JPH0551254A - Barium titanate-containing semiconductor porcelain composition - Google Patents
Barium titanate-containing semiconductor porcelain compositionInfo
- Publication number
- JPH0551254A JPH0551254A JP3235458A JP23545891A JPH0551254A JP H0551254 A JPH0551254 A JP H0551254A JP 3235458 A JP3235458 A JP 3235458A JP 23545891 A JP23545891 A JP 23545891A JP H0551254 A JPH0551254 A JP H0551254A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- barium titanate
- resistance
- semiconductor porcelain
- based semiconductor
- 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.)
- Pending
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- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明はチタン酸バリウム系半
導体磁器組成物に関する。This invention relates to a barium titanate-based semiconductor porcelain composition.
【０００２】[0002]
【従来の技術】正の抵抗温度特性を有するチタン酸バリ
ウム系半導体磁器は、キュリー点以上で抵抗値が急激に
増加するため、回路の過電流保護用やテレビのブラウン
管枠の消磁用など多くの用途に使用されている。こうし
たチタン酸バリウム系半導体磁器を製造するために用い
られる、耐電圧が高く、耐突入電流特性にすぐれたチタ
ン酸バリウム系半導体磁器組成物が特開昭５７−１５７
５０２号に開示されている。2. Description of the Related Art Barium titanate-based semiconductor porcelain having a positive resistance temperature characteristic has a resistance value that rapidly increases above the Curie point. Used for purposes. A barium titanate-based semiconductor ceramic composition used for producing such a barium titanate-based semiconductor ceramic having a high withstand voltage and excellent inrush current withstand characteristics is disclosed in JP-A-57-157.
No. 502.
【０００３】このチタン酸バリウム系半導体磁器組成物
は、ＢａＴｉＯ3 またはその固溶体に希土類元素、Ｎ
ｂ，Ｂｉ，Ｗ，Ｔｈ，Ｌａ，Ｙ，Ｃｅからなる半導体化
剤の１種類以上を微量置換したものからなり、具体的に
は、ＢａＴｉＯ3 を３０〜９５モル％、ＣａＴｉＯ3 を
３〜２５モル％、ＳｒＴｉＯ3 を１〜３０モル％、Ｐｂ
ＴｉＯ3 を１〜５０モル％含有する主成分に対し、マン
ガンをＭｎに換算して０．０３〜０．１０モル％、シリ
カをＳｉＯ2 に換算して０．５〜５モル％添加含有する
組成物である。This barium titanate-based semiconductor porcelain composition comprises BaTiO 3 or a solid solution thereof in which a rare earth element, N
b, Bi, W, Th, La, Y, becomes one or more semiconductor-forming agent consisting of Ce from those trace substituted, specifically, BaTiO 3 and 30 to 95 mol%, a CaTiO 3 3 to 25 Mol%, 1 to 30 mol% of SrTiO 3 , Pb
With respect to the main component containing 1 to 50 mol% of TiO 3 , 0.03 to 0.10 mol% of manganese is converted, and 0.5 to 5 mol% of silica is converted to SiO 2 and added. It is a composition.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、こうし
た従来の組成では、比抵抗が１０Ω・ｃｍ以上であっ
た。それに対し、現在ではさらに低抵抗の半導体磁器が
必要とされている。However, in such a conventional composition, the specific resistance was 10 Ω · cm or more. On the other hand, at present, semiconductor porcelain with lower resistance is required.
【０００５】それゆえに、この発明の主たる目的は、静
耐圧特性を保ちつつ、大幅に低抵抗化された、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組成
物を提供することである。Therefore, a main object of the present invention is to provide a barium titanate-based semiconductor porcelain composition having a positive resistance temperature coefficient which is significantly reduced in resistance while maintaining static withstand voltage characteristics. ..
【０００６】[0006]
【課題を解決するための手段】この発明は、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組成物に
おいて、ＢａＴｉＯ3 が５５〜８０モル％、ＣａＴｉＯ
3 が１３〜１８モル％、ＰｂＴｉＯ3 が３〜１２モル
％、ＳｒＴｉＯ3 が４〜１５モル％からなる主成分に、
半導体化剤として、Ｙ，Ｌａ，Ｃｅなどの希土類元素、
Ｎｂ，Ｂｉ，Ｓｂ，Ｗ，Ｔｈのうち少なくとも１種が
０．１５〜０．５モル％含有されているチタン酸バリウ
ム系半導体磁器に対して、マンガンがＭｎに換算して
０．００２〜０．０２５モル％、ＳｉＯ2 が０．２〜
０．７モル％、それぞれ添加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である。According to the present invention, in a barium titanate-based semiconductor ceramic composition having a positive resistance temperature characteristic, 55 to 80 mol% of BaTiO 3 and CaTiO 3 are contained.
3 is 13 to 18 mol%, PbTiO 3 is 3 to 12 mol%, and SrTiO 3 is 4 to 15 mol% as a main component.
As a semiconducting agent, rare earth elements such as Y, La and Ce,
For a barium titanate-based semiconductor ceramic containing 0.15 to 0.5 mol% of at least one of Nb, Bi, Sb, W, and Th, manganese is converted to Mn in an amount of 0.002 to 0. 0.025 mol%, SiO 2 0.2 to
The barium titanate-based semiconductor ceramic composition is characterized in that 0.7 mol% of each is added.
【０００７】ここで、主成分の組成範囲を限定した理由
は次のとおりである。The reason for limiting the composition range of the main component is as follows.
【０００８】つまり、ＢａＴｉＯ3 が５５モル％未満で
は半導体化が困難となり、比抵抗も高くなり、８０モル
％を超えると静耐圧特性が低くなる。That is, if BaTiO 3 is less than 55 mol%, it becomes difficult to form a semiconductor and the specific resistance becomes high, and if it exceeds 80 mol%, the static withstand voltage characteristic becomes poor.
【０００９】ＣａＴｉＯ3 が１３モル％未満では静耐圧
特性が低下し、１８モル％を超えると比抵抗の値が大き
くなる。If the content of CaTiO 3 is less than 13 mol%, the static pressure resistance is deteriorated, and if it exceeds 18 mol%, the specific resistance value becomes large.
【００１０】ＰｂＴｉＯ3 が３モル％未満では静耐圧特
性が低下し、１２モル％を超えると比抵抗が高くなる。If the content of PbTiO 3 is less than 3 mol%, the static pressure resistance property is deteriorated, and if it exceeds 12 mol%, the specific resistance is increased.
【００１１】ＳｒＴｉＯ3 が４モル％未満では静耐圧特
性が低下し、１５モル％を超えると比抵抗が高くなる。If SrTiO 3 is less than 4 mol%, the static pressure resistance is deteriorated, and if it exceeds 15 mol%, the specific resistance is increased.
【００１２】また、チタン酸バリウム系半導体磁器には
半導体化剤を微量含有させることは知られているが、半
導体化剤として、Ｙ，Ｌａ，Ｃｅなどの希土類元素、Ｎ
ｂ，Ｂｉ，Ｓｂ，Ｗ，Ｔｈのうち少なくとも１種が用い
られ、その含有範囲は０．１５〜０．５モル％とされ
る。ここで、半導体化剤の含有範囲を０．１５〜０．５
モル％としたのは、この範囲を外れると比抵抗を低くす
ることができなくなるからである。It is known that barium titanate-based semiconductor porcelain contains a small amount of a semiconducting agent, but as a semiconducting agent, rare earth elements such as Y, La and Ce, and N are used.
At least one of b, Bi, Sb, W, and Th is used, and the content range is 0.15 to 0.5 mol%. Here, the content range of the semiconductor agent is set to 0.15 to 0.5.
The reason why it is set to mol% is that if it is out of this range, the specific resistance cannot be lowered.
【００１３】さらに、チタン酸バリウム系半導体磁器に
添加物として、マンガンがＭｎに換算して０．００２〜
０．０２５モル％の範囲で添加含有されるが、０．００
２モル％未満では静耐圧特性が低下し、０．０２５モル
％を超えると比抵抗が１０Ω・ｃｍを超えることにな
る。Further, as an additive to barium titanate based semiconductor porcelain, manganese is converted into Mn in an amount of 0.002 to 0.002.
Although it is added and contained in the range of 0.025 mol%, 0.00
If it is less than 2 mol%, the static pressure resistance property is deteriorated, and if it exceeds 0.025 mol%, the specific resistance exceeds 10 Ω · cm.
【００１４】さらにまた、ＳｉＯ2 を０．２〜０．７モ
ル％の範囲としたのは、０．２モル％未満となり、０．
７モル％を超えると、いずれも比抵抗が１０Ω・ｃｍを
超えることになる。Further, the range of SiO 2 in the range of 0.2 to 0.7 mol% is less than 0.2 mol%,
If it exceeds 7 mol%, the specific resistance will exceed 10 Ω · cm.
【００１５】[0015]
【発明の効果】この発明によれば、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組成物において、
静耐圧特性を保ちつつ、大幅な低抵抗化が可能となる。According to the present invention, in a barium titanate-based semiconductor ceramic composition having a positive temperature coefficient of resistance,
It is possible to significantly reduce the resistance while maintaining the static breakdown voltage characteristics.
【００１６】この発明の上述の目的，その他の目的，特
徴および利点は、以下の実施例の詳細な説明から一層明
らかとなろう。The above and other objects, features and advantages of the present invention will become more apparent from the detailed description of the embodiments below.
【００１７】[0017]
【実施例】まず、原料として、高純度のＢａＣＯ3 ，Ｓ
ｒＣＯ3，Ｐｂ3 Ｏ4 ，ＴｉＯ2 ，Ｌａ2 Ｏ3 ，ＭｎＯ
2 ，ＳｉＯ2 ，ＣａＣＯ3を準備した。これらの各原料
を表１に示す比率の半導体磁器組成物が得られるように
配合し、配合物を得た。この配合物を純水およびジルコ
ニアボールとともに、ポリエチレン製ポットに入れて、
５時間粉砕し、混合して、混合物を得た。この混合物を
乾燥し、１１５０℃で２時間仮焼し、仮焼物を得た。こ
の仮焼物を再びポリエチレン製ポットに入れ、バイン
ダ，めのう玉石および純水でバインダ混合粉砕を５時間
行って、乾燥、造粒を行った後、プレス成形によって、
直径１４ｍｍ，厚さ０．８ｍｍの成形体を作製した。こ
の成形体を８℃／ｍｉｎで昇温し、１３５０℃で３０分
間保持したのち、８℃／ｍｉｎで降温し、半導体磁器と
した。EXAMPLES First, as a raw material, high-purity BaCO 3 , S
rCO 3 , Pb 3 O 4 , TiO 2 , La 2 O 3 , MnO
2 , SiO 2 , and CaCO 3 were prepared. Each of these raw materials was blended so that a semiconductor porcelain composition having a ratio shown in Table 1 was obtained to obtain a blend. Put this mixture in a polyethylene pot with pure water and zirconia balls,
Milled for 5 hours and mixed to obtain a mixture. This mixture was dried and calcined at 1150 ° C. for 2 hours to obtain a calcined product. This calcined product is put into a polyethylene pot again, and the binder is mixed and ground with a binder, agate boulders and pure water for 5 hours, dried and granulated, and then press-molded.
A molded body having a diameter of 14 mm and a thickness of 0.8 mm was produced. The molded body was heated at 8 ° C./min, held at 1350 ° C. for 30 minutes, and then cooled at 8 ° C./min to obtain a semiconductor porcelain.
【００１８】[0018]
【表１】 [Table 1]
【００１９】得られた半導体磁器の両主面にＩｎ−Ｇａ
合金の電極を形成し、試料とした。In-Ga is formed on both main surfaces of the obtained semiconductor ceramic.
An alloy electrode was formed and used as a sample.
【００２０】これらの試料について、常温（２５℃）に
おける比抵抗および静耐圧特性を測定し、表２に示し
た。なお、表１および表２中＊印を付したものはこの発
明の範囲外のものであり、それ以外はこの発明の範囲内
のものである。The specific resistance and static withstand voltage characteristics of these samples at room temperature (25 ° C.) were measured and shown in Table 2. It should be noted that those marked with * in Tables 1 and 2 are outside the scope of the present invention, and others are within the scope of the present invention.
【００２１】[0021]
【表２】 [Table 2]
【００２２】表２に示すように、この発明の範囲内であ
る試料番号２，３，４，５，８，９，１０，１３，１
４，１５，１８，１９，２０，２３，２４，２５，２
８，２９，３０では、静耐圧が３０Ｖ／ｍｍ以上、比抵
抗が１０Ω・ｃｍ以下である。As shown in Table 2, sample numbers 2, 3, 4, 5, 8, 9, 10, 13, 1 within the scope of the present invention.
4,15,18,19,20,23,24,25,2
In Nos. 8, 29 and 30, the static breakdown voltage was 30 V / mm or more and the specific resistance was 10 Ω · cm or less.
【００２３】本発明者らは、低抵抗素子を得るべく鋭意
検討し、Ｍｎ，ＳｉＯ2 量を従来より減らすことで、大
幅に低抵抗化できることを見いだした。すなわち、マン
ガンをＭｎに換算して０．００２〜０．０２５モル％、
ＳｉＯ2 を０．２〜０．７モル％と従来より添加量を減
らすことによって、従来のものよりさらに低抵抗化する
ことができた。また、この際にある程度の耐圧を有する
ことも必要であるため、ＢａＴｉＯ3 のＢａをＣａで１
３〜１８モル％、Ｐｂで３〜１２モル％、Ｓｒで４〜１
５モル％置換することで、静耐圧を実用上必要な３０Ｖ
／ｍｍ以上に保つことが可能となった。The inventors of the present invention have conducted extensive studies to obtain a low resistance element and found that the resistance can be significantly reduced by reducing the amounts of Mn and SiO 2 compared with the conventional ones. That is, 0.002 to 0.025 mol% of manganese converted to Mn,
By lowering the addition amount of SiO 2 to 0.2 to 0.7 mol% as compared with the conventional one, the resistance could be further lowered as compared with the conventional one. Further, at this time, it is necessary to have a certain withstand voltage, so that Ba of BaTiO 3 is replaced with Ca by 1
3-18 mol%, Pb 3-12 mol%, Sr 4-1
By substituting 5 mol%, static voltage is practically required at 30V
It has become possible to maintain at / mm or more.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂 部 行 雄 京都府長岡京市天神二丁目26番10号 株式 会社村田製作所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Sakabe 2-10-10 Tenjin 2-10, Tenjin, Nagaokakyo, Kyoto Prefecture Murata Manufacturing Co., Ltd.
Claims (1)
ウム系半導体磁器組成物において、 ＢａＴｉＯ3 が５５〜８０モル％、ＣａＴｉＯ3 が１３
〜１８モル％、ＰｂＴｉＯ3 が３〜１２モル％、ＳｒＴ
ｉＯ3 が４〜１５モル％からなる主成分に、半導体化剤
として、Ｙ，Ｌａ，Ｃｅなどの希土類元素、Ｎｂ，Ｂ
ｉ，Ｓｂ，Ｗ，Ｔｈのうち少なくとも１種が０．１５〜
０．５モル％含有されているチタン酸バリウム系半導体
磁器に対して、 マンガンがＭｎに換算して０．００２〜０．０２５モル
％、 ＳｉＯ2 が０．２〜０．７モル％、それぞれ添加されて
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 porcelain composition having a positive resistance temperature characteristic, wherein BaTiO 3 is 55 to 80 mol%, and CaTiO 3 is 13%.
-18 mol%, PbTiO 3 3-12 mol%, SrT
The main component composed of 4 to 15 mol% of iO 3 is used as a semiconducting agent, and rare earth elements such as Y, La and Ce, Nb and B are used.
At least one of i, Sb, W, and Th is 0.15 to 0.15.
With respect to the barium titanate-based semiconductor porcelain containing 0.5 mol%, manganese is converted to Mn in an amount of 0.002 to 0.025 mol%, and SiO 2 is included in an amount of 0.2 to 0.7 mol%. A barium titanate-based semiconductor porcelain composition characterized by being added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3235458A JPH0551254A (en) | 1991-08-21 | 1991-08-21 | Barium titanate-containing semiconductor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3235458A JPH0551254A (en) | 1991-08-21 | 1991-08-21 | Barium titanate-containing semiconductor porcelain composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0551254A true JPH0551254A (en) | 1993-03-02 |
Family
ID=16986402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3235458A Pending JPH0551254A (en) | 1991-08-21 | 1991-08-21 | Barium titanate-containing semiconductor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0551254A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022411A1 (en) * | 1996-11-20 | 1998-05-28 | Murata Manufacturing Co., Ltd. | Barium titanate-base semiconducting ceramic composition |
| US6455454B1 (en) * | 1999-04-28 | 2002-09-24 | Murata Manufacturing Co. Ltd. | Semiconductor ceramic, semiconductor ceramic element and circuit protection element |
| KR20030092719A (en) * | 2002-05-31 | 2003-12-06 | 현대자동차주식회사 | PTC compound for electric heater of vehicle |
| WO2023199677A1 (en) * | 2022-04-15 | 2023-10-19 | 株式会社村田製作所 | Chip-type electronic component |
-
1991
- 1991-08-21 JP JP3235458A patent/JPH0551254A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022411A1 (en) * | 1996-11-20 | 1998-05-28 | Murata Manufacturing Co., Ltd. | Barium titanate-base semiconducting ceramic composition |
| US6187707B1 (en) | 1996-11-20 | 2001-02-13 | Murata Manufacturing Co., Ltd. | Barium titanate-based semiconductive ceramic composition |
| CN1089735C (en) * | 1996-11-20 | 2002-08-28 | 株式会社村田制作所 | Barium titanate-base semiconducting ceramic composition |
| US6455454B1 (en) * | 1999-04-28 | 2002-09-24 | Murata Manufacturing Co. Ltd. | Semiconductor ceramic, semiconductor ceramic element and circuit protection element |
| KR20030092719A (en) * | 2002-05-31 | 2003-12-06 | 현대자동차주식회사 | PTC compound for electric heater of vehicle |
| WO2023199677A1 (en) * | 2022-04-15 | 2023-10-19 | 株式会社村田製作所 | Chip-type electronic component |
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