JPH08217536A - 正の抵抗温度係数を有する半導体磁器組成物及びその製造方法 - Google Patents

正の抵抗温度係数を有する半導体磁器組成物及びその製造方法

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Publication number
JPH08217536A
JPH08217536A JP7025694A JP2569495A JPH08217536A JP H08217536 A JPH08217536 A JP H08217536A JP 7025694 A JP7025694 A JP 7025694A JP 2569495 A JP2569495 A JP 2569495A JP H08217536 A JPH08217536 A JP H08217536A
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Japan
Prior art keywords
sodium
semiconductor porcelain
semiconductor
porcelain composition
composition
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JP7025694A
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English (en)
Inventor
Koji Hayashi
康二 林
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TDK Corp
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TDK Corp
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Priority to JP7025694A priority Critical patent/JPH08217536A/ja
Priority to MYPI96000435A priority patent/MY111923A/en
Priority to US08/598,213 priority patent/US5686367A/en
Priority to EP96101912A priority patent/EP0727791A3/en
Priority to KR1019960003148A priority patent/KR960031394A/ko
Priority to CN96105586A priority patent/CN1143255A/zh
Publication of JPH08217536A publication Critical patent/JPH08217536A/ja
Withdrawn legal-status Critical Current

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Abstract

(57)【要約】 【目的】一定の比抵抗値を有する半導体磁器組成物を安
定的に製造する。 【構成】酸化珪素，マンガンを含むチタン酸バリウム系
半導体磁器組成物に於いて，前記チタン酸バリウム系半
導体組成物１００部に対し，ナトリウム（Ｎａ）量が
０．０００５〜０．０２重量％となるようにナトリウム
化合物を添加した正の抵抗温度係数を有する半導体磁器
組成物。

Description

【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、正の抵抗温度係数を有
するチタン酸バリウム系半導体磁器及びその製造方法に
係り，特に，酸化珪素，マンガンを含むチタン酸バリウ
ム系半導体磁器組成物及びその製造方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】従来，
正の抵抗温度係数を有する半導体素子としてはチタン酸
バリウム系半導体磁器組成物が一般に知られている。チ
タン酸バリウム系半導体磁器組成物は，キュリー点を越
えると抵抗値が急激に増大して通過する電流を減少させ
ることから，回路の過電流保護用やテレビ受像機のブラ
ウン管の消磁用等の種々の用途に用いられている。一般
に，このような半導体素子を電気回路に使用する場合，
常温での抵抗値のバラツキが大きいと回路設計等に支障
をきたすため，抵抗値のバラツキを小さくする必要があ
る。
【０００３】更に，上記チタン酸バリウム系半導体磁器
組成物に，酸化珪素，マンガンを添加することにより耐
電圧特性，抵抗温度特性を向上させたものも知られてい
る（特公昭５３−２９３８６号公報）。酸化珪素，マン
ガンを添加したチタン酸バリウム系半導体磁器組成物
は，電気的特性には優れているが，常温で一定の比抵抗
値を有するものを安定的に製造するためには，仮焼成温
度及び本焼成温度を正確に管理する必要があった。
【０００４】しかし，仮焼成温度及び本焼成温度の管理
は容易でなく，仮焼成温度の変動により仮焼材料の比抵
抗値が変化した場合には，本焼成温度で最終的な半導体
磁器組成物の比抵抗値を調整しなければならないため，
本焼成温度の管理が煩雑となり，作業効率も良くなかっ
た。
【０００５】そこで，本発明は，仮焼成温度の変動によ
り仮焼材料の比抵抗値が変化した場合に，ナトリウムの
添加量を調整することににより，本焼成温度を変えるこ
となく最終的な半導体磁器組成物の比抵抗値を調整する
ことができる正の抵抗温度係数を有する半導体磁器組成
物及びその製造方法を提供することを目的とする。
【０００６】尚，本発明と同様にナトリウムを添加した
半導体磁器組成物としては特開平４−３１１００２号公
報に記載されたものがあるが，その目的は抵抗温度係数
を向上させることであり，その目的及びナトリウムの添
加量の点で本発明と明らかに異なる。
【０００７】
【課題を解決するための手段】請求項１記載の正の抵抗
温度係数を有する半導体磁器組成物は，酸化珪素，マン
ガンを含むチタン酸バリウム系半導体磁器組成物に於い
て，前記チタン酸バリウム系半導体組成物１００部に対
し，ナトリウム（Ｎａ）量が０．０００５〜０．０２重
量％となるようなナトリウム化合物を添加したことを特
徴とするものである。
【０００８】請求項２記載の正の抵抗温度係数を有する
半導体磁器組成物の製造方法は，仮焼成工程及び本焼成
工程からなる酸化珪素，マンガンを含むチタン酸バリウ
ム系半導体磁器組成物の製造方法に於いて，仮焼成工程
と本焼成工程との間に，前記チタン酸バリウム系半導体
組成物１００部に対し，ナトリウム（Ｎａ）量が０．０
００５〜０．０２重量％となるようなナトリウム化合物
を添加する工程を有することを特徴とするものである。
【０００９】
【作用】本発明の正の抵抗温度係数を有する半導体磁器
組成物によれば，チタン酸バリウム系半導体組成物１０
０部に対し，ナトリウム（Ｎａ）量が０．０００５〜
０．０２重量％となるようなナトリウム化合物を添加し
たものであるから，半導体磁器組成物の比抵抗値を容易
に調整することができる。
【００１０】又，本発明の正の抵抗温度係数を有する半
導体磁器組成物の製造方法によれば，チタン酸バリウム
系半導体組成物１００部に対し，ナトリウム（Ｎａ）量
が０．０００５〜０．０２重量％となるようなナトリウ
ム化合物を添加する工程を有するものであるから，一定
の比抵抗値を有する半導体磁器組成物を安定的に製造す
ることができる。
【００１１】つまり，ナトリウムを微量添加領域に於い
て添加することにより，ドナー成分である半導体化剤
（Ｙ２Ｏ３，Ｌａ２Ｏ３，Ｎｂ２Ｏ５等）とアクセプタ
成分であるマンガン（Ｍｎ）との半導体化の均衡を保
ち，破壊電圧の劣化を抑えつつ半導体磁器組成物の比抵
抗値を下げることができる。
【００１２】
【実施例】以下，本発明を実施例１及び実施例２により
説明する。
【００１３】（実施例１） （１）出発原料であるＢａＣＯ３，ＴｉＯ２，ＳｒＣＯ
３，Ｙ２Ｏ３，ＳｉＯ２，ＭｎＣＯ３を下記の式１を満
たすように配合したものを，ボールミルを用いて１５時
間混合した後，脱水，乾燥する。
【００１４】 （Ｂａ０．７９６Ｓｒ０．０２Ｙ０．００４）ＴｉＯ３＋ＳｉＯ２（０．４重 量％）＋Ｍｎ（０．０２重量％） （１） （２）混合した上記原料を，１１００℃，１１５０℃，
１２００℃の異なる仮焼成温度で２時間仮焼成し，３種
類の仮焼材料を作製する。
【００１５】（３）上記仮焼材料を粗粉砕したもの１０
０部に対して，水酸化ナトリウム（ＮａＯＨ）をナトリ
ウム（Ｎａ）に換算した成分で０〜０．０３重量％を添
加し再度ボールミルを用いて１５時間混合粉砕した後，
ナトリウムを漏出させることなく乾燥する。こうして得
られた材料に２重量％のアクリル系の有機結合剤を混合
して造粒し，成型圧力２ｔ／ｃｍ２で直径１４ｍｍ，厚
さ３ｍｍの円板状成型物を作製する。
【００１６】尚，本実施例では，有機結合剤としてアク
リル系の有機結合剤を用いたが，ポリビニールアルコー
ルであっても同様の効果が得られる。 （４）上記円板状成型物を，１３５０℃の本焼成温度で
２時間本焼成し，仮焼成温度及びナトリウムの添加量の
異なる２４種類の半導体磁器組成物を製作した。
【００１７】（５）上記半導体磁器組成物の両主面に，
ニッケル（Ｎｉ）の無電解メッキによりオーミック性電
極を設けた後に，このオーミック性電極の表面に銀ペー
ストを塗布し焼き付けることによって電極を形成する。
【００１８】こうして，得られた２４種類の半導体磁器
組成物の試料について，２５℃に於ける比抵抗と破壊電
圧を測定しものを表１に示した。
【００１９】
【表１】
【００２０】表１に示したようにナトリウムの添加量を
０．０００５重量％以上とした場合，ナトリウムの添加
量の増加に伴い半導体磁器組成物の比抵抗値が低くな
り，各仮焼温度（１１００℃，１１５０℃，１２００
℃）に於ける比抵抗値のバラツキが小さくなる傾向があ
る。又，破壊電圧は，ナトリウムの添加量の増加に伴い
低下する傾向がある。
【００２１】従って，仮焼成温度が低かった場合は，ナ
トリウムを添加せずに，又は添加量を少なくして本焼成
を行い，仮焼成温度が高かった場合は，ナトリウムの添
加量を多くして本焼成を行えば，本焼成温度を変えるこ
となく比抵抗値のバラツキの小さい半導体磁器組成物を
安定的に製造することができる。
【００２２】例えば，仮焼温度が１１００℃でナトリウ
ムを添加しなかった場合（試料Ｎｏ．１）の本焼成後の
比抵抗値は９０Ω・ｃｍで，仮焼温度が１２００℃でナ
トリウムを０．０２重量％添加した場合（試料Ｎｏ．２
３）の本焼成後の比抵抗値は８５Ω・ｃｍであり，両者
の比抵抗値はほぼ同一となる。
【００２３】又，常に一定量のナトリウム化合物を添加
した場合，ナトリウム化合物を添加しなかった場合に比
べ仮焼成温度の変動による最終的な半導体磁器組成物の
比抵抗値のバラツキを小さくすることもできる。
【００２４】一方，上記半導体磁器組成物を発熱用及び
電流制限用等の半導体素子として電気回路に使用する場
合，通常５００Ｖｄｃ以上の破壊電圧を要求されるが，
ナトリウムを０．０３重量％以上添加した場合には，前
記要求を満たすことができなくなる。
【００２５】従って，ナトリウムに換算した成分で０．
０００５〜０．０２重量％となるようにナトリウム化合
物を添加することが好ましい。
【００２６】（実施例２）出発原料であるＢａＣＯ３，
ＴｉＯ２，ＰｂＯ，Ｙ２Ｏ３，ＳｉＯ２，ＭｎＣＯ３を
下記の式２を満たすように配合したものを用いて，実施
例１と同様の工程により２１種類の半導体磁器組成物を
製作した。
【００２７】 （Ｂａ０．８４７Ｐｂ０．１５Ｙ０．００３）ＴｉＯ３＋ＳｉＯ２（０．８重 量％）＋Ｍｎ（０．０１重量％） （２） こうして，得られた２１種類の半導体磁器組成物の試料
について，２５℃に於ける比抵抗と破壊電圧を測定しも
のを表２に示した。
【００２８】
【表２】
【００２９】表２於いても，実施例１の場合と同様にナ
トリウムの添加量を０．０００５〜０．０２重量％とし
た場合，ナトリウムの添加量の増加に伴い半導体磁器組
成物の比抵抗値が低くなり，各仮焼温度（１０５０℃，
１１００℃，１１５０℃）に於ける比抵抗値のバラツキ
が小さくなる傾向がある。又，破壊電圧についても，実
施例１の場合と同様にナトリウムの添加量の増加に伴い
低下する傾向がある。
【００３０】従って，ナトリウムに換算した成分で０．
０００５〜０．０２重量％となるようにナトリウム化合
物を添加すれば，実施例１の場合と同様の効果を得るこ
とができる。
【００３１】尚，上述の実施例１及び実施例２において
は，ナトリウム化合物として水酸化ナトリウムを用いた
が，炭酸ナトリウム等のナトリウム化合物であっても同
様の効果が得られる。又，チタン酸バリウム系半導体磁
器組成物の材料としては，Ｂａの一部をＳｒ，Ｐｂ，Ｃ
ａ等で置換したもの，半導体化材料としてＹ，Ｌａ等の
希土類元素やＮｂ，Ｓｂその他の元素を含有させたも
の，添加物としてＳｉＯ２，Ａｌ２Ｏ３，Ｋ２Ｏ，Ｚｎ
Ｏ，Ｐ２Ｏ５，Ｆｅ等を添加したものなど種々のチタン
酸バリウム系材料を用いてもよい。
【００３２】
【発明の効果】本発明は，以上のように構成されている
ので，一定の比抵抗値を有する半導体磁器組成物を安定
的に製造することができる。
【００３３】つまり，以下の効果を奏する （１）ナトリウム化合物の添加量を調整することによ
り，仮焼成温度の変動による仮焼材料の比抵抗値の変化
を，本焼成温度を変えることなく補正することができ
る。
【００３４】（２）ナトリウム化合物を添加することに
より，仮焼成温度の変動による最終的な半導体磁器組成
物の比抵抗値のバラツキを抑制することができる。

Claims (2)

    【特許請求の範囲】
  1. 【請求項１】 酸化珪素，マンガンを含むチタン酸バリ
    ウム系半導体磁器組成物に於いて，前記チタン酸バリウ
    ム系半導体組成物１００部に対し，ナトリウム（Ｎａ）
    量が０．０００５〜０．０２重量％となるようなナトリ
    ウム化合物を添加したことを特徴とする正の抵抗温度係
    数を有する半導体磁器組成物。
  2. 【請求項２】 仮焼成工程及び本焼成工程からなる酸化
    珪素，マンガンを含むチタン酸バリウム系半導体磁器組
    成物の製造方法に於いて，仮焼成工程と本焼成工程との
    間に，前記チタン酸バリウム系半導体組成物１００部に
    対し，ナトリウム（Ｎａ）量が０．０００５〜０．０２
    重量％となるようなナトリウム化合物を添加する工程を
    有することを特徴とする正の抵抗温度係数を有する半導
    体磁器組成物の製造方法。
JP7025694A 1995-02-14 1995-02-14 正の抵抗温度係数を有する半導体磁器組成物及びその製造方法 Withdrawn JPH08217536A (ja)

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JP7025694A JPH08217536A (ja) 1995-02-14 1995-02-14 正の抵抗温度係数を有する半導体磁器組成物及びその製造方法
MYPI96000435A MY111923A (en) 1995-02-14 1996-02-06 Semiconducting ceramic composition having positive temperature coefficient of resistance and production process thereof
US08/598,213 US5686367A (en) 1995-02-14 1996-02-07 Semiconducting ceramic composition having positive temperature coefficient of resistance and production process thereof
EP96101912A EP0727791A3 (en) 1995-02-14 1996-02-09 Semiconducting ceramic composition with positive temperature coefficient and process for its production
KR1019960003148A KR960031394A (ko) 1995-02-14 1996-02-09 정의 온도저항계수를 갖는 반도체 세라믹 조성물 및 그 제조방법
CN96105586A CN1143255A (zh) 1995-02-14 1996-02-14 具有正电阻温度系数的半导体陶瓷合成物及其制造方法

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