JP4269485B2 - Lead barium titanate semiconductor ceramic composition - Google Patents
Lead barium titanate semiconductor ceramic composition Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、１２０〜４９０℃の温度で任意のキュリー点を有し、高温での使用においても優れたＰＴＣＲ特性を有するチタン酸バリウム鉛系半導体磁器組成物に関するものである。
【０００２】
【従来の技術】
従来、チタン酸バリウム系の半導体磁器組成物において、キュリー点を高温側にシフトさせるために、Ｂａの一部をＰｂで置換することが知られている。しかしながら、Ｐｂ置換する場合には焼成時のＰｂの揮発による特性の劣化が問題となっている。特に、Ｐｂ置換量が５０モル％を超えたキュリー点が３００℃以上のものにおいては、室温抵抗の急激な増加によりＰＴＣＲ特性の著しい劣化が生じる。
この問題を解決するために、例えば特開平４−２１５６５号公報には、チッ化ホウ素（ＢＮ）を０．８〜４．５モル％添加することにより、焼結性が改善されて半導体化が促進されることが開示されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、前記開示された磁器組成物は、焼成により粒子径が異なる成長をするため、大きな粒子の存在により耐電圧が低くＰＴＣＲサーミスタとして用いる場合には信頼性に課題を有していた。
【０００４】
【課題を解決するための手段】
前記課題を解決するために、本発明者らは鋭意検討を行った結果、軟化点が低いガラス物質を添加した場合には、１０００〜１２００℃と従来よりも低い温度で焼成することができるため、焼成時にＰｂの揮発が抑制され、Ｐｂ置換量が広範囲において、特に従来では達成し得なかったＰｂが６０〜９０モル％と高濃度領域において、低抵抗素子が得られることを見出し、高いキュリー温度を有する高温用のＰＴＣＲ材料用のチタン酸バリウム鉛系半導体磁器組成物を提供できることを見出した。本発明は、１２０〜４９０℃の温度で任意のキュリー点を有し、特に、高温での使用においても優れたＰＴＣＲ特性を有すると共に電流制限素子としても使用可能なチタン酸バリウム鉛系半導体磁器組成物を提供することを目的とする。本発明は、（Ｂａ1-xＰｂx）ＴｉＯ3（式中、ｘは０≦ｘ＜１である。）を母体としたチタン酸バリウム鉛系半導体磁器組成物において、チタン酸バリウム鉛系半導体磁器組成物は、前記母体に半導体化剤と軟化点が９５０℃以下のガラス物質とを混合し焼成したものであり、前記ガラス物質は母体に対して０．５〜３．０ｗｔ％の範囲であり、前記ガラス物質はホウケイ酸鉛ガラスであることを特徴とするチタン酸バリウム鉛系半導体磁器組成物に関する。また、（Ｂａ 1-x Ｐｂ x ）ＴｉＯ 3 （式中、ｘは０≦ｘ＜１である。）を母体としたチタン酸バリウム鉛系半導体磁器組成物において、チタン酸バリウム鉛系半導体磁器組成物は、前記母体に半導体化剤と軟化点が９５０℃以下のガラス物質とを混合し焼成したものであり、前記ガラス物質は母体に対して０．５〜３．０ｗｔ％の範囲であり、前記ガラス物質はＰｂ−Ｓｉ、Ｐｂ−Ｇｅ、Ｂ−Ｓｉ、Ｂ−Ｓｉ−Ｐｂ、Ｂ−Ｂａ及びＢａ−Ｐｂ−Ｓｉから選ばれる少なくとも１種以上であることを特徴とするチタン酸バリウム鉛系半導体磁器組成物に関する。
【０００５】
【発明の実施の形態】
本発明におけるガラス物質としては、軟化点が９５０℃以下のものであれば特に限定されないが、Ｐｂ、Ｂ及びＳｉから選ばれる少なくとも１種以上を含有するものが好ましい。ガラス物質の軟化点が過度に低い場合には得られたチタン酸バリウム鉛系半導体磁器組成物がＲＴＣＲ特性を示さなくなる場合があるので、ガラス物質の軟化点は３００℃以上が好ましい。また、ガラス物質の軟化点が９５０℃を超えて過度に高くなると焼成温度を１２００℃以下とすることができなくなる。
ガラス物質の具体的としては、Ｐｂ−Ｓｉ、Ｐｂ−Ｇｅ、Ｂ−Ｓｉ、Ｂ−Ｓｉ−Ｐｂ、Ｂ−Ｂａ及びＢａ−Ｐｂ−Ｓｉから選ばれる少なくとも１種以上が好ましい。
ガラス物質は、その添加量が過度に少ない場合には、焼結が十分に促進されず、また、過度に多い場合には、異相を形成することにより室温比抵抗の増加が起こることがある。このためガラス物質の添加量は母体であるチタン酸バリウム全重量に対して０．５〜３．０ｗｔ％の範囲で添加するのが好ましい。なお、焼結性を損なわない範囲であれば前記ガラス物質中に少量の不融物が含まれていてもよい。
【０００６】
本発明のチタン酸バリウム鉛系半導体磁器組成物におけるガラス成分の添加効果は次の通りと考えられる。
ガラス物質として添加された、例えばホウケイ酸鉛ガラスは、チタン酸バリウム鉛系半導体磁器組成物がペロブスカイト結晶構造を形成する温度や半導体化温度を下げて、焼成時のＰｂの蒸発を抑制する効果がある。また、添加されたホウケイ酸鉛ガラスは、３４０℃付近から軟化して粘性流動機構により、粒子構造の均一化ならびに粒成長を促進し、従来より低温での緻密化を達成する。結果として、公知試料に比べ低比抵抗化となり、耐電圧も高く良好となるものと推定される。また、高濃度Ｎｂ2Ｏ5の添加量でも半導体化を示す。
【０００７】
本発明における半導体化剤としては、Ｎｂ2Ｏ5、Ｙ2Ｏ3、Ｓｂ2Ｏ5、Ｌａ2Ｏ3のような３価または５価金属酸化物の少なくとも１種が挙げられる。半導体化剤の添加量が過度に多い場合や過度に少ない場合には、ＰＴＣＲ特性を示さなくなることがあるので、半導体化剤は母体に対して０．１１〜０．２２モル％の範囲で添加するのが好ましい。
【０００８】
本発明の組成物により作製した半導体磁器は、室温比抵抗（Ｒ25）が５〜２９０００Ω・ｃｍの値を示し、抵抗のジャンプ幅が３〜５桁と良好なＰＴＣＲ特性を有し、特に低抵抗素子が得られる。また、耐電圧が高いことにより高信頼性を有し、小型化が可能となる。
【０００９】
本発明のチタン酸バリウム鉛系半導体磁器組成物において、Ｐｂの置換量を大きくするとともにＴｃが高くなり、また抵抗のジャンプ幅も大きくなり、特にＢａの６０〜９０モル％をＰｂで置換することにより、高温での使用において優れたＰＴＣＲ特性を有する半導体磁器組成物を提供できる。
【００１０】
【実施例】
以下、本発明について、実施例を示して具体的に説明する。
【００１１】
実施例１
出発原料として市販のＰｂＯ、ＢａＣＯ3、ＴｉＯ2、Ｎｂ2Ｏ5、ホウケイ酸鉛ガラス（品番ＫＦ−２７；岩城硝子（株）製：Ｐｂ：Ｓｉ：Ｂ＝８３：０．４：１２（ｗｔ％）；軟化点３４０℃）の粉末を用いて表１に示す組成になるように秤量後、ボールミル混合を１８時間行った。脱媒した後、８００〜９５０℃で２０〜６０分仮焼を行った。
仮焼粉は、ボールミルで１８時間粉砕混合を行った。脱媒した後、バインダー水溶液を添加し、蒸発乾固後、フルイにより造粒し、２００ｋｇ／ｃｍ2の圧力で７ｍｍφ×１．２ｍｍｔのペレットに成形した。それを大気中で１０００〜１２００℃の温度で１時間保持する条件で焼成した。焼結体の両面にオーミック性銀電極を塗布し、６２０℃、１０分の条件で電極焼き付けを行った。得られた試料を用いて抵抗−温度特性および耐電圧の測定を行った。電気特性、密度を表２に示す。半導体化剤としてＮｂ以外の３価、５価の元素においても同様の効果が得られた。なお、表１、表２において※印を付したものは本発明の範囲外のもので比較のために記載した。比較試料の作製は実施例に記載した方法と同様に行った。
試料番号１〜４はＰｂＯを６０モル％とした母体に対し、半導体化剤としてＮｂ2Ｏ5を０．１３モル％、ホウケイ酸鉛ガラスを全重量に対し０．５〜４．０ｗｔ％添加したものである。
【００１２】
試料番号５〜９はＰｂＯを６０モル％とした母体に対し、半導体化剤としてＮｂ2Ｏ5を０．１１〜０．２２モル％、ホウケイ酸鉛ガラスを全重量に対し、１．０ｗｔ％添加したものである。
試料番号１０〜１４はＰｂＯを０〜９０モル％とした母体に対し、半導体化剤としてＮｂ2Ｏ5を０．１３〜０．１６モル％、ホウケイ酸鉛ガラスを全重量に対し、１．０ｗｔ％添加したものである。
表１に原料仕込み組成を示す。表２に電気特性、密度を示す。
試料番号１５〜２０はホウケイ酸鉛ガラスに代えて他のガラス物質を使用した場合である。ガラス物質の種類と添加量のほかは試料２の場合と同様に行った。表３にガラス物質の種類、軟化点、添加量および比抵抗を示す。
【００１３】
表１〜表３から明らかなようにチタン酸バリウム鉛系の母体に対して半導体化剤を０．１１〜０．２２モル％、ガラス物質を全重量に対し０．５〜１．５ｗｔ％の範囲で加えられた試料は、Ｔｃが１２７〜４９０℃の範囲で室温比抵抗（Ｒ25）が８〜２９０００Ω・ｃｍの値を有するＰＴＣＲ特性が得られた。表２から室温比抵抗が小さく、且つ耐電圧が高いことがわかる。
【００１４】
図１および図２は、ホウケイ酸鉛ガラスを全重量に対し１．０ｗｔ％添加した試料（試料番号２）と従来公知の試料（チッ化ホウ素；ＢＮ）の焼結体の粒子構造を示すＳＥＭ写真図を示したものである。従来公知の試料はＮｂ2Ｏ5を０．１３モル％とし、ホウケイ酸鉛ガラスに代えてＢＮを０．０８５ｗｔ％としたほかは試料番号２と同様な方法により作製した。従来公知の試料では２μｍ〜２０μｍ程度の粒子が混在しているのに対して、ホウケイ酸鉛ガラスを添加したものは１０μｍ程度の均一な粒子を形成する。
【００１５】
図３は、ホウケイ酸鉛ガラスを添加した試料と従来公知の試料（ＢＮ添加；添加量０．０６７、０．０８５、０．１７、０．３４ｗｔ％）の室温比抵抗値と耐電圧との関係を示す。これより、ホウケイ酸鉛ガラスを添加することにより均一な粒子成長が生じ、従来公知の試料に比べ低抵抗で耐電圧の向上がみられることがわかる。
【００１６】
本発明にかかる母体に対してＰｂが０．１〜９０ｍｏｌ％の範囲において、ホウケイ酸鉛ガラスを添加した場合には、Ｐｂ置換量が低濃度領域から高濃度領域までの広い範囲で低比抵抗であり、特に６０〜９０モル％の領域において室温比抵抗が小さいことがわかる。したがって、低温用ＰＴＣＲ材料だけでなく、３９５〜４９０℃というような高いキュリー温度を有する高温度用のＰＴＣＲ材料を提供できる。
【００１７】
図４は、本発明にかかる母体に対してＰｂを０〜９０モル％添加した半導体磁器（試料番号２、１０〜１４）の比抵抗−温度特性を示したものである。
【００１８】
【発明の効果】
チタン酸バリウム鉛に軟化点が９５０℃以下のガラス物質を添加することにより、Ｔｃ＝１２０〜４９０℃の高い温度領域で小さな室温比抵抗を有する良好なＰＴＣＲ特性を有する半導体磁器を提供できる。また、軟化点が９５０℃以下のガラス物質を添加することによって均一な粒子径を有する磁器が得られ、耐電圧が高い半導体磁器を提供できる。さらに、室温で低比抵抗であり電流制限素子としても使用することできる。このチタン酸バリウム鉛系半導体磁器組成物は安価な原料で容易に製造できるため、特に高温用のＰＴＣＲ材料として工業的価値は極めて大きい。
【００１９】
【表１】
【表２】
【表３】
【図面の簡単な説明】
【図１】本発明品の試料の粒子構造を示す図面に代わる写真図である。
【図２】従来品の試料の粒子構造を示す図面に代わる写真図である。
【図３】ホウケイ酸鉛ガラスを添加した試料と従来公知の試料の室温比抵抗値と耐電圧との関係を示す図である。
【図４】本発明品の試料の比抵抗−温度特性を示したものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lead barium titanate semiconductor ceramic composition having an arbitrary Curie point at a temperature of 120 to 490 ° C. and having excellent PTCR characteristics even when used at a high temperature.
[0002]
[Prior art]
Conventionally, in a barium titanate-based semiconductor ceramic composition, it is known that a part of Ba is replaced with Pb in order to shift the Curie point to a high temperature side. However, when Pb substitution is performed, deterioration of characteristics due to volatilization of Pb during firing is a problem. In particular, when the Pb substitution amount exceeds 50 mol% and the Curie point is 300 ° C. or higher, the PTCR characteristics are significantly deteriorated due to a rapid increase in the room temperature resistance.
In order to solve this problem, for example, in Japanese Patent Laid-Open No. 4-21565, by adding 0.8 to 4.5 mol% of boron nitride (BN), the sinterability is improved and the semiconductor is made. It is disclosed to be promoted.
[0003]
[Problems to be solved by the invention]
However, since the disclosed porcelain composition grows with different particle diameters by firing, the withstand voltage is low due to the presence of large particles, and there is a problem in reliability when used as a PTCR thermistor.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, when a glass material having a low softening point is added, the glass can be fired at 1000 to 1200 ° C., which is lower than the conventional temperature. It has been found that low resistance elements can be obtained in a high concentration region where Pb volatilization is suppressed during firing, Pb substitution amount is wide, especially in the high concentration region of 60 to 90 mol% which could not be achieved conventionally. It has been found that a barium lead titanate semiconductor ceramic composition for a high temperature PTCR material having a temperature can be provided. The present invention has an arbitrary Curie point at a temperature of 120 to 490 ° C., and has a barium lead titanate semiconductor ceramic composition that has an excellent PTCR characteristic even when used at a high temperature and can be used as a current limiting element. The purpose is to provide goods. The present invention, (wherein, x is 0 ≦ x <1 and is.) (Ba 1-x Pb x) TiO 3 in the barium titanate lead-based semiconductor ceramic composition as a host, barium titanate-lead based semiconductor The porcelain composition is obtained by mixing the base material with a semiconducting agent and a glass material having a softening point of 950 ° C. or lower and firing the mixture, and the glass material is in a range of 0.5 to 3.0 wt% with respect to the base material. Further, the present invention relates to a lead barium titanate semiconductor ceramic composition , wherein the glass substance is lead borosilicate glass . Further, in a barium lead titanate-based semiconductor ceramic composition based on (Ba 1-x Pb x ) TiO 3 (where x is 0 ≦ x <1), a barium lead titanate-based semiconductor ceramic composition The product is obtained by mixing the base material with a semiconducting agent and a glass material having a softening point of 950 ° C. or lower and firing the glass material, and the glass material is in a range of 0.5 to 3.0 wt% with respect to the base material. The glass material is at least one selected from Pb—Si, Pb—Ge, B—Si, B—Si—Pb, B—Ba and Ba—Pb—Si The present invention relates to a semiconductor ceramic composition.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The glass material in the present invention is not particularly limited as long as it has a softening point of 950 ° C. or lower, but preferably contains at least one selected from Pb, B and Si. When the softening point of the glass material is excessively low, the obtained barium lead titanate semiconductor ceramic composition may not exhibit RTCR characteristics. Therefore, the softening point of the glass material is preferably 300 ° C. or higher. Moreover, if the softening point of the glass substance is excessively higher than 950 ° C., the firing temperature cannot be reduced to 1200 ° C. or lower.
Specifically, the glass material is preferably at least one selected from Pb—Si, Pb—Ge, B—Si, B—Si—Pb, B—Ba, and Ba—Pb—Si.
When the glass material is added in an excessively small amount, the sintering is not sufficiently promoted, and when it is excessively large, an increase in room temperature resistivity may occur by forming a heterogeneous phase. For this reason, it is preferable to add the glass substance in the range of 0.5 to 3.0 wt% with respect to the total weight of the base barium titanate. Note that a small amount of infusible material may be included in the glass material as long as the sinterability is not impaired.
[0006]
The effect of adding the glass component in the barium lead titanate semiconductor ceramic composition of the present invention is considered as follows.
For example, lead borosilicate glass added as a glass substance has the effect of reducing the temperature at which the barium lead titanate-based semiconductor ceramic composition forms a perovskite crystal structure and the semiconductor temperature, thereby suppressing the evaporation of Pb during firing. is there. Also, the added lead borosilicate glass softens from around 340 ° C. and promotes uniform grain structure and grain growth by a viscous flow mechanism, and achieves densification at a lower temperature than before. As a result, it is presumed that the specific resistance is lower than that of the known sample, and the withstand voltage is high and good. In addition, the addition of high-concentration Nb 2 O 5 shows semiconductorization.
[0007]
Examples of the semiconducting agent in the present invention include at least one trivalent or pentavalent metal oxide such as Nb 2 O 5 , Y 2 O 3 , Sb 2 O 5 , and La 2 O 3 . When the addition amount of the semiconducting agent is excessively large or too small, the PTCR characteristic may not be exhibited. Therefore, the semiconducting agent is added in the range of 0.11 to 0.22 mol% with respect to the base. It is preferable to do this.
[0008]
The semiconductor ceramic produced by the composition of the present invention has a room temperature specific resistance (R 25 ) of 5 to 29000 Ω · cm, a resistance jump width of 3 to 5 digits and good PTCR characteristics, and particularly low A resistance element is obtained. In addition, the high withstand voltage enables high reliability and downsizing.
[0009]
In the barium lead titanate semiconductor ceramic composition of the present invention, the substitution amount of Pb is increased, the Tc is increased, and the jump width of resistance is increased. In particular, 60 to 90 mol% of Ba is substituted with Pb. Thus, a semiconductor ceramic composition having excellent PTCR characteristics when used at high temperatures can be provided.
[0010]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
[0011]
Example 1
Commercially available PbO, BaCO 3 , TiO 2 , Nb 2 O 5 , lead borosilicate glass (Part No. KF-27; manufactured by Iwaki Glass Co., Ltd .: Pb: Si: B = 83: 0.4: 12 (wt) %); Powder having a softening point of 340 ° C.) was weighed so as to have the composition shown in Table 1, and then ball mill mixing was performed for 18 hours. After removing the solvent, calcination was performed at 800 to 950 ° C. for 20 to 60 minutes.
The calcined powder was pulverized and mixed in a ball mill for 18 hours. After removing the solvent, an aqueous binder solution was added, evaporated to dryness, granulated with a sieve, and formed into 7 mmφ × 1.2 mmt pellets at a pressure of 200 kg / cm 2 . It was calcined in the atmosphere at a temperature of 1000 to 1200 ° C. for 1 hour. An ohmic silver electrode was applied to both surfaces of the sintered body, and electrode baking was performed at 620 ° C. for 10 minutes. Using the obtained sample, resistance-temperature characteristics and withstand voltage were measured. Table 2 shows the electrical characteristics and density. Similar effects were obtained with trivalent and pentavalent elements other than Nb as the semiconducting agent. In Tables 1 and 2, those marked with * are outside the scope of the present invention and are shown for comparison. The comparative sample was produced in the same manner as described in the examples.
Sample Nos. 1 to 4 added 0.13 mol% of Nb 2 O 5 as a semiconducting agent and 0.5 to 4.0 wt% of lead borosilicate glass as a semiconducting agent with respect to the base having 60 mol% of PbO. It is a thing.
[0012]
Sample Nos. 5 to 9 are based on 0.1% to 0.22 mol% of Nb 2 O 5 as a semiconducting agent and 1.0 wt% of lead borosilicate glass with respect to the total weight with respect to the base having 60 mol% of PbO. It is what was added.
Sample Nos. 10 to 14 are based on 0.1 to 0.16 mol% of Nb 2 O 5 as a semiconducting agent and lead borosilicate glass with respect to the total weight with respect to the base having 0 to 90 mol% of PbO. 0 wt% added.
Table 1 shows the raw material charging composition. Table 2 shows electrical characteristics and density.
Sample numbers 15 to 20 are cases in which other glass substances are used instead of lead borosilicate glass. The procedure was the same as in the case of Sample 2 except for the type of glass material and the amount added. Table 3 shows the types of glass substances, softening points, addition amounts, and specific resistances.
[0013]
As is apparent from Tables 1 to 3, 0.11 to 0.22 mol% of the semiconducting agent and 0.5 to 1.5 wt% of the glass material based on the total weight with respect to the lead barium titanate base. range added samples, Tc the room temperature resistivity (R 25) in the range of one hundred twenty-seven to four hundred and ninety ° C. was obtained PTCR characteristic having a value of 8~29000Ω · cm. Table 2 shows that the room temperature specific resistance is small and the withstand voltage is high.
[0014]
1 and 2 are SEMs showing the particle structures of a sintered body of a sample (sample number 2) to which 1.0 wt% of lead borosilicate glass is added based on the total weight and a conventionally known sample (boron nitride; BN). A photograph is shown. A conventionally known sample was prepared by the same method as Sample No. 2 except that Nb 2 O 5 was 0.13 mol% and BN was 0.085 wt% instead of lead borosilicate glass. In the conventionally known sample, particles having a size of about 2 μm to 20 μm are mixed, whereas those added with lead borosilicate glass form uniform particles of about 10 μm.
[0015]
FIG. 3 shows the room temperature specific resistance value and withstand voltage of a sample to which lead borosilicate glass is added and a conventionally known sample (BN addition; addition amount 0.067, 0.085, 0.17, 0.34 wt%). Show the relationship. From this, it can be seen that by adding lead borosilicate glass, uniform particle growth occurs, and the withstand voltage is improved with lower resistance than that of a conventionally known sample.
[0016]
When lead borosilicate glass is added in the range of 0.1 to 90 mol% of Pb with respect to the matrix according to the present invention, the Pb substitution amount is low in a wide range from a low concentration region to a high concentration region. It can be seen that the room temperature resistivity is particularly small in the region of 60 to 90 mol%. Therefore, not only a low-temperature PTCR material but also a high-temperature PTCR material having a high Curie temperature of 395 to 490 ° C. can be provided.
[0017]
FIG. 4 shows specific resistance-temperature characteristics of a semiconductor ceramic (
[0018]
【The invention's effect】
By adding a glass material having a softening point of 950 ° C. or lower to lead barium titanate, a semiconductor ceramic having good PTCR characteristics having a small room temperature resistivity in a high temperature range of Tc = 120 to 490 ° C. can be provided. Further, by adding a glass material having a softening point of 950 ° C. or lower, a ceramic having a uniform particle diameter can be obtained, and a semiconductor ceramic having a high withstand voltage can be provided. Furthermore, it has a low specific resistance at room temperature and can be used as a current limiting element. Since this barium lead titanate-based semiconductor ceramic composition can be easily manufactured with an inexpensive raw material, the industrial value is particularly great as a PTCR material for high temperatures.
[0019]
[Table 1]
[Table 2]
[Table 3]
[Brief description of the drawings]
FIG. 1 is a photograph instead of a drawing showing the particle structure of a sample of the present invention.
FIG. 2 is a photograph instead of a drawing showing the particle structure of a conventional sample.
FIG. 3 is a diagram showing a relationship between a room temperature specific resistance value and a withstand voltage of a sample added with lead borosilicate glass and a conventionally known sample.
FIG. 4 shows specific resistance-temperature characteristics of a sample of the present invention.
Claims (3)
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