JP2976702B2 - Semiconductor porcelain composition - Google Patents
Semiconductor porcelain compositionInfo
- Publication number
- JP2976702B2 JP2976702B2 JP4166832A JP16683292A JP2976702B2 JP 2976702 B2 JP2976702 B2 JP 2976702B2 JP 4166832 A JP4166832 A JP 4166832A JP 16683292 A JP16683292 A JP 16683292A JP 2976702 B2 JP2976702 B2 JP 2976702B2
- Authority
- JP
- Japan
- Prior art keywords
- balls
- semiconductor porcelain
- semiconductor
- composition
- porcelain
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】この発明は半導体磁器組成物に関
し、特にチタン酸バリウム系の半導体磁器組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor porcelain composition, and more particularly to a barium titanate-based semiconductor porcelain composition.
【０００２】[0002]
【従来の技術】従来、この種の半導体磁器組成物にに
は、Ｂａもしくは、Ｓｒ，Ｐｂ，Ｃａのうち少なくとも
１種以上およびＢａと、この合計原子モル数に対して等
モル以上のＴｉ、あるいはＺｒ、またはＴｉおよびＺｒ
と、半導体化剤と、微量の添加物とを含むものがあっ
た。2. Description of the Related Art Conventionally, semiconductor porcelain compositions of this type include at least one of Ba or Sr, Pb, Ca and Ba, and at least one mole of Ti, Or Zr, or Ti and Zr
And a semiconductor agent and a trace amount of an additive.
【０００３】このような従来の半導体磁器組成物からな
る半導体磁器は、正の抵抗−温度（ＰＴＣ）特性を有
し、その特性を利用して電流制御，電圧制御など広く利
用されている。[0003] Semiconductor porcelain made of such a conventional semiconductor porcelain composition has a positive resistance-temperature (PTC) characteristic, and is widely used for current control, voltage control and the like by utilizing the characteristic.
【０００４】[0004]
【発明が解決しようとする課題】ところが、このような
従来の半導体磁器では、抵抗の電圧依存性が大きいの
で、ＰＴＣ特性の勾配が減少し、それを用いた素子の温
度が急激に高くなって、耐破壊電圧が低くなり耐破壊電
圧特性が悪くかつ突入電流を生じさせる電圧も低くなり
突入電流特性も悪くなり、実際に使用するにあたって、
その機能を果たさないことがある。これは、このような
従来の半導体磁器の結晶粒径が大きく、不均一であるた
めである。However, in such a conventional semiconductor porcelain, since the voltage dependence of the resistance is large, the gradient of the PTC characteristic is reduced, and the temperature of the element using the same increases rapidly. However, the breakdown voltage is low, the breakdown voltage characteristics are poor, the voltage at which inrush current is generated is low, and the inrush current characteristics are also poor.
It may not fulfill its function. This is because such conventional semiconductor porcelains have large and non-uniform crystal grain sizes.
【０００５】それゆえに、この発明の主たる目的は、優
れた耐破壊電圧特性および突入電流特性を有する半導体
磁器を得ることができる、半導体磁器組成物を提供する
ことである。[0005] Therefore, a main object of the present invention is to provide a semiconductor porcelain composition capable of obtaining a semiconductor porcelain having excellent breakdown voltage characteristics and inrush current characteristics.
【０００６】[0006]
【課題を解決するための手段】この発明は、チタン酸バ
リウム系の半導体磁器組成物であって、（Ｂａ
1-x Ａx ）1.000 （Ｔｉ1-y Ｚｒy ）z Ｏ3 （ただし、
ＡはＳｒ，Ｐｂ，Ｃａのうち少なくとも１種以上、ｘ＜
１、ｙ≦１、０．９７００≦ｚ≦０．９９９９）と、半
導体化剤と、微量の添加物とを含む、半導体磁器組成物
である。The present invention relates to a barium titanate-based semiconductor ceramic composition comprising (Ba)
1-x A x) 1.000 ( Ti 1-y Zr y) z O 3 ( where
A is at least one of Sr, Pb and Ca, x <
1, y ≦ 1, 0.9700 ≦ z ≦ 0.9999), a semiconducting agent, and a small amount of an additive.
【０００７】[0007]
【作用】この発明にかかる半導体磁器組成物から得られ
る半導体磁器は、従来の半導体磁器に比べて、結晶粒径
が小さく結晶粒径のばらつきが少ない。そのため、この
発明にかかる半導体磁器組成物から得られる半導体磁器
は、優れた耐破壊電圧特性および突入電流特性を有す
る。The semiconductor porcelain obtained from the semiconductor porcelain composition according to the present invention has a smaller crystal grain size and less variation in crystal grain size than conventional semiconductor porcelain. Therefore, semiconductor porcelain obtained from the semiconductor porcelain composition according to the present invention has excellent breakdown voltage characteristics and inrush current characteristics.
【０００８】なお、このように、結晶粒径が小さく結晶
粒径のばらつきが少ない半導体磁器を得るためには、こ
の発明にかかる半導体磁器組成物の粉砕媒体として、た
とえばＺｒＯ2 ボール，ＴｉＯ2 ボール，Ａｌ2 Ｏ3 ボ
ール，ＳｉＣボール，Ｓｉ3Ｎ4 ボール，ＺｒＳｉＯ4
およびＳｉＯ2 ボールのうち少なくとも１種以上を用い
ればよい。As described above, in order to obtain a semiconductor porcelain having a small crystal grain size and a small variation in the crystal grain size, ZrO 2 balls, TiO 2 balls, etc. are used as grinding media for the semiconductor porcelain composition according to the present invention. , Al 2 O 3 ball, SiC ball, Si 3 N 4 ball, ZrSiO 4
And at least one of SiO 2 balls.
【０００９】[0009]
【発明の効果】この発明によれば、優れた耐破壊電圧特
性および突入電流特性を有する半導体磁器を得ることが
できる、半導体磁器組成物が得られる。According to the present invention, a semiconductor porcelain composition which can provide a semiconductor porcelain having excellent breakdown voltage characteristics and inrush current characteristics can be obtained.
【００１０】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 following detailed description of the embodiments.
【００１１】[0011]
【実施例】まず、原料として、主成分であるＢａＣ
Ｏ3 ，Ｐｂ3 Ｏ4 ，ＳｒＣＯ3 ，ＣａＣＯ3 およびＴｉ
Ｏ2 と、半導体化剤であるＹ2 Ｏ3 あるいはＬａ2 Ｏ3
と、微量の添加物として特性改善剤であるＭｎＯ2 およ
びＳｉＯ2 とを、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、さらに、粉砕媒体としてのＺｒ
Ｏ2 ボール，ＴｉＯ2 ボールあるいはフリントボールで
１０時間粉砕して、スラリーを得た。EXAMPLE First, as a raw material, BaC which is a main component was used.
O 3 , Pb 3 O 4 , SrCO 3 , CaCO 3 and Ti
O 2 and Y 2 O 3 or La 2 O 3 as a semiconducting agent
And a small amount of an additive, MnO 2 and SiO 2 , which are property improvers, are blended so as to obtain a semiconductor porcelain composition having a ratio shown in Table 1, and further, Zr as a grinding medium
A slurry was obtained by crushing with O 2 balls, TiO 2 balls or flint balls for 10 hours.
【００１２】[0012]
【表１】 [Table 1]
【００１３】このスラリーを、脱水乾燥し、５０メッシ
ュの篩で造粒した後、１１３０℃で仮焼し、バインダを
加え、１０００ｋｇ／ｃｍ2 で直径１７．５ｍｍ，厚み
３０ｍｍの円板状に成形して、成形体を得た。それか
ら、この成形体を、１３００〜１４００℃で焼成して、
磁器を得た。This slurry is dehydrated and dried, granulated with a 50-mesh sieve, calcined at 1130 ° C., added with a binder, and formed into a disk having a diameter of 17.5 mm and a thickness of 30 mm at 1000 kg / cm 2. Thus, a molded body was obtained. Then, this molded body is fired at 1300 to 1400 ° C.
I got porcelain.
【００１４】そして、その磁器の結晶粒径を求めるた
め、磁器をＳＥＭで写真撮影した後、画像解析し求め
た。さらに、その磁器の電気特性を測定するために、磁
器の両主面にＩｎ−Ｇａ電極を施し、２５℃の比抵抗，
キュリー点，耐破壊電圧特性および突入電流特性を調べ
た。なお、耐破壊電圧特性および突入電流特性について
は、耐破壊電圧と突入電流が生じる電圧とをそれぞれ測
定した。これらの結果を表２に表す。Then, in order to determine the crystal grain size of the porcelain, the porcelain was photographed with an SEM and image analysis was performed. Further, in order to measure the electrical characteristics of the porcelain, In-Ga electrodes were provided on both main surfaces of the porcelain, and the specific resistance at 25 ° C.
The Curie point, breakdown voltage characteristics and inrush current characteristics were examined. With respect to the breakdown voltage characteristics and the inrush current characteristics, the breakdown voltage and the voltage at which the inrush current occurred were measured. Table 2 shows the results.
【００１５】[0015]
【表２】 [Table 2]
【００１６】なお、表１および表２中、試料番号に＊印
をつけたものはこの発明の範囲外のものであり、それ以
外のものはこの発明の範囲内のものである。In Tables 1 and 2, those marked with an asterisk (*) are out of the scope of the present invention, and the others are within the scope of the present invention.
【００１７】これらの結果から明らかなように、粉砕媒
体としてＺｒＯ2 ボール，ＴｉＯ2ボールを用い、半導
体磁器組成物の組成をこの発明の範囲内にすることによ
って、結晶粒径が小さく結晶粒径のばらつきの少ない半
導体磁器が得られ、半導体磁器の耐電圧特性，突入電流
特性が向上することを確認した。As is apparent from these results, by using ZrO 2 balls and TiO 2 balls as grinding media and setting the composition of the semiconductor porcelain composition within the range of the present invention, the crystal grain size is reduced. It was confirmed that a semiconductor porcelain with less variation was obtained, and that the withstand voltage characteristic and the inrush current characteristic of the semiconductor porcelain were improved.
【００１８】それに対して、Ｂａ，Ｐｂ，ＳｒおよびＣ
ａの合計原子モル数に対して、ＴｉＯ2 の原子モル数が
０．９９９を超えると特性が劣化し、逆にＴｉＯ2 の原
子モル数が０．９７０未満では磁器が半導体化しないこ
とがわかった。On the other hand, Ba, Pb, Sr and C
When the atomic mole number of TiO 2 exceeds 0.999 with respect to the total atomic mole number of a, the characteristics are deteriorated, and when the atomic mole number of TiO 2 is less than 0.970, the porcelain does not turn into a semiconductor. Was.
【００１９】また、粉砕媒体としてフリントボールを用
いた場合には、半導体磁器の結晶粒径のばらつきが大き
くなることがわかった。It has also been found that when flint balls are used as the grinding media, the variation in the crystal grain size of the semiconductor porcelain increases.
【００２０】なお、半導体磁器組成物の主成分中のＴｉ
に代えて、Ｚｒ、またはＴｉおよびＺｒを用いても、同
様の結果が得られた。In addition, Ti in the main component of the semiconductor ceramic composition
The same result was obtained when Zr or Ti and Zr were used instead of
【００２１】また、半導体磁器組成物の主成分中にＰ
ｂ，ＳｒおよびＣａを同時に用いなくても、同様の結果
が得られた。In addition, P is contained in the main component of the semiconductor ceramic composition.
Similar results were obtained without using b, Sr and Ca simultaneously.
【００２２】さらに、粉砕媒体としてＡｌ2 Ｏ3 ボー
ル，ＳｉＣボール，Ｓｉ3 Ｎ4 ボール，ＺｒＳｉＯ4 ボ
ール，ＳｉＯ2 ボールを用いても、この発明の範囲内の
半導体磁器組成物から結晶粒径が小さく結晶粒径のばら
つきが少ない半導体磁器が得られ、半導体磁器の耐破壊
電圧特性および突入電流特性が向上することも確認し
た。Further, even when Al 2 O 3 balls, SiC balls, Si 3 N 4 balls, ZrSiO 4 balls, or SiO 2 balls are used as a grinding medium, the crystal grain size is determined from the semiconductor ceramic composition within the scope of the present invention. It was also confirmed that a semiconductor porcelain having a small variation in crystal grain size was obtained, and the breakdown voltage characteristics and the inrush current characteristics of the semiconductor porcelain were improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 阿 部 吉 晶 京都府長岡京市天神２丁目26番10号 株 式会社 村田製作所内 (56)参考文献 特開 平３−103357（ＪＰ，Ａ) 特開 昭55−134903（ＪＰ，Ａ) 特開 平５−254928（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C04B 35/46 C04B 35/49 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshiaki Abe 2-26-10 Tenjin, Nagaokakyo-shi, Kyoto Inside Murata Manufacturing Co., Ltd. (56) References JP-A-3-103357 (JP, A) JP-A-55-134903 (JP, A) JP-A-5-254928 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C04B 35/46 C04B 35/49
Claims (2)
であって、 （Ｂａ1-x Ａx ）1.000 （Ｔｉ1-y Ｚｒy ）z Ｏ3 （た
だし、ＡはＳｒ，Ｐｂ，Ｃａのうち少なくとも１種以
上、ｘ＜１、ｙ≦１、０．９７００≦ｚ≦０．９９９
９）、 半導体化剤、および微量の添加物を含む、半導体磁器組
成物。1. A semiconductor ceramic composition barium titanate, (Ba 1-x A x ) 1.000 (Ti 1-y Zr y) z O 3 ( provided that, A is Sr, Pb, among Ca At least one kind, x <1, y ≦ 1, 0.9700 ≦ z ≦ 0.999
9) A semiconductor porcelain composition comprising a semiconducting agent and a trace amount of an additive.
その粉砕媒体として、ＺｒＯ2 ボール，ＴｉＯ2 ボー
ル，Ａｌ2 Ｏ3 ボール，ＳｉＣボール，Ｓｉ3Ｎ4 ボー
ル，ＺｒＳｉＯ4 およびＳｉＯ2 ボールのうち少なくと
も１種以上を用いた、請求項１の半導体磁器組成物。2. When mixing and pulverizing each component of the composition,
2. The semiconductor porcelain according to claim 1, wherein at least one of ZrO 2 balls, TiO 2 balls, Al 2 O 3 balls, SiC balls, Si 3 N 4 balls, ZrSiO 4 and SiO 2 balls is used as the grinding medium. Composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4166832A JP2976702B2 (en) | 1992-06-01 | 1992-06-01 | Semiconductor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4166832A JP2976702B2 (en) | 1992-06-01 | 1992-06-01 | Semiconductor porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05330910A JPH05330910A (en) | 1993-12-14 |
| JP2976702B2 true JP2976702B2 (en) | 1999-11-10 |
Family
ID=15838488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4166832A Expired - Lifetime JP2976702B2 (en) | 1992-06-01 | 1992-06-01 | Semiconductor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2976702B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU7201594A (en) * | 1993-06-09 | 1995-01-03 | United States Of America, As Represented By The Secretary Of The Army, The | Novel ceramic ferroelectic composite material - bsto-zro2 |
| US5312790A (en) * | 1993-06-09 | 1994-05-17 | The United States Of America As Represented By The Secretary Of The Army | Ceramic ferroelectric material |
| EP2450327A4 (en) * | 2009-07-01 | 2014-06-11 | Murata Manufacturing Co | Semiconductor ceramic and positive-coefficient thermistor |
| JP6269078B2 (en) * | 2014-01-09 | 2018-01-31 | 株式会社村田製作所 | Method for producing functional metal oxide material |
-
1992
- 1992-06-01 JP JP4166832A patent/JP2976702B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05330910A (en) | 1993-12-14 |
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