JPH03215353A - Barium titanate-based semiconductor ceramic composition - Google Patents
Barium titanate-based semiconductor ceramic compositionInfo
- Publication number
- JPH03215353A JPH03215353A JP2007930A JP793090A JPH03215353A JP H03215353 A JPH03215353 A JP H03215353A JP 2007930 A JP2007930 A JP 2007930A JP 793090 A JP793090 A JP 793090A JP H03215353 A JPH03215353 A JP H03215353A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- barium titanate
- added
- based semiconductor
- ceramic composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 239000004065 semiconductor Substances 0.000 title claims description 23
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims description 20
- 239000000919 ceramic Substances 0.000 title claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 2
- 239000011572 manganese Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 abstract description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 4
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract 1
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 239000000654 additive Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、一定温度を越えると急激に電気抵抗値が変化
する正の抵抗温度特性を有するチタン酸バリウム系半導
体磁器に関し、特に必要な耐電圧を確保しながら、常温
における比抵抗を小さ《でき、ひいては低抵抗回路素子
として有用なチタン酸バリウム系半導体磁器組成物に関
する．〔従来の技術〕
一般にチタン酸バリウム系半導体磁器は、主成分として
のチタン酸バリウムに、半導体化剤としてＹ．Ｌａ，Ｃ
ｏ等の希土類元素．あるいはＮｂ，Ｂ ｉ．Ｓｂ，Ｗ，
Ｔｈ等のうち少なくとも一種以上を微量添加し、これを
高温で焼成して得られる．この半導体磁器は、常温にお
ける比抵抗が小さく、かつキュリー点を超えると著しい
正の抵抗温度変化を示す特性を有しており、例えば定温
度発熱用素子．電流制限用素子．温度制御用素子等とし
て使用されている．
また上記チタン酸バリウム系半導体磁器のキエリー点は
、その主成分であるチタン酸バリウムの影響により通常
１２０℃付近である．そしてこのキエリー点を高温側に
移行させるためにＢａの一部をｐｂで置換する方法が知
られている．逆に上記キエリー点を低温側に移行させる
ためにＢａの一部をＳｒで置換したり、ＴＩの一部をＺ
ｒ．Ｓｎ等で置換したりする方法も知られている．また
、マンガンを微量（Ｍｎに換真して０．０３〜０．１５
ｍｏＪ％》添加することにより、キュリー点を超えた後
の抵抗温度変化率を著しく増大させることも知られてい
る．さらにまた、Ｓｉｎ．を徽置（０．５〜５ ｍｏ
ｊ％》添加することで、常温における比抵抗を低く安定
したものにできることも知られている．
ここで、上記チタン酸バリウム系半導体磁器においては
、耐電圧が高く、かつ常温における比抵抗の小さい低抵
抗回路素子として有用なものが要求されている．従来、
このような比抵抗特性の向上を図るために、Ｂａの一部
をＣａ，又はＳｒで置換し、添加物としてＭ ｎ ＊
Ｓ ｔ Ｏ ｔを添加したものが提案されている．こ
れによれば常温における比抵抗が１０Ω・憶以下の特性
が得られる．また、特公昭６３−２８３２４号公報には
、Ｂａの一部をＰｂ，Ｓｒ．Ｃａで同時に置換し、これ
らＰｂ， Ｓｒ，Ｃａを共存状態で主成分のチタン酸バ
リウムに含脊させることにより、ＩＯＯＶ／ Ｗ以上の
耐電圧が得られることが記載されている．
〔発明が解決しようとする問題点〕
しかしながら上記従来のチタン酸バリウム系半導体磁器
において、上述したＢａの一部をＣａ，又はＳｒで置換
したものは、比抵抗では満足できる値が得られるものの
、耐電圧が最高のもので４８Ｖ／■しか得られず実用上
十分な値ではない．また、上記公報のようにＢａの一部
をＰｂ，Ｓｒ，Ｃａで同時に置換したものは、高い耐電
圧を得ることができるものの、比抵抗は３５Ω・値まで
しか下げることができない．従って、比抵・抗１０Ω・
１以下．耐電圧１００Ｖ／ Ｗ以上の両方を満足できる
チタン酸バリウム系半導体磁器の出現が要請されている
．本発明の目的は、高い耐電圧を有し、かつ比抵抗の小
さいチタン酸バリウム系半導体磁器組成物を優供するこ
とにある．
〔問題点を解決するための手段〕
本件発明者らは、上記目的を達成するために鋭意研究を
重ねたところ、Ｂ ａ Ｔ ｉ Ｏ ｓ ， Ｃ ａ
Ｔ ｉＯｓ ， Ｓ ｒＴ ｉ Ｏｓ ， Ｐ ｂＴ
Ｉ Ｏｓを主成分とし、これに添加する劇成分を選定
するとともに、これの添加量を限定すれば比抵抗，耐電
圧の両方の特性を満足できることを見出し、本発明を成
したものである．
そこで本発明は、チタン酸バリウム又はその固溶体から
なる主成分に、半導体化剤，マンガン，及びシリカが添
加含有されているチタン酸バリウム系半導体磁器組成物
において、上記主成分が、Ｂ ａ Ｔ ｉ Ｏ ｓ ３
０〜９５ｍｏ ｌ％、ＣａＴｉＯｓ ３〜２Ｓｍｏｌ％
、Ｓ ｒ Ｔ ｉ Ｏｓ １ 〜２５ｓ＋ｏＪ％、Ｐｂ
ＴｉＯｓｌ〜３０ｍｏ ＩＩ％からなり、咳主成分に半
導体化剤として、Ｙ．Ｌａ，Ｃｅ等の希土類元素あるい
はＮｂ，Ｂ ｔ，Ｓｂ，Ｗ，Ｔｈの酸化物のうち少なく
とも一種が０．２〜１．０ｍｏｌ％添加され、かつマン
ガンがＭｎＯ１に換算して０．００３ ｍｏｌ％以上０
．０３ｍｏｌ％未満、シリカがＳｉｌｌに換算して０．
５〜ξ゛わ０１％それぞれ添加含有されていることを特
徴としている．
ここで、本発明における各種の条件を限定した理由につ
いて説明する．
■ 上記ＢａＴｉＯ，，ＣａＴｉＯｓ ，ＳｒＴｉＯ
ｓ ｒ Ｐ ｂ Ｔ ｔ Ｏ ＠を主成分としたのは
、このＢａの一部をＣａ．Ｓｒ，Ｐｂで同時に置換する
ことにより、耐電圧値を向上させるためである．上記Ｐ
ｂ，Ｓｒは単独ではキュリー点をそれぞれ高温側，低温
側へ移行させるものであるが、これらＣａ，Ｓｒ，Ｐｂ
を共存状態で主成分に含有させることにより、耐電圧１
００Ｖ／ ｗａ以上を実現できる．
■ 上記各生成分の範囲の限定理由は以下の通りである
．
上記Ｂ ａ Ｔ ｉ Ｏ ｓを３０〜９５ｍｏＪ％とし
たのは、３０ｍｏ ｊ％未満では半導体化が困難となり
比抵抗も増大するからであり、９５ｍｏ ｊ％を超える
と電気的特性が著しく低下するからである．
また、上記ＣａＴＩＯｓを３ 〜２５ａ＋ｏ １ ９４
としたのは、３ｍｏｌ％未満ではその含有効果が得られ
ず、かつ２５ｍｏ ｊ％を超えると耐電圧特性，耐突入
電流特性の低下をもたらすからである．
さらに、上記ＳｒＴｉＯ，をｌ 〜２５ｓｏ ｊ％とし
たのは、ｌｓｏｊ％未満ではその改善特性の効果が少な
く、また２５ｍｏ ｊ％を超えると電気的特性が劣化す
るからである．
さらにまた、上記ＰｂＴｉＯ１を１〜３０ｓｏ ｊ％と
したのは、１ｍｏＪ％未満では特性改善の効果が少なく
実用に適さないからであり、また３Ｏｍｏ １％を超え
ると半導体化が困難となるからである．■ また、上記
マンガンの添加量をＭ ｎ Ｏ ＊に換算して０．００
３ ｍｏｌ％以上０．０３鋤ｏｊ％未満としたのは、上
記必要耐電圧を確保しながら、比抵抗を小さ《するため
である．このマンガンはキュリー点を超えた正の抵抗温
度特性の変化率を増大させる機能を有しているが、この
添加量が０．０３ｓｏｊ％以上となると、常温での比抵
抗が高くなり、また上記添加量が０．００３ＩＯ１％未
満では、その添加効果が得られず、かえって耐電圧特性
が劣化する．従って、マンガンの添加量を０．００３
ｍｏＪ％以上０．０３ｓｏ Ｊ％未満とすることにより
、比抵抗ｌＯΩ・１以下を実現できる．
■ 上記半導体化剤は、チタン酸バリウム系半導体磁器
組成物を得るために添加することは公知であり、これら
の添加量としては、０．２〜１．０ ｓｏｌ％の範囲が
比抵抗を低くする上で適当である．■ また、上記シリ
カをＳｉｎｇに換算して０．５〜５ｍｏｌ％としたのは
、半導体化剤の微量添加のわずかな変動によって生じる
比抵抗の変化を抑制し、かつ焼結体の異常粒成長を抑え
るためであり、この範囲を外れると上記効果が得られな
くなるからである．
〔作用〕
本発明に係るチタン酸バリウム系半導体磁器組成物によ
れば、上述のようにＢａＴｉＯ．，ＣａＴｉｅ．．Ｓｒ
ＴｉＯｓ ．ＰｂＴｉＯ１を主成分としたので、つまり
Ｂａの一部をＣａ．Ｓｒ．Ｐｂで同時に置換したので、
耐電圧を向上でき、さらに上記主成分に添加するマンガ
ンをＭｎＯｔに換冨して０．００３鵬０１％以上〜０．
０３ｍｏＪ％未満としたので、必要耐電圧を確保しなが
ら比抵抗を小さくでき、その結果耐電圧１００Ｖ／ ｍ
以上、比抵抗１０Ω・１以下の低抵抗回路素子を実現で
き、上述した要請に応えられる．
〔実施例〕
以下、本発明の実施例を説明する．
本実施例は、本発明における各主成分．各副成分の添加
量を見出した実験について説明する．まず、実験に使用
した試料の製造方法について説明する．
主成分としてＢ ａ Ｔ ｉ Ｏ ｓ（２７〜１０Ｇ
−ｏ Ｊ％）．Ｃ ａ Ｔ ｉ Ｏｓ （０〜２０ｍｏ
Ｊ％）．ＳｒＴｉＯｓ （０〜２５ｍｏ １％） ．
Ｐ ｂ Ｔ ｉ Ｏｓ （０〜２８ｍｏＪ％）、半導体
化剤としてＹｔ Ｏｓ （０．２〜１．５ ｍｏｂ％）
，Ｌａｔ Ｏｘ （０．３ｍｏＪ ％） ，
Ｃ ｅ ０１（０．３ ａｏｊ ％） ． Ｎ
ｄ＊ Ｏｓ（０ ．４ｍｏｌ％）、及び添加物としてＭ
ｎ ＣＯｓ （ＭｎＯｔに換算して０．０１〜０．
１５ｓｏｊ％）．Ｓ ｉ Ｏｘ（０．５〜８．０＊ｏｊ
％）を準備する．この各原材料を第１表に示す比率のチ
タン酸バリウム系半導体磁器組成物が得られるように配
合し、湿式混合する．
次に、上記スラリー状の原料を脱水乾燥し、１１５０℃
×２時間で仮焼成する．次いでこの仮焼結体を粉砕混合
し、これにバインダーを加えて造粒し、成形圧力１００
０ｋｇ／一で円板状にプレス成形する．次にこの円板状
の成形体をｌＯ℃／ｓｉｎで１３６０℃まで昇温しで所
定時間保持した後、１０℃／ｓｌａで冷却する焼成プロ
ファイルで焼成した．これにより直径１７．５ｍｘ厚さ
０．６■の円板状の半導体磁器を得る．そして、この半
導体磁器の両主面にＩｎ−Ｇａ合金からなる電極を付与
し、これを本実験用試料とした．
そして本実験では、上記各試料の常温中《２５℃》にお
ける比抵抗，耐電圧．キエリー点をそれぞれ測定した．
なお、上記耐電圧は試料に破壊が生じる寸前の最高印加
電圧値を測定した．第１表及び第２表はその結果を示し
、第１表は上記主成分．半導体化剤，及び添加物のそれ
ぞれの配合比率を示し、第２表は各測定結果を示す．表
中、試料Ｎａｐ〜１２、Ｎａｌ４〜１６、Ｎａｌ７．ｌ
８、及び＆２２〜２４は本発明の範囲内であり、これ以
外の本印は本発明の範囲外である．同表からも明らかな
ように、各主成分の添加量が所定範囲を外れた場合（Ｎ
ａｌ〜６）は、いずれも耐電圧が４５Ｖ／ｍ以下と低い
．また半導体化荊．添加物が所定範囲を外れた場合（
ｍｌ ３）は、比抵抗が１２．７Ω・国と高くなってい
る．さらに、シリカの添加量が所定範囲を超えた場合（
Ｎｌ２１）は、焼成時に融着をおこしている．また、マ
ンガンの添加量が所定範囲を超えた場合（Ｎａｌ９，２
０）は、比抵抗が７６．８， １２２０Ω・国と増大し
ている．これに対して、各添加量が本発明範囲内の場合
（Ｎ１７〜１２、Ｎａ１４〜１６、Ｉｋｌ７，１８、及
び−２２〜２４》は、いずれもキエリー点は１００〜１
１９℃、比抵抗は９．９〜４．６Ω・ロと低く、かつ耐
電圧は１０１〜１７９Ｖ／■と高《なっており、満足で
きる値が得られていることがわかる．〔発明の効果〕
以上のように本発明に係るチタン酸バリウム系半導体磁
器組成物によれば、Ｂ ａ Ｔ Ｉ Ｏｓ ３０〜９５
１１０４ ％． Ｃ ａ Ｔ Ｉ Ｏｓ
３ 〜２５ｍｏＪ ％， ＳｒＴｉ０，１〜２５ｓ
ｏ ｊ！％，ＰｂＴｉＯｓ １〜３０ｍｏｌ％ を主成
分とし、これに半導体化剤０．２〜１．０ｍｏｌ％を添
加するとともに、ＭｎをＭ ｎ Ｏ ｔに換算して０．
００３ｍｏｌ％以上０．０３ｍｏ ｊ％未満、Ｓ ｉ
Ｏｘ ０．５〜５−０１％をそれぞれ添加含有したので
、耐電圧ｌＯＧＶ／ ｖｍ以上、比抵抗１０Ω・１以下
の優れた特性が得られるとともに、低抵抗回路素子とし
て有用な半導体磁器が得られる効果がある．Detailed Description of the Invention [Field of Industrial Application] The present invention relates to barium titanate-based semiconductor porcelain, which has a positive resistance-temperature characteristic in which the electrical resistance value changes rapidly when a certain temperature is exceeded. This invention relates to a barium titanate-based semiconductor ceramic composition that can reduce specific resistance at room temperature while ensuring voltage, and is useful as a low-resistance circuit element. [Prior Art] Generally, barium titanate-based semiconductor porcelain contains barium titanate as a main component and Y.I. as a semiconductor agent. La,C
Rare earth elements such as o. Or Nb, B i. Sb,W,
It is obtained by adding a small amount of at least one kind of Th, etc. and firing it at a high temperature. This semiconductor porcelain has a characteristic that it has a low specific resistance at room temperature and exhibits a significant positive temperature change in resistance when it exceeds the Curie point, and can be used, for example, as a constant temperature heating element. Current limiting element. It is used as a temperature control element, etc. Furthermore, the Chierie point of the barium titanate-based semiconductor porcelain is usually around 120°C due to the influence of its main component, barium titanate. A method is known in which part of Ba is replaced with PB in order to shift this Chierly point to the high temperature side. Conversely, in order to shift the Chierly point to the low temperature side, part of Ba is replaced with Sr, and part of TI is replaced with Z.
r. A method of substituting with Sn or the like is also known. In addition, a trace amount of manganese (0.03 to 0.15 in terms of Mn)
It is also known that the addition of moJ% can significantly increase the rate of change in resistance with temperature after the Curie point has been exceeded. Furthermore, Sin. (0.5-5 mo
It is also known that the specific resistance at room temperature can be made low and stable by adding 1%. Here, the barium titanate-based semiconductor porcelain is required to have a high withstand voltage and a low specific resistance at room temperature, making it useful as a low-resistance circuit element. Conventionally,
In order to improve such resistivity characteristics, a part of Ba is replaced with Ca or Sr, and M n * is added as an additive.
It has been proposed that S t O t is added. According to this, a characteristic with a resistivity of 10 Ω or less at room temperature can be obtained. Further, in Japanese Patent Publication No. 63-28324, a part of Ba is replaced with Pb, Sr. It is stated that a withstand voltage of IOOV/W or higher can be obtained by simultaneously substituting Ca and impregnating barium titanate, the main component, in a coexisting state with Pb, Sr, and Ca. [Problems to be Solved by the Invention] However, in the above-mentioned conventional barium titanate-based semiconductor porcelain, in which a part of the Ba mentioned above is replaced with Ca or Sr, although a satisfactory value of resistivity can be obtained, The highest voltage withstand voltage is only 48V/■, which is not a sufficient value for practical use. Further, as in the above-mentioned publication, a product in which a part of Ba is replaced with Pb, Sr, and Ca at the same time can obtain a high withstand voltage, but the specific resistance can only be lowered to a value of 35 Ω. Therefore, specific resistance・resistance 10Ω・
1 or less. There is a demand for the emergence of barium titanate-based semiconductor ceramics that can satisfy both requirements of a withstand voltage of 100 V/W or more. An object of the present invention is to provide a barium titanate-based semiconductor ceramic composition that has high withstand voltage and low specific resistance. [Means for Solving the Problems] The inventors of the present invention have conducted intensive research to achieve the above object, and have found that B a Ti O s, C a
T iOs , S rT iOs , PbT
The present invention was made based on the discovery that by using IOs as the main component, selecting a powerful component to be added to it, and limiting the amount added, both specific resistance and dielectric strength characteristics could be satisfied. Accordingly, the present invention provides a barium titanate-based semiconductor ceramic composition in which a semiconducting agent, manganese, and silica are added to a main component consisting of barium titanate or a solid solution thereof, wherein the main component is B a Ti Os 3
0-95mol%, CaTiOs 3-2Smol%
, S r Ti Os 1 ~25s+oJ%, Pb
It consists of TiOsl~30mo II%, and Y. At least 0.2 to 1.0 mol% of rare earth elements such as La and Ce or oxides of Nb, Bt, Sb, W, and Th are added, and manganese is 0.003 mol% in terms of MnO1. More than 0
．． Less than 0.03 mol%, silica is 0.03% in terms of Sill.
It is characterized by the addition content of 5 to ξ゛01%. Here, the reasons for limiting various conditions in the present invention will be explained. ■ Above BaTiO, CaTiOs, SrTiO
The reason why s r P b T t O @ was used as the main component is that part of this Ba is Ca. This is to improve the withstand voltage value by replacing with Sr and Pb at the same time. Above P
b and Sr alone shift the Curie point to the high temperature side and low temperature side, but these Ca, Sr, and Pb
By containing in the main component in coexistence state, the withstand voltage 1
00V/wa or more can be achieved. ■ The reason for limiting the range of each generated component above is as follows. The reason why the above B a Ti O s is set to 30 to 95 moJ% is because if it is less than 30 mo j%, it will be difficult to make it into a semiconductor and the specific resistance will increase, and if it exceeds 95 mo j%, the electrical characteristics will deteriorate significantly. It is. In addition, the above CaTIOs are 3 to 25a+o 1 94
This is because if the content is less than 3 mol %, the effect of its inclusion cannot be obtained, and if it exceeds 25 mol %, the withstand voltage characteristics and inrush current characteristics deteriorate. Furthermore, the above SrTiO is set at 1 to 25 soj% because if it is less than 1soj%, the effect of improving the characteristics is small, and if it exceeds 25moj%, the electrical characteristics deteriorate. Furthermore, the reason why the above PbTiO1 is set to 1 to 30soj% is because if it is less than 1moJ%, the effect of improving characteristics is small and it is not suitable for practical use, and if it exceeds 1%, it becomes difficult to make it into a semiconductor. ．． ■ Also, the amount of manganese added above is converted to M n O * and is 0.00.
The reason for setting the content to be 3 mol% or more and less than 0.03 mol% is to reduce the specific resistance while ensuring the above-mentioned required withstand voltage. This manganese has the function of increasing the rate of change in the positive resistance-temperature characteristic above the Curie point, but if the amount added exceeds 0.03 soj%, the specific resistance at room temperature increases, and the above-mentioned If the amount added is less than 1% of 0.003IO, the effect of the addition cannot be obtained, and the withstand voltage characteristics deteriorate on the contrary. Therefore, the amount of manganese added is 0.003
By setting moJ% or more and less than 0.03so J%, a specific resistance of 1OΩ・1 or less can be achieved. ■ It is known that the above-mentioned semiconducting agent is added to obtain a barium titanate-based semiconducting ceramic composition, and the amount of these added is in the range of 0.2 to 1.0 sol% to lower the specific resistance. It is appropriate to do so. ■ In addition, the reason why the above silica is set at 0.5 to 5 mol% in terms of Sing is to suppress the change in resistivity caused by slight fluctuations in the addition of a small amount of the semiconducting agent, and to suppress the abnormal grain growth of the sintered body. This is to suppress the above effects, and if it is outside this range, the above effect will not be obtained. [Function] According to the barium titanate-based semiconductor ceramic composition according to the present invention, as described above, BaTiO. , CaTie. ．． Sr.
TiOs. Since the main component was PbTiO1, that is, a part of Ba was replaced by Ca. Sr. Since it was replaced with Pb at the same time,
The withstand voltage can be improved, and the manganese added to the above main component can be replaced with MnOt to increase the dielectric strength from 0.003% to 0.01%.
Since it is less than 0.03moJ%, the specific resistance can be reduced while ensuring the necessary withstand voltage, resulting in a withstand voltage of 100V/m
As described above, it is possible to realize a low-resistance circuit element with a specific resistance of 10Ω·1 or less, meeting the above-mentioned requirements. [Examples] Examples of the present invention will be described below. This example describes each main component in the present invention. We will explain the experiment in which we found the amount of each subcomponent added. First, we will explain the method for manufacturing the samples used in the experiment. B a Ti O s (27~10G
-o J%). CaTiOs (0~20mo
J%). SrTiOs (0-25mo 1%).
P b Ti Os (0 to 28 moJ%), Yt Os (0.2 to 1.5 mob%) as a semiconducting agent
, Lat Ox (0.3moJ%) ,
C e 01 (0.3 aoj%). N
d*Os (0.4 mol%), and M as an additive
n COs (0.01 to 0.0 in terms of MnOt)
15soj%). S i Ox(0.5~8.0*oj
%). These raw materials are blended and wet-mixed so as to obtain a barium titanate-based semiconductor ceramic composition having the ratio shown in Table 1. Next, the slurry-like raw material was dehydrated and dried at 1150°C.
× Temporary firing for 2 hours. Next, this pre-sintered body is pulverized and mixed, a binder is added thereto, granulated, and a molding pressure of 100
Press into a disc shape at 0 kg/1. Next, this disc-shaped compact was heated to 1360°C at lO°C/sin, held for a predetermined time, and then fired using a firing profile in which it was cooled at 10°C/sla. As a result, a disk-shaped semiconductor porcelain with a diameter of 17.5 m and a thickness of 0.6 cm was obtained. Then, electrodes made of In-Ga alloy were provided on both main surfaces of this semiconductor ceramic, and this was used as a sample for this experiment. In this experiment, we investigated the specific resistance and withstand voltage of each sample at room temperature (25°C). The Chierly points were measured respectively.
The above withstand voltage was measured at the maximum applied voltage value just before the sample was destroyed. Tables 1 and 2 show the results, and Table 1 shows the above main components. The compounding ratios of the semiconducting agent and additives are shown, and Table 2 shows the results of each measurement. In the table, samples Nap~12, Nal4~16, Nal7. l
8, and &22 to 24 are within the scope of the present invention, and other marks are outside the scope of the present invention. As is clear from the table, when the amount of each main component added is outside the specified range (N
al~6) all have low withstand voltages of 45 V/m or less. Also, semiconductor technology. If the additive is outside the specified range (
ml 3) has a high specific resistance of 12.7Ω. Furthermore, if the amount of silica added exceeds the specified range (
Nl21) causes fusion during firing. In addition, if the amount of manganese added exceeds the specified range (Nal9,2
0), the specific resistance has increased to 76.8, 1220Ω・country. On the other hand, when each addition amount is within the range of the present invention (N17-12, Na14-16, Ikl7,18, and -22-24), the Chierie point is 100-1.
At 19°C, the specific resistance was low at 9.9 to 4.6 Ω·b, and the withstand voltage was high at 101 to 179 V/■, indicating that satisfactory values were obtained. [Effects of the Invention] As described above, according to the barium titanate-based semiconductor ceramic composition of the present invention, B a T I Os 30-95
1104%. C a T I Os
3-25moJ%, SrTi0,1-25s
oj! %, PbTiOs 1 to 30 mol% as a main component, to which a semiconducting agent of 0.2 to 1.0 mol% is added, and Mn is converted to MnOt to be 0.
003mol% or more and less than 0.03mol%, Si
Since 0.5 to 5-01% of Ox is added and contained, excellent characteristics such as withstand voltage of 1OGV/vm or more and specific resistance of 10Ω・1 or less can be obtained, and a semiconductor ceramic useful as a low resistance circuit element can be obtained. effective.
Claims (1)
に、半導体化剤，マンガン，及びシリカが添加含有され
ているチタン酸バリウム系半導体磁器組成物において、
上記主成分は、ＢａＴｉＯ＿３が３０〜９５ｍｏｌ％、
ＣａＴｉＯ＿３が３〜２５ｍｏｌ％、ＳｒＴｉＯ＿３が
１〜２５ｍｏｌ％、ＰｂＴｉＯ＿３が１〜３０ｍｏｌ％
からなり、上記主成分に対して半導体化剤として、Ｙ，
Ｌａ，Ｃｅ等の希土類元素あるいはＮｂ，Ｂｉ，Ｓｂ，
Ｗ，Ｔｈの酸化物のうち少なくとも一種が０．２〜１．
０ｍｏｌ％添加含有され、かつマンガンがＭｎＯ＿２に
換算して０．００３ｍｏｌ％以上０．０３ｍｏｌ％未満
、シリカがＳｉＯ＿２に換算して０．５〜５ｍｏｌ％そ
れぞれ添加含有されていることを特徴とするチタン酸バ
リウム系半導体磁器組成物。(1) A barium titanate-based semiconductor ceramic composition in which a semiconducting agent, manganese, and silica are added to the main component consisting of barium titanate or a solid solution thereof,
The above main components include 30 to 95 mol% of BaTiO_3;
CaTiO_3 is 3-25 mol%, SrTiO_3 is 1-25 mol%, PbTiO_3 is 1-30 mol%
Y, as a semiconducting agent for the above main component.
Rare earth elements such as La, Ce or Nb, Bi, Sb,
At least one of the oxides of W and Th has a content of 0.2 to 1.
Titanium, characterized in that it contains 0 mol % of manganese or more and less than 0.03 mol % in terms of MnO_2, and 0.5 to 5 mol % of silica in terms of SiO_2. Barium acid semiconductor ceramic composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007930A JPH0818865B2 (en) | 1990-01-16 | 1990-01-16 | Barium titanate-based semiconductor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007930A JPH0818865B2 (en) | 1990-01-16 | 1990-01-16 | Barium titanate-based semiconductor porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03215353A true JPH03215353A (en) | 1991-09-20 |
| JPH0818865B2 JPH0818865B2 (en) | 1996-02-28 |
Family
ID=11679244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007930A Expired - Lifetime JPH0818865B2 (en) | 1990-01-16 | 1990-01-16 | Barium titanate-based semiconductor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0818865B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016084562A1 (en) * | 2014-11-26 | 2016-06-02 | 株式会社村田製作所 | Barium titanate semiconductor ceramic, barium titanate semiconductor ceramic composition, and ptc thermistor for temperature detection |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0388770A (en) * | 1989-08-31 | 1991-04-15 | Central Glass Co Ltd | Barium titanate-based semiconductor porcelain composition and thermistor |
-
1990
- 1990-01-16 JP JP2007930A patent/JPH0818865B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0388770A (en) * | 1989-08-31 | 1991-04-15 | Central Glass Co Ltd | Barium titanate-based semiconductor porcelain composition and thermistor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016084562A1 (en) * | 2014-11-26 | 2016-06-02 | 株式会社村田製作所 | Barium titanate semiconductor ceramic, barium titanate semiconductor ceramic composition, and ptc thermistor for temperature detection |
| JPWO2016084562A1 (en) * | 2014-11-26 | 2017-09-21 | 株式会社村田製作所 | Barium titanate semiconductor ceramic, barium titanate semiconductor ceramic composition, and temperature sensitive positive temperature coefficient thermistor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0818865B2 (en) | 1996-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100320723B1 (en) | Barium Titanate-base Semiconducting Ceramic Composition | |
| US4379319A (en) | Monolithic ceramic capacitors and improved ternary ceramic compositions for producing same | |
| JPS6328324B2 (en) | ||
| US4096098A (en) | Semiconductor ceramic composition | |
| JP2541344B2 (en) | Electronic parts using barium titanate based semiconductor porcelain | |
| JPH03215353A (en) | Barium titanate-based semiconductor ceramic composition | |
| JPH03215354A (en) | Barium titanate-based semiconductor ceramic composition | |
| JP2014205585A (en) | Semiconductor ceramic composition and method of producing the same | |
| JP3003201B2 (en) | Barium titanate-based semiconductor porcelain composition | |
| JP2014034505A (en) | Semiconductor ceramic composition and method of producing the same | |
| JP2990679B2 (en) | Barium titanate-based semiconductor porcelain composition | |
| JPH04104951A (en) | Barium titanate-based semiconductive porcelain material | |
| JP3273468B2 (en) | Barium titanate-based semiconductor porcelain composition | |
| JP2536679B2 (en) | Positive characteristic thermistor material | |
| JP3036051B2 (en) | Barium titanate-based semiconductor porcelain composition | |
| JPH03215356A (en) | Barium titanate-based semiconductor ceramic composition | |
| JPH0551254A (en) | Barium titanate-containing semiconductor porcelain composition | |
| JPS6117087B2 (en) | ||
| JPS581483B2 (en) | Titanium Sambarium Keihand Taijiki | |
| JPH03218964A (en) | Semiconductor porcelain and production thereof | |
| JPH01236607A (en) | Porcelain composition for reduction-reoxidation type semiconductor capacitor | |
| JPH01228104A (en) | Positive temperature coefficient thermistor material and its manufacturing method | |
| JP2000315601A (en) | Semiconductor ceramic, element thereof and circuit protection element | |
| JPH0458507A (en) | Dielectric porcelain capacitor | |
| JPH0794020A (en) | Composition for barium titanate semiconductor ceramic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090228 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090228 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100228 Year of fee payment: 14 |
|
| EXPY | Cancellation because of completion of term |