JPH11176608A - Manufacture of positive temperature coefficient thermistor compound - Google Patents
Manufacture of positive temperature coefficient thermistor compoundInfo
- Publication number
- JPH11176608A JPH11176608A JP9340346A JP34034697A JPH11176608A JP H11176608 A JPH11176608 A JP H11176608A JP 9340346 A JP9340346 A JP 9340346A JP 34034697 A JP34034697 A JP 34034697A JP H11176608 A JPH11176608 A JP H11176608A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- temperature coefficient
- positive temperature
- coefficient thermistor
- compound
- 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.)
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- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｐｂを含有するチ
タン酸バリウム鉛系の正特性サーミスタ組成物の製造方
法に関する。The present invention relates to a method for producing a barium lead titanate-based positive temperature coefficient thermistor composition containing Pb.
【０００２】[0002]
【従来の技術】ＢａＴｉＯ3に、Ｙ，Ｎｄ等の半導体元
素を添加した正特性サーミスタは、大きな正の温度係数
を有する温度領域をＰｂの添加で調整することができ、
温度の測定、過電流防止、モータ起動等の回路素子ある
いは定温発熱ヒータ等に用いられている。正特性サーミ
スタは、キュリー温度を境に、電気抵抗値が１０3〜１
０8倍程度大きくなる特徴を有しており、実用に際して
は室温比抵抗、キュリー温度、抵抗温度係数、抵抗変化
幅を目的により適切な値をもつように組成、製法を調整
して用いられる（特開平６−５３００６号公報参照）。2. Description of the Related Art A positive temperature coefficient thermistor in which semiconductor elements such as Y and Nd are added to BaTiO 3 can adjust a temperature region having a large positive temperature coefficient by adding Pb.
It is used as a circuit element for measuring temperature, preventing overcurrent, starting a motor, or a constant-temperature heating heater. The positive temperature coefficient thermistor has an electric resistance of 10 3 to 1 at the Curie temperature.
0 has 8 times larger features, the practical use room temperature resistivity, Curie temperature, the temperature coefficient of resistance, the composition of the resistance change range to have an appropriate value depending on the purpose, be used to adjust the process ( See JP-A-6-53006).
【０００３】[0003]
【発明が解決しようとする課題】Ｐｂを含有するチタン
酸バリウム鉛系組成物は、焼結中にＰｂの揮発が著しい
ので、焼成方法として、成形体の周囲にＰｂＯ、ＰｂＺ
ｒＯ3等の雰囲気調整用の粉末を置いたり、同様の目的
でダミーを置くことがなされていた。しかしながら、こ
れらの方法は、作業が煩わしく、セッターの消耗が激し
いという問題点がある。In a barium lead titanate-based composition containing Pb, volatilization of Pb is remarkable during sintering.
A powder for adjusting the atmosphere such as rO 3 has been placed, and a dummy has been placed for the same purpose. However, these methods are problematic in that the operation is cumbersome and the setter is greatly consumed.
【０００４】また、一般的には、図１に示すように、さ
や３内の底面にセッター２を敷き、その上に成形体１を
寝かせて配置したり、図２に示すように成形体１を立て
て並べたりしている。その際、例えば、図２の場合に
は、図３に示すように、セッター２に接した面はＰｂの
揮発が少ないのでｔ2のように、接していない面は、Ｐ
ｂの揮発が多くなり、収縮率の差が生じ、ｔ1のように
ｔ2より短くなって抵抗値にバラツキが生じてしまう。
また、このような場合に、全体としてみると、そりやう
ねりが大きくなって、歩留まりが悪くなるという問題が
ある。さらに、これらＰｂを含んだものは、焼成物のＰ
ｂによりセッターやさやが反応しやすく、消耗が激しい
という問題もあった。In general, as shown in FIG. 1, a setter 2 is laid on the bottom surface of a sheath 3 and a molded body 1 is placed on the setter 2 or, as shown in FIG. Or standing up. At that time, for example, in the case of Figure 2, as shown in FIG. 3, since the surface in contact with the setter 2 is less volatilization of Pb as t 2, the surface not in contact, P
b volatilization becomes large, the difference in shrinkage occurs, variation occurs in the resistance value is shorter than t 2 as t 1.
Further, in such a case, there is a problem that the warp and the swell are increased as a whole and the yield is deteriorated. Further, those containing Pb are used as P
There was also a problem that the setter and pod were easily responsive due to b, and the consumption was severe.
【０００５】そこで、本発明は、収縮率を調整して焼成
及び半導体化する温度を低下したチタン酸バリウム鉛系
の正特性サーミスタ組成物の製造方法を提供するもので
ある。Accordingly, the present invention provides a method for producing a barium lead titanate-based positive temperature coefficient thermistor composition in which the shrinkage rate is adjusted to reduce the temperature at which firing and conversion to a semiconductor are performed.
【０００６】[0006]
【課題を解決するための手段】本発明の正特性サーミス
タ組成物の製造方法は、（Ｂａ１−ｘ−ｙＰｂｘＣａ
ｙ）ＴｉＯ3（但し、０．２≦ｘ≦１．０、 ０≦ｙ≦
０．２である。）で示されるチタン酸バリウム鉛系化合
物に半導体化元素を含有させた組成物に、ＰｂＯを０．
１〜１０．０ｍｏｌ％添加した後、成形し、焼成するこ
とを特徴とする。正特性サーミスタ組成物には、Ｂ2Ｏ3
を０．１〜４．５ｍｏｌ％、又はＧｅＯ2を０．１〜
４．０ｍｏｌ％単独あるいは両方添加することが好まし
い。According to the present invention, there is provided a method for producing a positive temperature coefficient thermistor composition, comprising the steps of (Ba1-xyPbxCa)
y) TiO 3 (however, 0.2 ≦ x ≦ 1.0, 0 ≦ y ≦
0.2. PbO is added to a composition containing a barium lead titanate-based compound represented by the formula (1) and a semiconducting element.
After the addition of 1 to 10.0 mol%, the composition is molded and fired. The positive temperature coefficient thermistor composition includes B 2 O 3
The 0.1~4.5mol%, or from 0.1 to GeO 2
It is preferable to add 4.0 mol% alone or both.
【０００７】さらに、ＳｉＯ2を０．０１〜３．０ｍｏ
ｌ％、又はＭｎを０．０１〜０．１５ｍｏｌ％単独ある
いは両方添加してもよい。Further, SiO 2 is used in an amount of 0.01 to 3.0 mol.
1% or Mn may be added alone or in an amount of 0.01 to 0.15 mol%.
【０００８】[0008]
【発明の実施の形態】本発明において、ＰｂＯを０．１
〜１０ｍｏｌ％添加するのは、ＰｂＯが０．１ｍｏｌ％
未満では雰囲気の調整の効果が不十分であり、１０ｍｏ
ｌ％を超えると結晶粒が異常に粒成長を引き起こすため
である。なお、実施例では、ＰｂＯを用いているが、Ｐ
ｂ3Ｏ4、ＰｂＯ2を用いることによりＰＴＣ特性を向上
させることができる。しかし、これらは高価であるの
で、用途に応じて適宜使い分ける。 Ｂ2Ｏ3を０．１〜
４．５ｍｏｌ％、ＧｅＯ2を０．１〜１．５ｍｏｌ％と
したのは、それぞれの下限値未満では焼結性、半導体化
の効果が不十分であり、また、それぞれの上限値を超え
ると、素子の比抵抗が大きくなり、実用性がなくなるた
めである。なお、実施例で、Ｂ2Ｏ3を用いているが、Ｂ
Ｎ、Ｂ4Ｃ、金属Ｂを用いてもよく、特にＢＮを用いる
と、粉末の分散がよくなり、素子の抵抗値のバラツキを
抑えることができる。DETAILED DESCRIPTION OF THE INVENTION In the present invention, PbO is 0.1%.
The addition of -10 mol% is based on 0.1 mol% of PbO.
If it is less than 10 m, the effect of adjusting the atmosphere is insufficient, and
If the content exceeds 1%, the crystal grains cause abnormal grain growth. In this embodiment, PbO is used.
b 3 O 4, PbO 2 can improve PTC characteristics by using a. However, since these are expensive, they are appropriately used depending on the application. 0.1 The B 2 O 3
The reason that 4.5 mol% and GeO 2 are 0.1 to 1.5 mol% is that the sinterability and the effect of semiconductor conversion are insufficient if the respective lower limit values are less than the respective lower limit values, and if the respective upper limit values are exceeded. This is because the specific resistance of the element becomes large and the practicality is lost. In the embodiment, B 2 O 3 is used.
N, B 4 C, or metal B may be used. In particular, when BN is used, dispersion of the powder is improved, and variation in the resistance value of the element can be suppressed.
【０００９】本発明の実施例においては、半導体化元素
としてＹ2Ｏ3を例として示したが、好ましくはＳｂ2Ｏ3
を添加すると効果的で、その他ＷＯ3やＮｂ2Ｏ5、Ｔａ2
Ｏ5や他の希土類元素を使用してももちろん差し支えな
い。また、半導体化元素が３価の場合、Ａサイトの元
素、５価の場合、Ｂサイトの元素で置換し、置換モル数
に対してＰｂ、Ｓｒ、Ｔｉ、Ｚｒ等の元素で原子化補償
してもよい。In the embodiments of the present invention, Y 2 O 3 has been described as an example of a semiconductor element, but preferably Sb 2 O 3
Is effective when WO 3 , Nb 2 O 5 , Ta 2
Of course, no problem even when using the O 5 and other rare earth elements. When the semiconducting element is trivalent, it is substituted with an A-site element and when it is pentavalent, it is substituted with a B-site element, and atomization is compensated for the substitution mole number with an element such as Pb, Sr, Ti, or Zr. You may.
【００１０】Ｃａは結晶粒を微細化し、耐電圧特性を向
上させる効果がある。組成範囲を０≦ｙ≦０．２とした
のは、０．２を超えると素子の比抵抗が大きくなり、実
用性がなくなるためである。[0010] Ca has the effect of making the crystal grains fine and improving the withstand voltage characteristics. The reason why the composition range is set to 0 ≦ y ≦ 0.2 is that if it exceeds 0.2, the specific resistance of the device becomes large, and practicality is lost.
【００１１】また、ＳｉＯ2は焼結温度を低下させ、結
晶粒の異常粒成長を抑制するという効果があり、０．０
１〜３．０ｍｏｌ％としたのは、０．０１ｍｏｌ％未満
では異常粒成長抑制効果が不十分であり、３．０ｍｏｌ
％を超えると逆に結晶粒の異常粒成長を引き起こす。[0011] Further, SiO 2 has the effect of lowering the sintering temperature and suppressing the abnormal growth of crystal grains.
The reason for setting the content to 1 to 3.0 mol% is that if it is less than 0.01 mol%, the effect of suppressing abnormal grain growth is insufficient, and
%, On the contrary, abnormal grain growth of crystal grains is caused.
【００１２】また、Ｍｎは、キュリー温度以上での抵抗
温度係数を増大させる効果があるが、Ｍｎの添加は比抵
抗をも増大させるため、実用的な素子比抵抗（１０ｋΩ
・ｃｍ以下）の範囲で前記効果を得るには、その組成範
囲を０．０１〜０．１５ｍｏｌ％とする必要がある。Mn has the effect of increasing the temperature coefficient of resistance above the Curie temperature, but the addition of Mn also increases the specific resistance.
(Cm or less), it is necessary to set the composition range to 0.01 to 0.15 mol% in order to obtain the above effect.
【００１３】[0013]
【実施例】出発原料として高純度のＢａＣＯ3、ＣａＣ
Ｏ3、ＰｂＯ、ＴｉＯ2、ＳｉＯ２、Ｙ2Ｏ3、Ｂ2Ｏ3、Ｇ
ｅＯ2を準備した。EXAMPLES High-purity BaCO 3 and CaC as starting materials
O 3 , PbO, TiO 2 , SiO 2 , Y 2 O 3 , B 2 O 3 , G
eO 2 was prepared.
【００１４】これら各原料を表１に示した組成になるよ
うにそれぞれ配合し、２４時聞ボールミルを用いて混合
した。Each of these raw materials was blended so as to have the composition shown in Table 1 and mixed using a 24 hour ball mill.
【００１５】[0015]
【表１】 混合物を脱水乾燥後、大気中６００〜９００℃で約１〜
３時間仮焼した後、バインダーとともに、表１に示す量
のＰｂＯを添加し、再度２４時聞粉砕し混合した。乾燥
後、２００メッシュの粉末に造粒し、１０００ｋｇ／ｃ
ｍ2の圧力で直径１０ｍｍ、厚さ１．５ｍｍに成形し
た。さらに、組成に応じて、大気中、１１００〜１３０
０℃、０．５〜２時間での条件で焼成した。こうして得
られた試料にＩｎ−Ｇａ合金を塗布し、常温〜５５０℃
までの比抵抗−温度特性を測定した。 表１から明らか
なように、本発明の製造方法による組成物は、桁数がＰ
ｂＯを添加しないものに比べて大きく、ＰＴＣの特性が
向上しており、また、室温比抵抗も優れている。[Table 1] After dehydration and drying of the mixture, about 1 to about
After calcining for 3 hours, the amount of PbO shown in Table 1 was added together with the binder, and the mixture was again ground at 24 hours and mixed. After drying, granulate to 200 mesh powder and 1000kg / c
It was formed to a diameter of 10 mm and a thickness of 1.5 mm at a pressure of m 2 . Furthermore, depending on the composition, in the atmosphere, 1100 to 130
Baking was performed at 0 ° C. for 0.5 to 2 hours. An In-Ga alloy is applied to the sample thus obtained, and the temperature is from room temperature to 550 ° C.
The resistivity-temperature characteristics up to were measured. As is clear from Table 1, the composition according to the production method of the present invention has a digit number of P
It is larger than that without bO added, has improved PTC characteristics, and has excellent room temperature resistivity.
【００１６】[0016]
【発明の効果】Ｐｂを含有するチタン酸バリウム鉛系組
成物にＰｂＯを過剰に添加し、焼成時に焼結体の周囲を
ＰｂＯの雰囲気とすることで、正特性サーミスタ組成物
の全体の収縮率をコントロールすることができる。Ｐｂ
Ｏの過剰により、焼成温度及び半導体化温度を下げて、
セッターやさやへの影響を少なくすることができる。The PbO-containing barium lead titanate-based composition is excessively doped with PbO and the atmosphere around the sintered body is set to a PbO atmosphere during firing, so that the overall shrinkage of the positive temperature coefficient thermistor composition is reduced. Can be controlled. Pb
Due to the excess of O, the firing temperature and the semiconductor conversion temperature are lowered,
The influence on the setter and pod can be reduced.
【図１】成形体を寝かせてセッターに並べた状態を示す
図である。FIG. 1 is a diagram showing a state in which molded articles are laid down and arranged on a setter.
【図２】成形体を立ててセッターに並べた状態を示す図
である。FIG. 2 is a view showing a state in which molded bodies are set up and arranged on a setter.
【図３】成形体の収縮した状態を示す模式図である。FIG. 3 is a schematic view showing a contracted state of a molded body.
１：成形体 ２：セッター ３：さや 1: molded body 2: setter 3: sheath
Claims (4)
3（但し、０．２≦ｘ≦１．０、 ０≦ｙ≦０．２であ
る。）で示されるチタン酸バリウム鉛系化合物に半導体
化元素を含有させた組成物に、ＰｂＯを０．１〜１０．
０ｍｏｌ％添加した後、成形し、焼成することを特徴と
する正特性サーミスタ組成物の製造方法。1. (Ba1-xyPbxCay) TiO
3 (however, 0.2 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.2) A composition obtained by adding a barium lead-based compound to a semiconducting element and containing PbO in an amount of 0. 1-10.
A method for producing a positive temperature coefficient thermistor composition, comprising adding 0 mol%, forming, and firing.
ることを特徴とする請求項１記載の正特性サーミスタ組
成物の製造方法。2. The method for producing a positive temperature coefficient thermistor composition according to claim 1, wherein 0.1 to 4.5 mol% of B 2 O 3 is added.
することを特徴とする請求項１又は２記載の正特性サー
ミスタ組成物の製造方法。3. The method for producing a positive temperature coefficient thermistor composition according to claim 1, wherein 0.1 to 4.0 mol% of GeO 2 is added.
又はＭｎを０．０１〜０．１５ｍｏｌ％添加することを
特徴とする請求項１、２及び３記載の正特性サーミスタ
組成物の製造方法。4. An amount of SiO 2 of 0.01 to 3.0 mol%,
4. The method for producing a positive temperature coefficient thermistor composition according to claim 1, wherein Mn is added in an amount of 0.01 to 0.15 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9340346A JPH11176608A (en) | 1997-12-10 | 1997-12-10 | Manufacture of positive temperature coefficient thermistor compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9340346A JPH11176608A (en) | 1997-12-10 | 1997-12-10 | Manufacture of positive temperature coefficient thermistor compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11176608A true JPH11176608A (en) | 1999-07-02 |
Family
ID=18336064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9340346A Withdrawn JPH11176608A (en) | 1997-12-10 | 1997-12-10 | Manufacture of positive temperature coefficient thermistor compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11176608A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004110952A1 (en) * | 2003-06-16 | 2004-12-23 | Toho Titanium Co., Ltd. | Barium titanate based semiconductor porcelain composition |
-
1997
- 1997-12-10 JP JP9340346A patent/JPH11176608A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004110952A1 (en) * | 2003-06-16 | 2004-12-23 | Toho Titanium Co., Ltd. | Barium titanate based semiconductor porcelain composition |
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