TW200423159A - Mn-Zn ferrite - Google Patents

Mn-Zn ferrite Download PDF

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Publication number
TW200423159A
TW200423159A TW093102203A TW93102203A TW200423159A TW 200423159 A TW200423159 A TW 200423159A TW 093102203 A TW093102203 A TW 093102203A TW 93102203 A TW93102203 A TW 93102203A TW 200423159 A TW200423159 A TW 200423159A
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Taiwan
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mass
mol
manganese
resistance
zinc fertilizer
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TW093102203A
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Osamu Kobayashi
Osamu Yamada
Kiyoshi Ito
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Minebea Co Ltd
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Publication of TW200423159A publication Critical patent/TW200423159A/zh

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Description

200423159 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於具有軟磁性之代表性的氧化物磁性材料 ，較詳言之係關於針對適於開關電源變壓器等所用之低損 耗材、各種感應元件、EMI對策用阻抗元件、電波吸收材 等錳鋅肥粒鐵。 【先前技術】 具有軟磁性之代表性的氧化物磁性材料，係爲錳鋅肥 粒鐵。此猛鋅肥粒鐵，較之以往一般係化學量論組成5 0 111〇1多之？6203，平均性係含有52〜55 111〇1%之[6203與 10〜24 mol%之ZnO與剩餘部MnO之基本成分組成。且 通常係將Fe203、ZnO、MnO之各原料粉末以預定之比例 混合後，經過預燒、粉碎、成分調整、造粒、成型之各步 驟成預定形狀，其後使氮流入，於基於下記（1)式控制氧 分壓之還原性環境中，於1 2 0 0〜1 4 0 0 °C維持2〜4小時焙 燒並進行焙燒後之冷卻所製造。 log P〇2=- 1 45 40/ (T + 273 ) + b ⑴ 此（1)式中之T係溫度（°c )、P〇2係氧分壓、b係常數 、通常此常數係採用7〜8。 在此有關錳鋅肥粒鐵之錳成分一般皆知係可能以 Mn3 +或Mn2 +存在，Mn3 +與Mn2 +存在比依頼焙燒時之環環 -5- (2) (2)200423159 氧分壓，Mn3 +明顯損及錳鋅肥粒鐵之軟磁性等。又亦皆知 Mn3 +與Mn2+之間有電子授受，此爲使電阻降低之原因。 即爲確保優良軟磁性且確保高電阻，爲能極力控制Μη34 之生成須控制焙燒時之環境（氧分壓），該（1)式中之常數 b = 7〜8，係考量此點並工業性之可實現性而規定之。此常 數b爲7〜8，其意爲須將焙燒中之氧分壓控制於狹小範 圍，致焙燒處理極麻煩，製造成本亦增加。 反之，含較50 mol%多之Fe203之一般性錳鋅肥粒鐵 ，鐵成分係可能以Fe3 +或Fe2 +存在，若於該還原性環境進 行焙燒，Fe3 +之一部份被還原生成Fe2+。此Fe2+。係具有 正結晶磁各向異性，具有消去Fe3 +之負結晶磁各向異性提 高軟磁性之效果反而明顯降低電阻。又錳之情況相同， Fe3 +與Fe2 +間有電子授受，此爲使電阻明顯降低之原因。 但近年隨著電子機器之小型高性能化，有處理信號被 高頻率化之傾向，須即使於高頻率區域具有優異之磁特性 之磁性材料。 將錳鋅肥粒鐵作爲磁心材料之用時，隨著使用頻率區 域變高渦流流動，藉此損耗變大。因此，提高得作爲磁心 材料之用之頻率的上限，須儘量加大該電阻（電阻率）。但 該一般性之錳鋅肥粒鐵，因Fe203亦多於化學量論組成之 50 mol%過量，存在許多之Fe2+，該Fe3 +與Fe2 +間（離子 間）易有電子授受，其電阻率係約1 Ωιη級之小値。因此， 可使用頻率數kHz程度爲界限，超過此之頻率區域起始磁 導率明顯降低，結果產生作爲軟磁性材料之特性全失之問 -6 - 200423159
題。 因此，如於特許文獻1或特許文獻2，係揭示將 Fe203設爲低於50 mol%，並加上CaO、Si02爲副成分以 期高電阻化之錳鋅肥粒鐵，又於特許文獻3，係揭示將 Fe203設爲低於50 mol%，並加上Ti02或Sn02，再加上 CaO、Si02爲副成分以期高電阻化之錳鋅肥粒鐵。 [特許文獻1] 特開平7-23 0909號公報 [特許文獻2] 特開平1 0-208926號公報 [特許文獻3] 特許第3 1 0 8 8 03號公報 【發明內容】..... 〔發明所欲解決之課題〕 但若根據該特許文獻1及特許文獻2所載之錳鋅肥粒 鐵，因用途爲偏向軛用芯材，限於100kHz以下之頻率區 域使用（參照各特許文獻之實施例），無保證於超過1MHz 之類之局頻率區域可得優良磁特性（軟磁性）。即於超過 1 MHz之類之高頻率區域不能作爲磁心材料之用。 又於特許文獻1建議得將C a Ο及S i Ο 2添加至最大 0.50重量％止，但該實施例添加之最大Ca〇量係低於0.10 重量％，對添加多於0.20 mass%之CaO並無實績。此特許 文獻1記載添加Μη203使其與Fe2〇3之和爲略5〇mol%， (4) (4)200423159 但若自此所規定之Fe203 45.0〜48.5 mol%反算，Μπ203使 即Μη3 +量爲1.4〜5.0 mol%，含如此多之Μη3 +時，很難 使軟磁性與電阻並存。 反之，若根據於該特許文獻3所載之錳鋅肥粒鐵，因 降低 CaO 爲 0.005 〜0.20 mass%、Si〇2 爲 0.005 〜0.05 mass%，現今有一高電阻化效果不足之問題。又爲提高電 阻，僅提高CaO或Si02之添加量，結果焙燒時產生反常 粒成長之磁特性（軟磁性）明顯劣化。 本發明係鑑於該以往之問題點，其目的爲提供具有大 電阻，即使於超過1 MHZ之高頻率區域可得優良軟磁性之 錳鋅肥粒鐵。 〔用以解決課題之解決手段〕 爲達成該目的，有關本發明之錳鋅肥粒鐵，其特徵爲 基本成分組成係由 Fe203 44·0〜49.8 mol%、ZnO 4.0〜 26·5 mol%、Ti02 及 Sn02 中之 1 種或 2 種 0.1 〜4.0 mol% 、Μ η 2 Ο 3 〇 . 5 m ο 1 %，剩餘部爲Μ η Ο所成，副成分係含有 CaO 0.20 〜1.00 mass % (但不包括 0·20 mass%)，且電阻率 爲1·5χ104Ωιη以上，表面電阻爲1·5χ107Ωηι以上者。 本發明將F e Ο含量控制於0 · 2 0 m ο 1 %以下爲宜。 本發明之副成分可含有Si02 0.0 1〜0.10 mass %所構 成。 再者本發明之副成分亦可含有 V205 〇·〇1〜〇·20 mass%、Mo03 0.01 〜0.20 mass%、Zr 02 0.01 〜0.20 mass% -8- (5) (5)200423159 、Ta205 0·01 〜0.20 mass%、Hf〇2 〇·〇1 〜〇·20 mass%、
Nb2〇5 0.01 〜0.20 mass%及 CuO 0.01 〜6.00 mass%中之 1 種或2種以上。 〔發明之實施形態〕 如上所述，若將Fe203超過50 mol%—般性的錳鋅肥 粒鐵，若於該式（1 )之常數b爲7〜8之還原性環境焙燒， 幾乎不生成使軟磁性劣化之Μη3+，結果生成使電阻明顯 降低之Fe2+。此因多於50 mol%分之Fe203 SP Fe3 +被還元 。對此，本發明因將Fe203設爲低於50 mol%之44.0〜 49.8 mol%，即使於該式（1)之常數b爲7〜8之還原性環 境進行焙燒幾乎不生成Fe2+。 又若於式（1)之常數b大於8之氧化性環境進行焙燒 ，結果Mn2 +被氧化致生成Mn3+。Mn3 +係加上使晶格變形 等理由使起始磁導率明顯降低，電阻亦降低。但本發明因 含適量之Ti02及/或Sn02 ’ Ti4 +或Sn4 +固溶於尖晶石格 子中，藉此Mn3 +被還原生成Mn2+。 即若根據本發明，控制使電阻明顯降低之Fe2 +之生成 ，加上亦控制使軟磁性與電阻劣化之Mn3 +之生成’使優 良軟磁性與高電阻並存。此結果於本發明可得電阻率爲 1.5χ1〇4Ωγπ以上、表面電阻爲1·5χ107Ωπι明顯之高電阻 。但，Ti02及/或Sn02其含量若低於〇·1 mol%該效果小 ，若多於4.0 mol%因起始磁導率反而降低，設於〇·1〜4.0 m ο 1 %之範圍。 200423159
此時Mn3 +之量，因成爲使該優良軟磁性與高電阻並 存之重要指標，故本發明將此Mn3 +量即Μη203控制0.5 m ο 1 %以下。 錳鋅肥粒鐵中之鐵成分，一般表記爲含FeO(Fe2 + )之 Fe203，Fe2 +係因如上述爲使電阻降低之主要原因，故此 FeO量以控制於0.2 mol %以下爲宜。 主要成分之ZnO係影響居里溫度或磁飽和，但若太 少始磁導率降低，反之過多係使磁飽和或居里溫度降低。 電源變壓器用肥粒體多用於80〜100 °C程度之環境，因居 里溫度或磁飽和高尤爲重要，故該範圍設爲 4.0〜26.5 mol%。 本發明之特徵如上述副成分係含CaO多於0.20 mol% 。此CaO係離析晶粒界有助於高電阻化，其含量多於 0.20 mol%時，產生反常粒成長使磁特性明顯劣化。爲此 ，以往將此CaO控制於0.20 mol%以下，但本發明因將 Fe203控制於低於50 mol%(49.8 mol%)，且將Μη203控制 於微量（〇·5 mol%以下），依所期將Fe0控制於微量（0.2 mol%以下），故即使含CaO多於〇.2〇 mass%，亦不產生反 常粒成長。再者含CaO以多於0.50 mass%有助於高電阻 化爲宜。但該含量因過多致軟磁性降低，故CaO設於該 範圍0.20〜1.00 mass%(但不包括0.20 mass%)。又，因 Sn〇2亦有助高電阻化，得依所期將此811〇2含0 01〜0.10 mass% ° 本發明之副成分亦可含有V2〇5、Mo〇3、Zr〇2、Ta2〇5 -10- (7) (7)200423159 、Hf〇2、Nb205及CuO中之1種或2種以上’此類具有促 進焙燒作用或高電阻化作用。但因此類之含量若太少該效 果小，反之過多結果產生反常粒成長，對ν2〇5、Mo03 ' Zr02、Ta205、Hf02、Nb205 及 V205 以含 0.01 〜〇·2〇 mass%之範圍，對CuO以含0.01〜6.00 mass%之範圍爲宜 〇 本發明，將如上述般之焙燒及焙燒後之冷卻’得於該 (1)式之常數b使用7〜15之範圍內之任一値求出之氧分 壓環境中進行。此其意爲較之一般所用之常數b = 7〜8’ 較易控制環境，該分可達到製造成本之降低。但若選擇大 於15之値爲常數時，肥粒鐵中之Mn3 +呈多於0.5 mol%， 致使起始磁導率急速降低。 製造錳鋅肥粒鐵時，預先將主要成分之Fe203、ZnO 及MnO之各原料粉末以預定之比率秤量、混合後，將此 混合粉未預燒、微粉碎。該預燒溫度依目標組成稍有差異 ，但於8 5 0〜1 000 °C之溫度範圍內選擇適當的溫度。混合 粉末之微粉碎得先以通用之球磨機，再使用高速球磨機 (attirter)。再於此微細之混合粉末添加適量之Ti2〇2、Sn2 、CaO、Si02等必要之粉末加以混合，製得目標成分之混 合粉末。之後根據通常之肥粒鐵製造過程進行造粒、成型 ，再於1 000〜1 3 00 °C進行焙燒。又得各自採用該造粒添 加聚乙烯醇、聚丙烯酸醯胺、甲基纖維素、聚乙靖經基、 甘油等黏合劑之方法，或成型加80PMa以上之壓力進行 等之方法。 -11 - (8) (8)200423159 該焙燒及焙燒後之冷卻，於焙燒爐中使氮氣等惰氣氣 體流入控制氧分壓。此時該（1)式之常數因選擇7〜1 5之 範圍內之任一値，與焙燒以往一般之Fe2〇3多於50 mol% 錳鋅肥粒鐵時選擇之常數b(7〜8)相較，該容限相當大， 得易進行氧分壓之控制。此時根據該（1 )式之焙燒後之冷 卻，係低於5 00°C之溫度，因可不依氧濃度無視氧化或還 原之反應，若至5 00°C即足夠。 【實施方式】 [實施例] 將預定量之Fe203、ZnO及MnO之各原料粉末用高速 球磨機（attriter)混合後，空氣中於85 0 °C預燒2小時，再 用高速球磨機粉碎1小時，製得混合粉末。接著將Ti〇2 、Sn02、CaO、Si02、CuO、Nb2〇5、V205、Zr02 等粉末 以適當之比例添加混合於此混合粉末進行成分調整，再用 高速球磨機混合1小時。再於此混合粉末加上聚乙烯醇造 粒，於80MPa之壓力成型爲外徑25mm、高度5mm之環 形芯（成型體）。其後將此成型體放入焙燒爐，放出氮，調 整環境將該（1)式中之常數b爲9所求出之作爲氧分壓， 於1 2 0 0 °C焙燒2小時及進行焙燒後之冷卻，製得本發明 試料1〜7與比較例1〜4。 且對如上製得之各試料，藉由螢光X射線分析確認 最後之成分組成，並藉由滴定法分析Mn2〇3量與Fe〇量 。又對該各試料，測定於1 MHZ之起始磁導率、電阻率及 -12- (9) 200423159 表面電阻。此類結果總括示於表1及表2。
試料區分 基本成分組成（mol%) 滴定成分 (mol%) 副成分(mass%) Fe2〇3 MnO ZnO Ti02 Sn〇2 ΜΠ2〇3 FeO CaO Si02 其他 比較1 51.0 36.7 12.2 0.1 0.9 1.0 0.10 0.04 本發明1 49.8 37.6 12.5 0.1 0.3 0.2 0.25 // 本發明2 47.0 39.0 13.0 1.0 0.1 0.1 1.00 // 比較2 // a // // // // 1.50 // 本發明3 // // // // // // 0.60 CuOrl.OO 本發明4 // // // // // // // Nb2〇5：〇.〇5 本發明5 // // // 1.0 // // n V2〇5：〇.〇5 本發明6 n // // 1.0 // // 11 0.04 Zr〇2：0.05 比較3 // 39.8 13.2 0.6 0 n // 比較4 // 35.8 12.2 5.0 0 0.3 11 // 本發明7 44.0 38.8 13.2 4.0 0 0 0.80 // 誇 備考）基本成分組成中、Fe203含FeO、MnO含Μη203。
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--— 試料區分 起始磁導率 電阻率 表面電阻 (Ω m) (Ω ) --生較1 30 l.lxlO1 1.2 χ 1 02 _明 1 720 1·6χ104 1.7χ107 _明 2 820 7·7χ104 9.1χ1〇7 較2 450 l.lxlO5 1 .3x1 〇8 兔發明3 790 3·8χ105 2.9x1〇8 負明4 800 3.5χ105 2.7x1〇8 本發明5 890 3·6χ105 2.6χ1〇8 本發明6 830 3·4χ105 2·6χ1〇8 _比較3 3 80 1·2χ104 1.4x1〇7 比較4 330 1 .3x1 Ο4 1.4x1〇7 本發明7 8 10 4.4χ104 3·2χ1〇8
自表1及表2所示之結果，確知本發明試料1〜7， Μπ2〇3皆爲〇·5 mol%以下、FeO爲0.2 mol%以下。本發 明試料1〜7之起始磁導率皆爲700以上、電阻率爲ι.5χ 1 0 4 Ω m、表面電阻爲1 · 5 X 1 0 7 Ω m，得到優良軟磁性與高電 阻。 對此，比較試料1因Fe2〇3爲50 mol%以上之〜般个生 之錳鋅肥粒鐵，電阻明顯降低。比較試料2係Ca〇含量 多，產生反常粒成長，起始磁導率明顯降低。比較試料2 -14- (11)200423159 因不含 Ti02〕 化且電阻降低 ’同樣地軟磁 〔發明之效果 如上之說 Fe203控制低 m ο 1 % 以下），| 產生反常粒成 電阻爲1 . 5 X 1 及/或Sn02， 高頻率區域可 5： Sn〇2 ’多存有Mn2〇3即Mn3+，軟磁性劣 。再者’比較試料4反之因Sn〇2含量過多 性劣化且電阻降低。 ) 明，若根據有關本發明之錳鋅肥粒鐵，將 於50 mol%，且將Μη203控制於微量（0.5 丨卩使副成分含有CaO多於0.20 mass%，亦不 長，可得電阻率爲1.5χ104Ωπι以上，表面 〇7Ωιη以上之高電阻。因使其含適當之Ti02 起始磁導率亦相當高，即使於1 MHZ之類之 得優良軟磁性。
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Claims (1)

  1. 200423159 ⑴ 拾、申請專利範圍 1 · 一種錳鋅肥粒鐵，其特徵爲基本成分組成係由 Fe203 44.0 〜49.8 mol%、ΖηΟ 4,0 〜26.5 mol%、Ti02 及 Sn〇2 中之 1 種或 2 種 0.1 〜4.0 mol%、Mri2〇3 0.5 mol%， 剩餘部MnO所成，副成分含有CaO 0.20〜1.00 mass % (但 不包括0.20 mass%)，且電阻率爲1·5χ104Ωηι以上，表面 電阻爲1·5χ107Ωιη以上者。 2.如申請專利範圍第1項之錳鋅肥粒鐵，其中FeO含 量係0.2 m ο 1 %以下。 3 .如申請專利範圍第1或2項之錳鋅肥粒鐵，其中副 成分係含有Si〇2 0.01〜0·10 mass%。 4.如申請範圍第1至3項中任一項之錳鋅肥粒鐵，其 中副成分係含有 V2O5 〇·〇1〜〇·2〇 mass%、M0O3 0.01〜 0.20 mass%、Zr〇2 〇·〇1 〜〇·20 mass%、Ta2〇5 〇·〇1 〜〇·2〇 mass%、Hf〇2 0.01 〜0·20 mass% ' Nb2〇5 〇 〇1 〜〇·2〇 mass %及CuO 〇·〇1〜6.00 mass%中之1種或2種以上。 200423159 柒、（一） (二） 、本案指定代表圖為：無 、本代表圖之元件代表符號簡單說明： 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：
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CN101687665B (zh) * 2007-05-31 2012-07-04 国立大学法人东京大学 磁性氧化铁颗粒、磁性材料及电波吸收材料
CN102875138B (zh) * 2012-09-27 2014-07-16 无锡宏昌五金制造有限公司 一种高频钛合金材料
CN102982954B (zh) * 2012-11-23 2016-11-02 天长市昭田磁电科技有限公司 一种含有HfO2的铁磁芯的制造方法
CN103693951B (zh) * 2013-09-02 2015-05-27 横店集团东磁股份有限公司 一种抗电磁干扰的锰锌铁氧体材料及其制备方法
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KR20170066538A (ko) * 2014-11-06 2017-06-14 가부시키가이샤 무라타 세이사쿠쇼 적층 코일 부품
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CN111164050B (zh) * 2017-09-29 2023-05-30 保德科技股份有限公司 Mn－Zn系铁氧体颗粒、树脂成形体、软磁性混合粉及磁芯

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