007〜0.07(wt%)のP(五酸化リン),0.12(wt%)以下(但し、0を含まず)のNaO(酸化ナトリウム),0.004〜0.020(wt%)のSiO(酸化珪素),0.03〜0.12(wt%)のCaO(酸化カルシウム)を必須要素とすると共に、他要素として異なるナトリウム複合酸化物原料であるNaCOとNaNbO及びNaTaOのうちの少なくとも1種とをPを含む酸化鉄原料に対して同時に添加して生成される0.020wt%以下(但し、0を含まず)のNb並びに0.060(wt%)以下(但し、0を含まず)のTaのうちの少なくとも1種を含んで成っている。
【0016】
但し、この低損失酸化物磁性材料の副成分に関して、他要素のNb並びにTaが2種である場合、総量で0.060(wt%)以下(但し、0を含まず)であることが好ましい。
【0017】
このような低損失酸化物磁性材料を製造する場合、Pを0.01〜0.1(wt%)含有する酸化鉄原料に対し、Nb並びにTaのうちの少なくとも1種を得るためにNaCO(炭酸ナトリウム)とNaNbO(ニオブ酸ナトリウム)及びNaTaO(タンタル酸ナトリウム)のうちの少なくとも1種とによる異なるナトリウム複合酸化物原料を混合する混合工程と、混合工程で得られる混合体を予焼,解砕,造粒して成形プレスすることにより得られるプレス成形体を酸素分圧10.0%以下,温度条件1200〜1400(℃)において焼成する焼成工程とを実施すれば良い。これによって上述した組成の低損失酸化物磁性材料が得られる。
【0018】
ここでの低損失酸化物磁性材料の組成(製造過程で用いられる原料に関するものを含む)において、主成分に関してFeを換算で52〜54(mol%),MnOを換算で33〜37(mol%),ZnOを残部として範囲限定した理由は、Feが換算で52mol%以下であったり、或いはMnOが換算で37mol%以上であると電力損失が増大して好ましくないし、又Feが換算で54mol%以上であったり、或いはMnOが換算で33mol%以下であっても電力損失のミニマム温度が低くなって好ましくないためである。
【0019】
一方、副成分に関して、製造過程における酸化鉄原料粉末におけるPの含有量を0.01〜0.1(wt%)の範囲[尚、焼結体として得られたものでは0.007〜0.07(wt%)の範囲に減じられる]に限定した理由は、その含有量が0.01wt%以下であればフェライトの高性能化に適するが、そのような酸化鉄原料粉末を用いることは高価になり過ぎるからであり、又その含有量が0.1wt%を超過していれば必須要素であるNaOを含有させても粒成長の制御が困難となって磁気特性が劣化するためである。
【0020】
更に、SiOの含有量を0.004wt%以上,CaOの含有量を0.03wt%以上とした理由は、それぞれ0.004wt%,0.03wt%以下であると充分な電気抵抗が得られず、渦電流損失が増大して磁気特性が劣化するためであり、又SiOの含有量を0.020wt%以下,CaOの含有量を0.12wt%以下とした理由は、それぞれ0.020wt%,0.12wt%を超過するとNaOを含有させても著しく結晶粒径が不均一となって磁気特性が劣化するためである。因みに、NaOはこれを添加することによってPの悪影響を除去できるものであるが、酸化物形態だけでなく炭酸塩,硝酸塩,塩化物の形態で添加しても同様な効果がある。しかしながら、こうした形態で添加した場合には、製造過程における焼結体組織に若干のばらつきが認められる。
【0021】
そこで、製造過程ではNb並びにTaのうちの少なくとも1種を安定して得られるようにするため、異なるナトリウム複合酸化物原料としてNaCOとNaNbO及びNaTaOのうちの少なくとも1種とを用いる。副成分の他要素であるNb並びにTaが得られれば、これにより粒界相の形成度が向上して渦電流損失の改善が計られる。即ち、製造過程にあってNaOは大気中で不安定であり、その特性により工業的には余り使用に適していないが、NaCOは価格も安価で大気中で安定しており、不足するNa成分を補うのに適している。このようにナトリウム複合酸化物粉末を用いる場合、添加量が微量であっても炭酸塩等の形態のものと共に添加すると焼結体組織のばらつきを抑制する効果,即ち、粒成長の制御を容易に行うことができ、これにより結晶粒径が均一な組織を得易くなる。
【0022】
尚、Nb並びにTaのうちの少なくとも1種に上限値を設けたり、或いはそれらの2種による総量に関して上限値を設けている理由は、それらの上限値を越えて添加(含有)された場合、逆に粒成長の制御が困難となってヒステリシス損失や渦電流損失の増大を引き起こすためである。
【0023】
以上、幾つかの異なるMn−Zn系フェライトから成る低損失酸化物磁性材料の組成並びにその特性について説明したが、更に以下はこうした低損失酸化物磁性材料の製造過程に関する幾つかの実施例に基づいて、組成並び特性に関する根拠を具体的に説明する。
【0024】
<実施例1>
実施例1では、先ず低損失酸化物磁性材料の主成分として、Fe,MnO,ZnOがそれぞれ換算で53.0mol%,35.5mol%,11.5mol%のスピネル型フェライトに対し、Pの含有量がそれぞれ0.012,0.022,0.030,0.035,0.051,0.067,0.074(wt%)となるように、Pの含有量がそれぞれ0.012,0.034,0.96(wt%)の酸化鉄原料を適当に混合して用いると共に、副成分としてNaOが換算で0.035wt%となるようにNaTaOを0.024(wt%),NaCOを0.056(wt%),SiOを0.016wt%,CaOを0.08wt%となるようにそれぞれ添加し、その上で上述した主成分の組成となるように補正し、これらを混合して混合体を得た。
【0025】
次に、この混合工程で得られた混合体を予焼,解砕,造粒して成形プレスした後、酸素分圧10.0%以下,温度条件1200〜1400(℃)において焼成して焼結体を得た。ここでの焼成工程により焼結体として総計6種類の低損失酸化物磁性材料が得られる。
【0026】
そこで、得られた各低損失酸化物磁性材料に関して、Pの含有量をパラメータとした場合、周波数100kHz,磁束密度2000G,温度80℃の条件下でPの含有量に対する電力損失PCV(kW/m)の特性を調べたところ、図1に示すような結果になった。
【0027】
図1からは、Pの含有量が0.07wt%以上,即ち、0.1wt%以上のPを含有する酸化鉄原料を用いた場合には電力損失PCVが著しく増大していることが判る。
【0028】
<実施例2>
実施例2では、実施例1の場合と同様な主成分のスピネル型フェライトに対し、Pが0.025(wt%)となるような酸化鉄原料を用いると共に、副成分としてSiOを0.016wt%,CaOを0.08wt%,NaTaOを0.024(wt%),NaCOをNaO量でそれぞれ0,0.017,0.051,0.085,0.136,0.203,0.255(wt%)となるように添加し、実施例1の場合と同様な手順で総計7種類の低損失酸化物磁性材料を得た。
【0029】
そこで、得られた各低損失酸化物磁性材料に関して、NaOの含有量をパラメータとした場合、周波数100kHz,磁束密度2000G,温度80℃の条件下でNaOの含有量に対する電力損失PCV(kW/m)の特性を調べたところ、図2に示すような結果になった。
【0030】
図2からは、NaOの含有量が0.12wt%以上であれば電力損失PCVが著しく増大していることが判る。
【0031】
<実施例3>
実施例3では、実施例1の場合と同様な主成分のスピネル型フェライトに対し、Pが0.025(wt%)となるような酸化鉄原料を用いると共に、副成分としてNaO換算で0.035wt%となるようにNaTaOを0.024wt%,NaCOを0.056wt%,CaOを0.08wt%,SiOの含有量をパラメータとしてそれぞれ0.002,0.004,0.010,0.016,0.020,0.030(wt%)となるように添加し、実施例1と場合と同様な手順で総計6種類の低損失酸化物磁性材料を得た。
【0032】
そこで、得られた各低損失酸化物磁性材料に関して、SiOの含有量をパラメータとした場合、周波数100kHz,磁束密度2000G,温度80℃の条件下でSiOの含有量に対する電力損失PCV(kW/m)の特性を調べたところ、図3に示すような結果になった。
【0033】
図3からは、SiOの含有量が0.004〜0.02(wt%)では電力損失PCVが小さく良好であることが判る。
【0034】
<実施例4>
実施例4では、実施例1の場合と同様な主成分のスピネル型フェライトに対し、Pが0.025(wt%)となるような酸化鉄原料を用いると共に、副成分としてNaO換算で0.035wt%となるようにNaTaOを0.024(wt%),NaCOを0.056(wt%),SiOを0.016wt%,CaOの含有量をパラメータとしてそれぞれ0.02,0.03,0.05,0.08,0.010,0.012,0.15(wt%)となるよう添加し、実施例1の場合と同様な手順で総計7種類の低損失酸化物磁性材料を得た。
【0035】
そこで、得られた各低損失酸化物磁性材料に関して、CaOの含有量をパラメータとした場合、周波数100kHz,磁束密度2000G,温度80℃の条件下でCaOの含有量に対する電力損失PCV(kW/m)の特性を調べたところ、図4に示すような結果になった。
【0036】
図4からは、CaOの含有量が0.03〜0.12(wt%)では電力損失PCVが小さく良好であることが判る。
【0037】
<実施例5>
実施例5では、実施例1の場合と同様な主成分のスピネル型フェライトに対し、Pが0.025(wt%)となるような酸化鉄原料を用いると共に、副成分として総量でNaO換算で含有量が0.12wt%以下(0を含まず)となるようにNaNbO,NaTaO,NaCOのうちのNaNbOが0.40wt%以下,NaTaOが0.140wt%以下,或いは2種の合計で0.140wt%以下,残部NaCOが0.210(wt%)以下(0を含まず),SiOが0.016wt%,CaOが0.08wt%となるようにそれぞれ添加し、実施例1の場合と同様な手順で総計22種類の低損失酸化物磁性材料を得た。
【0038】
そこで、得られた各低損失酸化物磁性材料に関して、ナトリウム複合酸化物(NaNbO,NaTaO,NaCO)の含有量をパラメータとした場合、周波数100kHz,磁束密度2000G,温度80℃の条件下でナトリウム複合酸化物の含有量に対する電力損失PCV(kW/m)の特性を調べたところ、表1に示すような結果になった。
【0039】
【表1】

Figure 0003590941
【0040】
表1からは、ナトリウム複合酸化物を適量含有させれば、電力損失PCVが小さく良好となることが判る。
【0041】
【発明の効果】
以上に説明したように、本発明によれば、副成分にPを含有するMn−Zn系フェライトに対し、副成分の必須要素としてNaO,SiO,CaOや副成分の他要素として異なるナトリウム複合酸化物原料であるNaCOとNaNbO及びNaTaOのうちの少なくとも1種とをPを含む酸化鉄原料に対して同時に添加して生成されるNb並びにTaのうちの少なくとも一種を適量含有することにより、スイッチング電源材料として求められる高電気抵抗である特性を充分に満足し、使用周波数が100kHz付近の高周波数帯域においても優れた磁気特性を有すると共に、電力損失が小さくて発熱量を抑制可能な低損失酸化物磁性材料が得られるようになる。このようなMn−Zn系フェライトから成る低損失酸化物磁性材料は、Pのみを含有するMn−Zn系フェライトと比べて結晶粒径が均一化され、充分に粒界相の電気抵抗が向上される上、ヒステリシス損失や渦電流損失の低減化が計られるようになる。
【0042】
又、本発明では、このような低損失酸化物磁性材料を製造するために、混合工程において、異なるナトリウム複合酸化物原料であるNaCOとNaNbO及びNaTaOのうちの少なくとも1種とを用いてPを含む酸化鉄原料に対して混合させることで副成分の他要素であるNb並びにTaのうちの少なくとも1種を安定して得られるようにしているので、優れた磁気特性を有する低損失酸化物磁性材料が従来に無く簡単に得られるようになる。
【図面の簡単な説明】
【図1】本発明の実施例1に係る各低損失酸化物磁性材料に関してPの含有量に対する電力損失PCV(kW/m)の特性を調べた結果を示したものである。
【図2】本発明の実施例2に係る各低損失酸化物磁性材料に関してNaOの含有量に対する電力損失PCV(kW/m)の特性を調べた結果を示したものである。
【図3】本発明の実施例3に係る各低損失酸化物磁性材料に関してSiOの含有量に対する電力損失PCV(kW/m)の特性を調べた結果を示したものである。
【図4】本発明の実施例4に係る各低損失酸化物磁性材料に関してCaOの含有量に対する電力損失PCV(kW/m)の特性を調べた結果を示したものである。[0001]
TECHNICAL FIELD OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention is mainly used as a switching power supply material (transformer material) for electric / communication equipment and the like, and is composed of a spinel-type crystal structure Mn-Zn ferrite containing a main component and an auxiliary component. The present invention relates to a low-loss oxide magnetic material containing P 2 O 5 (phosphorus pentoxide) and a method for producing the same.
[0002]
[Prior art]
Conventionally, Mn-Zn ferrite has been mainly used as this kind of low-loss oxide magnetic material. When this Mn-Zn-based ferrite is used as a switching power supply material, the driving frequency band is generally in the range of about several tens to 200 (kHz). The Mn-Zn ferrite itself is required to have high performance in such a use frequency band and to be inexpensive to manufacture, but in such a frequency band, eddy current loss and hysteresis loss generally tend to occur. Therefore, how to reduce both of them is an extremely important issue.
[0003]
Therefore, in order to reduce the eddy current loss, it is essential to improve the electric resistance of the spinel phase and the electric resistance of the grain boundary phase of the sintered body.
[0004]
In order to improve the electrical resistance of the spinel phase itself, it is important how to suppress the hopping phenomenon due to electrons between Fe 2+ and Fe 3+. or measure the reduction of Fe 2+ by increasing or Ti 4+, thereby suppressing the occurrence of hopping phenomenon by substituting Fe 3+ contain a Sn 4+.
[0005]
However, in the case of the former method, the magnetic permeability μi is remarkably deteriorated due to the extreme decrease of Fe 2+ , and the coercive force Hc is increased to cause deterioration of the magnetic characteristics. In the case of the latter method, the temperature at which the power loss value becomes minimum in the temperature characteristics of the power loss (called the minimum point) remarkably moves to the low temperature side due to the addition of Ti 4+ , Sn 4+, and the like. As a result, the temperature characteristics deteriorate. Further, in both of these methods, there is a fundamental drawback that the electrical resistance of the sintered body does not increase so much even if the electrical resistance of the spinel phase itself is improved.
[0006]
On the other hand, when improving the electrical resistance of the grain boundary phase, a high-resistance grain boundary phase is formed by adding SiO 2 and CaO. This technique is most effective in improving the resistance of the ferrite sintered body, and is therefore most frequently used. In this method, the crystal grain growth can be controlled by adding appropriate amounts of SiO 2 and CaO, a uniform crystal grain structure can be obtained, and the hysteresis loss (P h ) can be reduced.
[0007]
[Problems to be solved by the invention]
For low loss oxide magnetic material described above, generally when the P 2 O 5 in Mn-Zn ferrite is contained tends to grain size heterogeneity at the manufacturing process, whereby the hysteresis loss (P h) Not only increases, but also the eddy current loss (P e ) deteriorates significantly.
[0008]
In particular, if such is P 2 O 5 in Mn-Zn ferrite to be contained, the crystal grain size in the manufacturing process be added SiO 2, CaO in order to improve the electrical resistance of the grain boundary phase It is more likely to be non-uniform, which significantly degrades both the hysteresis loss (P h ) and the eddy current loss (P e ).
[0009]
Generally, P 2 O 5 is mainly contained in a large amount in the iron oxide raw material in many cases, and the price is lower than that in which no iron oxide raw material is contained. However, when the iron oxide raw material containing P 2 O 5 is used, it is impossible to make the crystal grain size uniform and sufficiently improve the electric resistance of the grain boundary phase. As a result, P 2 O 5 to become difficult to suppress the heat generation amount inviting an increase in power loss when the Mn-Zn ferrite and switching power supply material containing, not applicable in various OA equipment such as a low loss is required It has become. As described above, the Mn-Zn ferrite containing P 2 O 5 cannot be a low-loss oxide magnetic material having a uniform crystal grain size and exhibiting excellent magnetic properties, that is, a high-quality magnetic property. is the current situation.
[0010]
The present invention has been made to solve such a problem, and the technical problem is that even when an iron oxide material containing P 2 O 5 is used, power loss is small in an operating frequency band and excellent magnetic characteristics are obtained. An object of the present invention is to provide a low-loss oxide magnetic material having the same and a method for producing the same.
[0011]
[Means for Solving the Problems]
According to the present invention, in a low-loss oxide magnetic material comprising a spinel-type Mn—Zn-based ferrite including a main component and an auxiliary component, the main component is 52 to 54 (mol%) Fe 2 O 3 , 33 to 37 (mol%) MnO and the balance ZnO, and the subcomponents are 0.007 to 0.07 (wt%) P 2 O 5 , 0.12 (wt%) or less (where 0 is (Not including) Na 2 O, 0.004 to 0.020 (wt%) SiO 2 , and 0.03 to 0.12 (wt%) CaO as essential elements and different sodium composites as other elements. 0.020 wt% or less (provided that an oxide material Na 2 CO 3 and at least one of NaNbO 3 and NaTaO 3 are simultaneously added to an iron oxide material containing P 2 O 5) Nb of not including 0) O 5 and 0.060 (wt%) or less (not inclusive of 0) comprises at least one of of Ta 2 O 5 which has a, and the Nb 2 O 5 and two by the Ta 2 O 5 Is a low-loss oxide magnetic material having a total amount of 0.060 (wt%) or less (excluding 0).
[0012]
On the other hand, according to the present invention, in the method for producing a low-loss oxide magnetic material, Nb 2 O is added to an iron oxide raw material containing 0.01 to 0.1 (wt%) of P 2 O 5. 5 and a mixing step of mixing the sodium compound oxide material different by at least one of Na 2 CO 3 and NaNbO 3 and NaTaO 3 to obtain at least one of Ta 2 O 5, in the mixing step A firing step of firing the press-formed body obtained by pre-firing, crushing, granulating and pressing the resulting mixture under an oxygen partial pressure of 10.0% or less and a temperature condition of 1200 to 1400 (° C.). And a method for producing a low-loss oxide magnetic material containing the same.
[0013]
[Action]
In the low-loss oxide magnetic material of the present invention, when P 2 O 5 is contained as a sub-component in a spinel-type Mn—Zn-based ferrite containing a main component and a sub-component, inexpensive oxidation is performed in the production process. If the content of P 2 O 5 in the iron raw material (Fe 2 O 3 raw material) is in the range of 0.01 to 0.01 (wt%), 0.12 wt% or less (however, 0 (Not including), Na 2 O, 0.004 to 0.020 (wt%) of SiO 2 and 0.03 to 0.12 (wt%) of CaO, so that the electric resistance is high and excellent. Mn-Zn ferrite (low-loss oxide magnetic material) having excellent magnetic properties is obtained, and Na 2 CO 3 and NaNbO 3 , which are different sodium composite oxide raw materials as other components of the subcomponent, NaT 0.020 (wt%) or less of Nb 2 O 5 and 0.060 (wt%) produced by simultaneously adding at least one of aO 3 to an iron oxide raw material containing P 2 O 5 At least one of the following Ta 2 O 5 When these two types are contained, if the condition that the total amount is 0.060 (wt%) or less (excluding 0) is satisfied, the electric resistance is further increased and excellent magnetic properties are obtained. It has been found that an Mn-Zn ferrite having the same can be obtained.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the low-loss oxide magnetic material of the present invention will be described in detail with reference to the drawings by way of examples.
[0015]
First, the outline of the low-loss oxide magnetic material of the present invention will be briefly described. This low-loss oxide magnetic material is composed of a spinel-type Mn—Zn-based ferrite having a main component and an auxiliary component, and the main components are 52 to 54 (mol%) Fe 2 O 3 and 33 to It consists of 37 (mol%) MnO and the balance ZnO. The sub-components are 0.007 to 0.07 (wt%) of P 2 O 5 (phosphorus pentoxide), 0.12 (wt%) or less (excluding 0) of Na 2 O (sodium oxide). ), 0.004 to 0.020 (wt%) of SiO 2 (silicon oxide) and 0.03 to 0.12 (wt%) of CaO (calcium oxide) as essential elements and different sodium as other elements. 0.020 wt% or less (provided that Na 2 CO 3, which is a composite oxide material, and at least one of NaNbO 3 and NaTaO 3 are simultaneously added to an iron oxide material containing P 2 O 5) , and comprise at least one of of Ta 2 O 5 which has a Nb 2 O 5 and 0.060 nOT iNCLUDED) 0 (wt%) or less (not inclusive of 0).
[0016]
However, with respect to the sub-components of the low-loss oxide magnetic material, when Nb 2 O 5 and Ta 2 O 5 of the other elements are two, the total amount is 0.060 (wt%) or less (however, 0 is not included). ) Is preferable.
[0017]
When such a low-loss oxide magnetic material is manufactured, an iron oxide raw material containing 0.01 to 0.1 (wt%) of P 2 O 5 is added to Nb 2 O 5 and Ta 2 O 5 . Na 2 CO 3 (sodium carbonate) and NaNbO 3 in order to obtain at least one (sodium niobate), and NaTaO 3 at least one mixing step of mixing the different sodium compound oxide material according to one of (sodium tantalate) And press molding obtained by pre-firing, pulverizing, granulating and pressing the mixture obtained in the mixing step and firing at an oxygen partial pressure of 10.0% or less and a temperature condition of 1200 to 1400 (° C.). And a baking step. As a result, a low-loss oxide magnetic material having the composition described above is obtained.
[0018]
In the composition of the low-loss oxide magnetic material (including the material related to the raw materials used in the production process), 52 to 54 (mol%) of Fe 2 O 3 and 33 to 37 of MnO are converted for the main component. (Mol%), the reason for limiting the range with ZnO as the balance is that Fe 2 O 3 is not more than 52 mol% in terms of conversion, or MnO is not more than 37 mol% in terms of conversion, which is not preferable because the power loss increases. This is because even if Fe 2 O 3 is 54 mol% or more in terms of conversion or MnO is 33 mol% or less in terms of conversion, the minimum temperature of the power loss becomes low, which is not preferable.
[0019]
On the other hand, with respect to the sub-components, the range of the content of P 2 O 5 in the iron oxide raw material powder in the production process 0.01~0.1 (wt%) [Note, which was obtained as a sintered body 0.007 To 0.07 (wt%)] The reason is that if the content is 0.01 wt% or less, it is suitable for improving the performance of ferrite, but such an iron oxide raw material powder is used. This is because it is too expensive, and if the content exceeds 0.1 wt%, it becomes difficult to control the grain growth even if Na 2 O, which is an essential element, is contained, and the magnetic properties deteriorate. To do that.
[0020]
Furthermore, the reason that the content of SiO 2 is 0.004 wt% or more and the content of CaO is 0.03 wt% or more is that when the content is 0.004 wt% or less and 0.03 wt% or less, sufficient electric resistance is obtained. The reason for this is that the eddy current loss increases and the magnetic properties deteriorate, and the reason why the content of SiO 2 is 0.020 wt% or less and the content of CaO is 0.12 wt% or less is 0.020 wt% or less, respectively. %, More than 0.12 wt%, even if Na 2 O is contained, the crystal grain size becomes remarkably non-uniform and magnetic properties deteriorate. Incidentally, Na 2 O can remove the adverse effect of P 2 O 5 by adding Na 2 O, but the same effect can be obtained by adding not only in the form of oxide but also in the form of carbonate, nitrate or chloride. is there. However, when added in such a form, slight variations are observed in the structure of the sintered body during the manufacturing process.
[0021]
Therefore, in order to obtain stable at least one of Nb 2 O 5 and Ta 2 O 5 in the manufacturing process, of Na 2 CO 3 and NaNbO 3 and NaTaO 3 as different sodium complex oxide material And at least one of the following. If Nb 2 O 5 and Ta 2 O 5 which is another element of subcomponent obtained, thereby improving the eddy current loss to improve the formation of the grain boundary phase is timed. That is, Na 2 O is unstable in the air during the manufacturing process, and is not industrially suitable for use due to its characteristics. However, Na 2 CO 3 is inexpensive and stable in the air. It is suitable for supplementing a deficient Na component. In the case of using the sodium composite oxide powder as described above, even when the addition amount is very small, when added together with a carbonate or the like, the effect of suppressing the variation in the structure of the sintered body, that is, the grain growth can be easily controlled. This makes it easier to obtain a structure having a uniform crystal grain size.
[0022]
The reason why an upper limit value is provided for at least one of Nb 2 O 5 and Ta 2 O 5 or an upper limit value is provided for the total amount of the two types is that the addition amount exceeds the upper limit value ( This is because, if it is contained, it is difficult to control the grain growth, which causes an increase in hysteresis loss and eddy current loss.
[0023]
The composition and characteristics of the low-loss oxide magnetic material composed of several different Mn-Zn-based ferrites have been described above. The following description is based on some examples relating to the manufacturing process of such a low-loss oxide magnetic material. Then, the grounds regarding the composition and characteristics will be specifically described.
[0024]
<Example 1>
In Example 1, first, as a main component of the low-loss oxide magnetic material, Fe 2 O 3 , MnO, and ZnO were converted to 53.0 mol%, 35.5 mol%, and 11.5 mol% of spinel type ferrite, respectively. as the content of P 2 O 5 is 0.012,0.022,0.030,0.035,0.051,0.067,0.074 (wt%), respectively, of P 2 O 5 Iron oxide raw materials having contents of 0.012, 0.034 and 0.96 (wt%) are appropriately mixed and used, and NaTaO is added so that Na 2 O becomes 0.035 wt% in conversion as a sub-component. 3 , 0.024 (wt%), Na 2 CO 3 to 0.056 (wt%), SiO 2 to 0.016 wt%, and CaO to 0.08 wt%, respectively. Composition of main component So as to correct, to obtain a mixture and mixing them.
[0025]
Next, the mixture obtained in this mixing step is pre-fired, crushed, granulated, and pressed by molding, and then fired at an oxygen partial pressure of 10.0% or less and temperature conditions of 1200 to 1400 (° C.). I got a body. By this firing step, a total of six types of low-loss oxide magnetic materials are obtained as sintered bodies.
[0026]
Therefore, when the content of P 2 O 5 is used as a parameter for each of the obtained low-loss oxide magnetic materials, the power with respect to the content of P 2 O 5 under the conditions of a frequency of 100 kHz, a magnetic flux density of 2000 G, and a temperature of 80 ° C. When the characteristics of the loss PCV (kW / m 3 ) were examined, the results shown in FIG. 1 were obtained.
[0027]
From Figure 1, P 2 content of O 5, 0.07 wt% or more, i.e., significantly increases the power loss P CV in the case of using the iron oxide raw material containing P 2 O 5 more than 0.1 wt% You can see that it is.
[0028]
<Example 2>
In the second embodiment, an iron oxide raw material having P 2 O 5 of 0.025 (wt%) is used for the spinel ferrite of the same main component as in the first embodiment, and SiO 2 is used as a sub-component. 0.016 wt%, 0.08 wt% of CaO, 0.024 (wt%) of NaTaO 3 , and Na 2 CO 3 in the amount of Na 2 O of 0, 0.017, 0.051, 0.085, 0, respectively. .136, 0.203, and 0.255 (wt%), and a total of seven types of low-loss oxide magnetic materials were obtained in the same procedure as in Example 1.
[0029]
Therefore, when the content of Na 2 O is used as a parameter for each of the obtained low-loss oxide magnetic materials, the power loss P with respect to the content of Na 2 O under the conditions of a frequency of 100 kHz, a magnetic flux density of 2,000 G, and a temperature of 80 ° C. When the characteristics of CV (kW / m 3 ) were examined, the results were as shown in FIG.
[0030]
FIG. 2 shows that the power loss PCV is significantly increased when the content of Na 2 O is 0.12 wt% or more.
[0031]
<Example 3>
In the third embodiment, an iron oxide raw material such that P 2 O 5 is 0.025 (wt%) is used for the spinel-type ferrite of the same main component as in the first embodiment, and Na 2 is used as an auxiliary component. NaTaO 3 is 0.024 wt%, Na 2 CO 3 is 0.056 wt%, CaO is 0.08 wt%, and the content of SiO 2 is set to 0.002,0 so that it becomes 0.035 wt% in terms of O. 0.0004, 0.010, 0.016, 0.020, and 0.030 (wt%), and a total of six types of low-loss oxide magnetic materials were prepared in the same procedure as in Example 1. Obtained.
[0032]
Therefore, when the content of SiO 2 is used as a parameter for each of the obtained low-loss oxide magnetic materials, the power loss P CV (with respect to the content of SiO 2 at a frequency of 100 kHz, a magnetic flux density of 2000 G, and a temperature of 80 ° C.) kW / m 3 ), the result was as shown in FIG.
[0033]
From Figure 3, the content of SiO 2 is seen that 0.004 to 0.02 (wt%) in the power loss P CV is less favorable.
[0034]
<Example 4>
In the fourth embodiment, an iron oxide raw material having P 2 O 5 of 0.025 (wt%) is used with respect to the spinel type ferrite of the same main component as in the first embodiment, and Na 2 is used as an auxiliary component. NaTaO 3 is 0.024 (wt%), Na 2 CO 3 is 0.056 (wt%), SiO 2 is 0.016 wt%, and the content of CaO is set as parameters so that it becomes 0.035 wt% in terms of O. 0.02, 0.03, 0.05, 0.08, 0.010, 0.012, and 0.15 (wt%) were added, respectively, and a total of 7 were obtained in the same procedure as in Example 1. Various kinds of low-loss oxide magnetic materials were obtained.
[0035]
Therefore, when the content of CaO is used as a parameter for each of the obtained low-loss oxide magnetic materials, the power loss P CV (kW / kW) with respect to the content of CaO under the conditions of a frequency of 100 kHz, a magnetic flux density of 2,000 G, and a temperature of 80 ° C. When the characteristics of m 3 ) were examined, the results shown in FIG. 4 were obtained.
[0036]
From Figure 4, the content of CaO is seen that 0.03 to 0.12 (wt%) in the power loss P CV is less favorable.
[0037]
<Example 5>
In Example 5, an iron oxide raw material having a P 2 O 5 of 0.025 (wt%) was used for the spinel-type ferrite of the same main component as in Example 1, and a total amount of sub-components was used. in terms of Na 2 O content is less 0.12 wt% (0 not including) become as NaNbO 3, NaTaO 3, Na 2 NaNbO 3 of the CO 3 or less 0.40 wt%, NaTaO 3 is 0. 140Wt% or less, or 0.140wt% 2 kinds in total below remainder Na 2 CO 3 is 0.210 (wt%) or less (not including 0), SiO 2 is 0.016wt%, CaO is 0.08wt %, And a total of 22 types of low-loss oxide magnetic materials were obtained in the same procedure as in Example 1.
[0038]
Therefore, for each low-loss oxide magnetic material obtained, sodium complex oxide (NaNbO 3, NaTaO 3, Na 2 CO 3) If the parameter content, frequency 100kHz, the magnetic flux density 2000 G, a temperature 80 ℃ When the characteristics of the power loss PCV (kW / m 3 ) with respect to the content of the sodium composite oxide were examined under the conditions, the results shown in Table 1 were obtained.
[0039]
[Table 1]
Figure 0003590941
[0040]
From Table 1, it can be seen that when an appropriate amount of the sodium composite oxide is contained, the power loss PCV is small and good.
[0041]
【The invention's effect】
As described above, according to the present invention, Na 2 O, SiO 2 , CaO and other sub-components are required as an essential component of the sub-component with respect to the Mn—Zn-based ferrite containing P 2 O 5 as a sub-component. Nb 2 O produced by simultaneously adding Na 2 CO 3 , which is a different sodium composite oxide material, and at least one of NaNbO 3 and NaTaO 3 to an iron oxide material containing P 2 O 5 5 and by a suitable amount at least one of a Ta 2 O 5, sufficiently satisfying the high electrical resistance at a characteristic required as the switching power supply materials, magnetism used frequency is excellent in the high frequency band around 100kHz It is possible to obtain a low-loss oxide magnetic material having characteristics and a small power loss and capable of suppressing a calorific value. Low loss oxide magnetic material comprising such Mn-Zn ferrite, the crystal grain size as compared with the Mn-Zn ferrite containing only P 2 O 5 is made uniform, sufficient electric resistance of the grain boundary phase And the reduction of hysteresis loss and eddy current loss can be achieved.
[0042]
Further, in the present invention, in order to produce such low-loss oxide magnetic material, in the mixing step, at least one of Na 2 CO 3 and NaNbO 3 and NaTaO 3 are different sodium complex oxide material And mixing with the iron oxide raw material containing P 2 O 5 so that at least one of Nb 2 O 5 and Ta 2 O 5 , which are the other components of the subcomponent, can be stably obtained. As a result, a low-loss oxide magnetic material having excellent magnetic properties can be easily obtained as never before.
[Brief description of the drawings]
FIG. 1 shows the results of examining the characteristics of power loss PCV (kW / m 3 ) with respect to the content of P 2 O 5 for each low-loss oxide magnetic material according to Example 1 of the present invention. .
FIG. 2 shows the results of examining the characteristics of power loss PCV (kW / m 3 ) with respect to Na 2 O content for each low-loss oxide magnetic material according to Example 2 of the present invention.
FIG. 3 shows the results of examining the characteristics of power loss PCV (kW / m 3 ) with respect to the content of SiO 2 for each low-loss oxide magnetic material according to Example 3 of the present invention.
FIG. 4 shows the result of examining the characteristics of power loss PCV (kW / m 3 ) with respect to the content of CaO for each low-loss oxide magnetic material according to Example 4 of the present invention.

Claims (2)

主成分及び副成分を含むスピネル型結晶構造のMn−Zn系フェライトから成る低損失酸化物磁性材料において、前記主成分は、52〜54(mol%)のFe,33〜37(mol%)のMnO,及び残部ZnOから成り、前記副成分は、0.007〜0.07(wt%)のP,0.12(wt%)以下(但し、0を含まず)のNaO,0.004〜0.020(wt%)のSiO,及び0.03〜0.12(wt%)のCaOを必須要素とすると共に、他要素として異なるナトリウム複合酸化物原料であるNaCOとNaNbO及びNaTaOのうちの少なくとも1種とを前記Pを含む酸化鉄原料に対して同時に添加して生成される0.020wt%以下(但し、0を含まず)のNb並びに0.060(wt%)以下(但し、0を含まず)のTaのうちの少なくとも1種を含んで成り、且つ該Nb並びに該Taによる2種は総量で0.060(wt%)以下(但し、0を含まず)であることを特徴とする低損失酸化物磁性材料。In low-loss oxide magnetic material comprising a main component and Mn-Zn ferrite having a spinel type crystal structure containing secondary components, the main component, Fe 2 O 3 of 52~54 (mol%), 33~37 ( mol %) Of MnO and the balance of ZnO, and the subcomponents are 0.007 to 0.07 (wt%) of P 2 O 5 , 0.12 (wt%) or less (excluding 0). Na 2 O, 0.004 to 0.020 (wt%) of SiO 2 , and 0.03 to 0.12 (wt%) of CaO as essential elements, and as another element, a different sodium composite oxide material 0.020 wt% or less (however, 0 is included) produced by simultaneously adding certain Na 2 CO 3 and at least one of NaNbO 3 and NaTaO 3 to the iron oxide raw material containing P 2 O 5 Nb 2 O 5 and 0.060 (wt%) or less (but not including 0) of at least one of Ta 2 O 5 , and the Nb 2 O 5 and the two kinds of Ta 2 O 5 are A low-loss oxide magnetic material having a total amount of 0.060 (wt%) or less (but not including 0). 請求項1記載の低損失酸化物磁性材料を製造するための方法において、前記Pを0.01〜0.1(wt%)含有する酸化鉄原料に対し、前記Nb並びに前記Taのうちの少なくとも1種を得るために前記NaCOと前記NaNbO及び前記NaTaOのうちの少なくとも1種とによる前記異なるナトリウム複合酸化物原料を混合する混合工程と、前記混合工程で得られる混合体を予焼,解砕,造粒して成形プレスすることにより得られるプレス成形体を酸素分圧10.0%以下,温度条件1200〜1400(℃)において焼成する焼成工程とを含むことを特徴とする低損失酸化物磁性材料の製造方法。A method for producing a low loss oxide magnetic material of claim 1, wherein the P 2 O 5 and 0.01 to 0.1 (wt%) relative to the iron oxide raw material containing, the Nb 2 O 5 and wherein the Na 2 CO 3 and the NaNbO 3 and mixing step of mixing the different sodium complex oxide material according to at least one of said NaTaO 3 to obtain at least one of said Ta 2 O 5, A pressed product obtained by pre-baking, crushing, granulating and pressing the mixture obtained in the mixing step is fired under an oxygen partial pressure of 10.0% or less and a temperature condition of 1200 to 1400 (° C.). And baking a low-loss oxide magnetic material.
JP22047795A 1995-08-29 1995-08-29 Low-loss oxide magnetic material and method for producing the same Expired - Fee Related JP3590941B2 (en)

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