JP5019023B2 - Mn−Zn系フェライト材料 - Google Patents
Mn−Zn系フェライト材料 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims description 32
- 229910000859 α-Fe Inorganic materials 0.000 title claims description 32
- 230000007547 defect Effects 0.000 claims description 24
- 150000001768 cations Chemical class 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 11
- 230000005284 excitation Effects 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 230000006866 deterioration Effects 0.000 description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 239000011572 manganese Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000011162 core material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910018669 Mn—Co Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Description
磁場劣化とは、1MHz以上といった高周波領域で顕著な現象であり、焼結後に磁場を印加すると、電力損失が増大し、これとともにインダクタンスが増大するというものである。この現象は、印加された磁場によって磁区構造が変化し、誘導磁気異方性が低下するためと考えられる。
このような磁場劣化は、スイッチング電源のメイントランスやチョーク、あるいは電源用トランス等においては、特に安定性が要求されるため、上記のような磁場劣化をなるべく抑えることが望まれる。
本発明は、このような技術的課題に基づいてなされたもので、1MHz以上の高周波域で、磁場劣化の少ないMn−Zn系フェライト材料を提供することを目的とする。
(Zna 2+,Tib 4+,Mnc 2+,Mnd 3+,Fee 2+,Fef 3+,Cog 2+,Coh 3+)3O4+δ…組成式(1)
ただし、a+b+c+d+e+f+g+h=3、δ=a+2b+c+(3/2)d+e+(3/2)f+g+(3/2)h−4、[g:h=1:2]
また本発明の本発明のMn−Zn系フェライト材料において、室温から125℃における温度範囲において、励磁磁束密度50mT、測定周波数2MHzにおける電力損失が3000[kW/m3]以下であり、かつ磁場劣化率が100%以下であるのが好ましい。ここで磁場劣化率とは、飽和磁束密度程度まで励磁させた直後における電力損失の、励磁前の電力損失に対する増加率であり、励磁直後(磁場劣化後)の電力損失をPcvr、励磁前の初期の電力損失をpcvとしたとき、
〔Pcvr−Pcv〕/〔Pcv〕×100〔%〕
で表される。
Fe2O3:53〜54mol%
Fe2O3は本発明のMn−Zn系フェライト材料の主成分をなす必須の構成であり、その量が少なすぎても、また多すぎても高温での損失Pcvが大きくなってしまう。また、その量が54mol%を超えると、後述する実施例3で示すように、磁場劣化率が増大してしまう。したがって本発明では、Fe2O3量を53〜54mol%とする。
ZnOも本発明のMn−Zn系フェライト材料の主成分をなすものである。ZnOの量によってMn−Zn系フェライト材料の周波数特性を制御することができる。即ち、ZnO量が少ないほど、高周波域での損失Pcvが小さくなる。ZnOが7mol%を超えた場合、2MHz以上の高周波域における損失Pcvが劣化するため、ZnOの上限を7mol%とした。また、ZnO量が1mol%を下回ると、磁場劣化率が大きくなり、磁場が印加されたときの安定性が損なわれる。好ましいZnO量は2〜7mol%、さらに好ましいZnO量は5〜7mol%である。
Co:Co3O4換算で0.15〜0.65wt%(1500〜6500ppm)
Co量が少なすぎると、損失Pcvの低減効果が十分に得られないため下限をCo3O4換算で0.15wt%とする。また、Co量を増大させると、磁場劣化率が増大する。よって、CoはCo 3 O 4 換算で0.65wt%以下とする。好ましいCo量はCo3O4換算で0.15〜0.50wt%、さらに好ましいCo量はCo3O4換算で0.15〜0.30wt%である。
Siは結晶粒界に偏析して粒界抵抗を増大させ電流損失を低減させる効果がある。この効果により高周波域における損失を低減させる効果が得られる。この効果を得るために、SiをSiO2換算で0.01wt%以上添加する。しかしながら、Siの過剰な添加は異常粒成長を誘発する。そのため、SiはSiO2換算で0.045wt%以下とする。好ましいSi量はSiO2換算で0.01〜0.03wt%、さらに好ましいSi量はSiO2換算で0.01〜0.02wt%である。
Caは結晶粒界に偏析して粒界抵抗を増大させ電流損失を低減させる効果、異常粒成長を抑える効果がある。この効果を得るために、CaをCaCO3換算で0.05wt%以上添加する。しかしながら、Caの過剰な添加は高周波粋における損失を増大させるため、CaはCaCO3換算で0.40wt%以下とする。好ましいCa量はCaCO3換算で0.10〜0.30wt%、さらに好ましいCa量はCaCO3換算で0.10〜0.20wt%である。
主成分の原料としては、酸化物又は加熱により酸化物となる化合物の粉末を用いる。具体的には、Fe2O3粉末、Mn3O4粉末およびZnO粉末等を用いることができる。用意する各原料粉末の平均粒径は0.1〜3μmの範囲で適宜選択すればよい。
また、安定温度を調整することにより、Mn−Zn系フェライト材料の平均結晶粒径を変動させることができる。安定温度を上げれば、粒成長が進み、平均結晶粒径を増大させることができる。また、同一の安定温度であっても、SiO2、CaCO 3量を減らすことで、粒成長を促進させることができ、これによっても平均結晶粒径の調整を行うことができる。
配合および粉砕用メディア:スチールボール使用
配合時間:16時間
仮焼き温度および時間:850℃、3時間
粉砕時間:16時間
成形:成形体密度3g/cm3
試料寸法:T10形状(外形20mm、内径10mm、高さ5mmのトロイダル形状)
以上で得られた焼結体について陽イオン欠陥量δを以下の方法により上記組成式(1)に基づいて求めた。
すなわち、δ値の算出は、組成分析と、Fe2+とMn3+の定量によって行う。組成分析については、上記焼結体を粉砕し、粉末状にした後、蛍光X線分析装置(リガク(株)製、サイマルティック3530)を用いガラスビード法によって測定した。Fe2+とMn3+の定量は、上記焼結体を粉砕、粉末状にし、酸に溶解後、K2Cr2O7溶液により、電位差滴定を行ない定量した。その他、Zn2+、Ti4+、Co2+、3+については、組成分析より得られたZnが全て2価のイオン、Tiが全て4価のイオン、Coが2価と3価が1対2の比率で存在するものと仮定している。また、Fe3+、Mn2+量は、組成分析により得られたFe、Mn量により、上記電位差滴定によって求められたFe2+、Mn3+量をそれぞれ差し引いた値とした。
以上で得られたトロイダル形状の焼結体に銅線ワイヤーを一次側および二次側共に3ターン巻き付け、B−Hアナライザ(岩崎通信機器(株)製 SY−8217)を用いて初期損失(Pcv)を測定した。なお、励磁磁束密度(Bm)を25〜125mT、測定周波数(f)を2MHzとした。また測定は、恒温槽を用いて行った。
続いて、前記の焼結体に巻き付けた銅線ワイヤーに、500A/mの直流電流を流し、焼結体に直流磁場を印加する。
そして、磁場劣化率を、
〔磁場劣化後損失(Pcvr)−初期損失(Pcv)〕/〔初期損失(Pcv)〕
という式により算出した。
表2および図2より、また、図2に平均結晶粒径と損失Pcvとの関係を示す。表2および図2より、平均結晶粒径が8μm以下になると、磁場劣化率が大きくなる。また、平均結晶粒径が15μmよりも大きくなると、高温での損失Pcvが大きくなってしまう。これらの結果より、好ましい平均結晶粒径は、8μmよりも大きく、かつ15μm以下であり、より好ましい平均結晶粒径は12μm以上15μm以下、さらに好ましい平均結晶粒径は13μm以上15μm以下である。
CaはCaCO3換算で0.40wt%以下とする。また、CaCO3を過度に減らすと異常粒成長が生じるため、好ましいCa量はCaCO3換算で0.10〜0.30wt%、さらに好ましいCa量はCaCO3換算で0.10〜0.20wt%である。
Claims (3)
- 主成分として、
Fe2O3:53〜54mol%、
ZnO:1〜7mol%、
残部:MnOを含み、
副成分として、
CoをCo 3 O 4 換算で0.15〜0.65wt%、
SiをSiO2換算で0.01〜0.045wt%、
CaをCaCO3換算で0.05〜0.40wt%を含み、
下記フェライト組成式(1)におけるδ値(陽イオン欠陥量)が、3×10−3≦δ≦7×10−3であり、
かつ平均結晶粒子径が8μmより大きく15μm以下であることを特徴とするMn−Zn系フェライト材料。
(Zna 2+,Tib 4+,Mnc 2+,Mnd 3+,Fee 2+,Fef 3+,Cog 2+,Coh 3+)3O4+δ…組成式(1)
ただし、a+b+c+d+e+f+g+h=3、δ=a+2b+c+(3/2)d+e+(3/2)f+g+(3/2)h−4、[g:h=1:2] - 前記δ値が、3×10−3≦δ<5×10−3であることを特徴とする請求項1に記載のMn−Zn系フェライト材料。
- 室温から125℃における温度範囲において、励磁磁束密度50mT、測定周波数2MHzにおける電力損失が3000[kW/m3]以下であり、
かつ飽和磁束密度程度まで励磁させた直後における電力損失の、励磁前の電力損失に対する増加率である磁場劣化率が100%以下であることを特徴とする請求項1または2に記載のMn−Zn系フェライト材料。
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