JPH08213205A - Barium titanate semiconductor ceramics and manufacture thereof - Google Patents
Barium titanate semiconductor ceramics and manufacture thereofInfo
- Publication number
- JPH08213205A JPH08213205A JP6036509A JP3650994A JPH08213205A JP H08213205 A JPH08213205 A JP H08213205A JP 6036509 A JP6036509 A JP 6036509A JP 3650994 A JP3650994 A JP 3650994A JP H08213205 A JPH08213205 A JP H08213205A
- Authority
- JP
- Japan
- Prior art keywords
- atomic ratio
- barium titanate
- withstand voltage
- antimony
- 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.)
- Pending
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、チタン酸バリウム系半
導体磁器、および該磁器の製造方法に関する。上記チタ
ン酸バリウム系半導体磁器は、常温では比抵抗が小さ
く、ある温度（以降”Ｔｃ”と記す）を越えると急激に
抵抗が上昇するという、正の抵抗温度特性（以降”ＰＴ
Ｃ特性”と記す）を有しており、温度制御、電流制限、
定温度発熱などの用途に素子として広く使用されてい
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barium titanate-based semiconductor porcelain and a method for manufacturing the porcelain. The barium titanate-based semiconductor porcelain has a small specific resistance at room temperature, and the resistance increases rapidly when the temperature exceeds a certain temperature (hereinafter referred to as “Tc”).
C characteristic ”), temperature control, current limiting,
Widely used as an element for applications such as constant temperature heat generation.
【０００２】[0002]
【従来の技術】上記用途において、高い電圧でも使用可
能な耐電圧の高い素子、すなわち耐電圧強度の高いＰＴ
Ｃ特性を有する半導体磁器が要望されている。一方、電
気製品の小型軽量化に伴い、小型で低抵抗の素子、すな
わち室温における比抵抗の低いＰＴＣ特性を有する半導
体磁器も要望されている。したがって、ＰＴＣ特性を有
する半導体磁器の特性として、耐電圧強度をより高くす
ること、および室温における比抵抗（以下、特に明記し
ない限り、室温における比抵抗のことを”比抵抗”と略
す）をより低くすることが重要な課題とされている。2. Description of the Related Art In the above application, an element having a high withstand voltage that can be used even at a high voltage, that is, a PT having a high withstand voltage
There is a demand for semiconductor porcelain having C characteristics. On the other hand, with the reduction in size and weight of electrical products, there is also a demand for small-sized and low-resistance elements, that is, semiconductor porcelain having a PTC characteristic with low specific resistance at room temperature. Therefore, as the characteristics of the semiconductor porcelain having PTC characteristics, higher withstand voltage strength and specific resistance at room temperature (hereinafter, the specific resistance at room temperature is abbreviated as "specific resistance" unless otherwise specified) are more preferable. Making it low is an important issue.
【０００３】ＰＴＣ特性を有するチタン酸バリウム系の
半導体磁器は、一般的に、主成分となるバリウムの炭酸
塩またはシュウ酸塩と、チタンの酸化物またはシュウ酸
塩とを、Ｔｃのシフトの目的やグレイン制御の目的で、
必要に応じてストロンチウムや鉛、またはカルシウムの
炭酸塩またはシュウ酸塩を添加したり、半導化剤となる
微量のＹ，Ｃｅなどの希土類元素やＮｂ，Ｔａ，Ｓｂの
酸化物、および、ＰＴＣ特性の抵抗変化桁数を大きくす
る特性改善剤となるＭｎ，Ｆｅ，Ｃｒ，Ｃｕなどの酸化
物、液相焼結助剤となるＳｉ，Ａｌなどの酸化物を種々
添加混合し、仮焼、粉砕、成形、焼成して得られる。A barium titanate-based semiconductor porcelain having a PTC characteristic generally has a main component of barium carbonate or oxalate and a titanium oxide or oxalate for the purpose of shifting Tc. And for the purpose of grain control,
If necessary, strontium, lead, or calcium carbonate or oxalate is added, or trace amounts of rare earth elements such as Y and Ce, which are semiconducting agents, and oxides of Nb, Ta, and Sb, and PTC. Oxides such as Mn, Fe, Cr and Cu, which are characteristic improving agents that increase the number of digits of resistance change of characteristics, and various oxides such as Si and Al, which are liquid phase sintering aids, are added and mixed, and calcined, It is obtained by crushing, molding and firing.
【０００４】しかしながら、上記従来方法で得られるＰ
ＴＣ特性を有するチタン酸バリウム系半導体磁器は、通
常、１３００℃以上の焼成を必要とし、このためグレイ
ン分布が広くなってしまい、しかも、５μｍ以上の径を
有する大きなグレインが生成してしまう。However, P obtained by the above conventional method
Barium titanate-based semiconductor porcelain having TC characteristics usually needs to be fired at 1300 ° C. or higher, which widens the grain distribution and produces large grains having a diameter of 5 μm or more.
【０００５】その結果、耐電圧強度の高いＰＴＣ特性を
有するチタン酸バリウム系の半導体磁器を得ることは困
難であった。しかも、ＰＴＣ特性を有するチタン酸バリ
ウム系半導体磁器を製造する上で、耐電圧強度の高い磁
器を得ようとすると、比抵抗も高くなる傾向にあるた
め、耐電圧強度が高いにもかかわらず比抵抗の低い磁器
を得ることは、非常に困難であった。As a result, it has been difficult to obtain a barium titanate-based semiconductor porcelain having PTC characteristics with high withstand voltage strength. Moreover, in manufacturing barium titanate-based semiconductor porcelain having PTC characteristics, if a porcelain having a high withstand voltage strength is to be obtained, the specific resistance tends to be high. It was very difficult to obtain a porcelain with low resistance.
【０００６】耐電圧強度／（室温）比抵抗で表した場
合、その値は耐電圧強度が高ければ高いほど下がる傾向
にあり、耐電圧強度が１００〜２００Ｖ／ｍｍ程度のと
きは耐電圧強度／比抵抗が１０以上のものも得られる場
合があるが、耐電圧強度が２００Ｖ／ｍｍを越える場合
は１０以上のものを得ることは非常に困難であった。特
に、耐電圧強度が５００Ｖ／ｍｍ以上の磁器を得ようと
する場合は比抵抗が非常に高くなってしまい、耐電圧強
度／比抵抗が５以上のものを得ることは不可能であっ
た。When expressed in terms of withstand voltage strength / (room temperature) specific resistance, the value tends to decrease as the withstand voltage strength increases, and when the withstand voltage strength is about 100 to 200 V / mm, the withstand voltage strength / A specific resistance of 10 or more may be obtained, but when the withstand voltage strength exceeds 200 V / mm, it was very difficult to obtain a specific resistance of 10 or more. In particular, when trying to obtain a porcelain having a withstand voltage strength of 500 V / mm or more, the specific resistance became very high, and it was impossible to obtain a withstand voltage strength / specific resistance of 5 or more.
【０００７】たとえば、特開平４−２６１０１号公報で
は、ＴｉＯ2 ，ＳｉＯ2 ，Ａｌ2 Ｏ3 およびＭｎＯ2 を
含有させたＢａＴｉＯ3 とＳｒＴｉＯ3 とからなる半導
体磁器において、ＤｙおよびＳｂを配合させることによ
り、耐電圧強度が高く、かつ比抵抗の低い磁器を得よう
としているが、その比抵抗は５０Ωｃｍ前後、耐電圧強
度は２００Ｖ／ｍｍ前後であり、耐電圧強度としてはま
だ満足できるものではなく、平均グレイン径も６〜１５
μｍと大きい。For example, in Japanese Unexamined Patent Publication No. 26101/1992, Dy and Sb are mixed in a semiconductor ceramic made of BaTiO 3 and SrTiO 3 containing TiO 2 , SiO 2 , Al 2 O 3 and MnO 2. Therefore, it is attempted to obtain a porcelain having a high withstand voltage strength and a low specific resistance, but the specific resistance is around 50 Ωcm and the withstand voltage strength is around 200 V / mm, which is not yet satisfactory as the withstand voltage strength. , The average grain size is also 6 to 15
It is as large as μm.
【０００８】また、特公昭６０−２５００４号公報で
は、出発原料として、バリウムとチタンの複合シュウ酸
塩と半導化剤となるＳｂの酸化物とを粉砕混合して仮焼
した粉体を用い、その仮焼条件や成形圧などを制御し、
１３５０℃で焼成することにより、相対密度が６０〜９
５％で、平均グレイン径が１〜５μｍの、比較的高耐電
圧強度の磁器を得ており、最高で５００Ｖ／ｍｍ付近の
ものもある。Further, in Japanese Patent Publication No. 60-25005, as a starting material, a powder obtained by pulverizing and mixing a complex oxalate of barium and titanium and an oxide of Sb as a semiconducting agent and calcining is used. , Control the calcination conditions and molding pressure,
By firing at 1350 ° C., the relative density is 60-9.
A porcelain having a relatively high withstand voltage strength with an average grain diameter of 5% and an average grain diameter of 1 to 5 μm has been obtained.
【０００９】しかしながら、最高の耐電圧強度を有して
いる磁器の相対密度が７８％と低いので、磁器の強度と
いう面で問題である。また、比抵抗が１００Ωｃｍ以上
で全体的に高く、さらに、用いる原料の半導化剤が不均
一なためか、１３５０℃という高温での焼成が必要とさ
れており、グレイン分布が１〜１０μｍと広い。その結
果、耐電圧強度／比抵抗の比の値が５未満と、あまり良
特性のものは得られていなかった。However, since the relative density of the porcelain having the highest withstand voltage strength is as low as 78%, there is a problem in the strength of the porcelain. In addition, the specific resistance is 100 Ωcm or more, which is high overall, and because the raw material to be used is not uniform in the semiconducting agent, firing at a high temperature of 1350 ° C. is required, and the grain distribution is 1 to 10 μm. wide. As a result, a value of ratio of withstand voltage strength / specific resistance of less than 5 was not obtained, which had very good characteristics.
【００１０】[0010]
【発明が解決しようとする課題】以上のように、高耐圧
強度を有し、かつ比抵抗の低いＰＴＣ特性を有するチタ
ン酸バリウム系の半導体磁器は得られていない。したが
って、本発明の目的は、高耐電圧強度を有し、かつ比抵
抗の低いＰＴＣ特性を有するチタン酸バリウム系の半導
体磁器とその製造方法を提供することにある。As described above, a barium titanate-based semiconductor porcelain having a high withstand voltage strength and a PTC characteristic with a low specific resistance has not been obtained. Therefore, an object of the present invention is to provide a barium titanate-based semiconductor porcelain having high withstand voltage strength and PTC characteristics with low specific resistance, and a method for manufacturing the same.
【００１１】より具体的には、耐電圧強度が５００Ｖ／
ｍｍ以上で、かつ耐電圧強度／比抵抗が５以上の、従来
にない優れたＰＴＣ特性を有するチタン酸バリウム系の
半導体磁器、さらには、耐電圧強度が５００Ｖ／ｍｍ以
上で、かつ耐電圧強度／比抵抗が１０以上の、従来にな
い優れたＰＴＣ特性を有するチタン酸バリウム系の半導
体磁器、と該磁器の製造方法とを提供することにある。More specifically, the withstand voltage strength is 500 V /
mm or more, and withstand voltage strength / specific resistance of 5 or more, barium titanate-based semiconductor porcelain having excellent PTC characteristics that have never been seen, and further, withstand voltage strength of 500 V / mm or more and withstand voltage strength The object of the present invention is to provide a barium titanate-based semiconductor porcelain having a specific resistance of 10 or more and an unprecedentedly excellent PTC characteristic, and a method for producing the porcelain.
【００１２】[0012]
【課題を解決するための手段】本発明者らは、上記目的
を達成するために鋭意研究を重ねたところ、半導化剤元
素としてアンチモンを選定し、Ｓｂが均一に存在するよ
うに主成分であるチタン酸バリウムを湿式反応により合
成する過程中でアンチモン化合物を添加して生成させ
た、平均粒子径が０．３μｍ以下のチタン酸バリウム粉
体を原料として用い、さらにＢａ／Ｔｉ原子比とＳｂ／
Ｔｉ原子比とを厳密に限定した時に、本発明の目的とす
る特性を有する、グレイン径が小さく、しかもグレイン
分布がそろったチタン酸バリウム系半導体磁器が、１２
５０℃以下という従来より低い焼成温度で得られること
を見いだし、本発明に到達した。[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object. As a result, antimony is selected as a semiconducting agent element so that Sb is uniformly present in the main component. Barium titanate powder having an average particle size of 0.3 μm or less, which was produced by adding an antimony compound in the process of synthesizing barium titanate by a wet reaction, was used as a raw material, and the Ba / Ti atomic ratio was Sb /
When the Ti atomic ratio is strictly limited, a barium titanate-based semiconductor porcelain having a small grain size and a uniform grain distribution, which has the characteristics of the present invention, is obtained.
The present invention has been accomplished by discovering that it can be obtained at a firing temperature of 50 ° C. or lower, which is lower than the conventional one.
【００１３】すなわち本発明は、半導化剤としてアンチ
モンを含有し、ペロブスカイト型結晶構造を有するチタ
ン酸バリウム系半導体磁器において、Ｂａ／Ｔｉ原子比
とＳｂ／Ｔｉ原子比とが図１のＡＢＣＤで囲まれた範囲
内にあり、かつ、その平均グレイン径が１〜２μｍであ
り、かつ、最大グレイン径が５μｍ以下であることを特
徴とする、耐電圧強度が５００Ｖ／ｍｍ以上で、かつ耐
電圧強度／比抵抗が５以上の特性を有するチタン酸バリ
ウム系半導体磁器である。That is, according to the present invention, in a barium titanate-based semiconductor ceramic containing antimony as a semiconducting agent and having a perovskite type crystal structure, the Ba / Ti atomic ratio and the Sb / Ti atomic ratio are ABCD in FIG. Within the enclosed range, the average grain diameter is 1 to 2 μm, and the maximum grain diameter is 5 μm or less, the withstand voltage strength is 500 V / mm or more, and the withstand voltage is A barium titanate-based semiconductor ceramic having a strength / specific resistance of 5 or more.
【００１４】本発明はまた、半導化剤としてアンチモン
を含有し、ペロブスカイト型結晶構造を有するチタン酸
バリウム系半導体磁器において、Ｂａ／Ｔｉ原子比とＳ
ｂ／Ｔｉ原子比とが図１のａｂｃｄで囲まれた範囲にあ
り、かつ、その平均グレイン径が１〜２μｍであり、か
つ、最大グレイン径が５μｍ以下であることを特徴とす
る、耐電圧強度が５００Ｖ／ｍｍ以上で、かつ、耐電圧
強度／比抵抗が１０以上の特性を有するチタン酸バリウ
ム系半導体磁器である。The present invention also provides a barium titanate-based semiconductor ceramic containing antimony as a semiconducting agent and having a perovskite type crystal structure, in which the Ba / Ti atomic ratio and the S content are S.
b / Ti atomic ratio is in the range surrounded by abcd in FIG. 1, the average grain diameter is 1 to 2 μm, and the maximum grain diameter is 5 μm or less. A barium titanate-based semiconductor porcelain having a strength of 500 V / mm or more and a withstand voltage strength / specific resistance of 10 or more.
【００１５】さらに本発明は、アンチモンをＳｂ／Ｔｉ
原子比としてＳｂ／Ｔｉ＝０．０５〜０．４５％含有す
るチタン化合物の溶液またはスラリーと、バリウム化合
物とを湿式反応させ、必要に応じて仮焼することによ
り、平均粒子径が０．３μｍ以下で、かつ、Ｓｂ／Ｔｉ
原子比およびＢａ／Ｔｉ原子比が、図１のＡＢＣＤ好ま
しくはａｂｃｄで囲まれた範囲にある、アンチモンを均
一に含有したペロブスカイト結晶構造を有したチタン酸
バリウム粉体を得、該粉体を成形した後、成形体を１１
５０〜１２５０℃で焼成することを特徴とする半導体磁
器の製造方法に関する。Further, in the present invention, antimony is added to Sb / Ti.
A titanium compound solution or slurry containing Sb / Ti = 0.05 to 0.45% as an atomic ratio is wet-reacted with a barium compound, and calcined if necessary, so that the average particle diameter is 0.3 μm. Below, and Sb / Ti
A barium titanate powder having a perovskite crystal structure uniformly containing antimony having an atomic ratio and a Ba / Ti atomic ratio in a range surrounded by ABCD, preferably abcd in FIG. 1 is obtained, and the powder is molded. Then, the molded body is
The present invention relates to a method for manufacturing a semiconductor porcelain, which comprises firing at 50 to 1250 ° C.
【００１６】本発明において、各条件を限定した理由に
ついては、以下の通りである。Ｓｂ／Ｔｉ原子比とＢａ
／Ｔｉ原子比とを図１のＡＢＣＤで囲まれた範囲内に限
定すると、耐電圧強度が５００Ｖ／ｍｍ以上で、しかも
耐電圧強度／比抵抗が５以上の特性を有する磁器が得ら
れる。The reason why each condition is limited in the present invention is as follows. Sb / Ti atomic ratio and Ba
When the / Ti atomic ratio is limited to the range surrounded by ABCD in FIG. 1, a porcelain having characteristics of withstand voltage strength of 500 V / mm or more and withstand voltage strength / specific resistance of 5 or more can be obtained.
【００１７】たとえアンチモンを均一に添加し、Ｂａ／
Ｔｉ原子比を制御しても、Ｓｂ／Ｔｉ原子比が０．０５
％未満の場合には、１２５０℃以下の焼成ではグレイン
径が２μｍ以下と小さい磁器は得られるものの、半導化
が不十分となり、比抵抗が高くなる。また、１２５０℃
を越える温度で焼成すると、グレイン径が大きくなり、
結果として高耐電圧強度のものが得られない。すなわ
ち、耐電圧強度が５００Ｖ／ｍｍ以下となってしまう。Even if antimony is added uniformly, Ba /
Even if the Ti atomic ratio is controlled, the Sb / Ti atomic ratio is 0.05.
If it is less than 1%, calcination at 1250 ° C. or less can obtain a porcelain having a small grain diameter of 2 μm or less, but the semiconductivity becomes insufficient and the specific resistance becomes high. Also, 1250 ℃
When fired at a temperature above, the grain size increases,
As a result, high withstand voltage strength cannot be obtained. That is, the withstand voltage strength becomes 500 V / mm or less.
【００１８】また、上記Ｂａ／Ｔｉ原子比の条件で、Ｓ
ｂ／Ｔｉ原子比が０．４５％を越える場合も同様で、１
２５０℃以下の焼成では、結果的に耐電圧強度／比抵抗
の比が５未満と小さくなり、１２５０℃を越える温度で
焼成すると、グレイン径が大きくなって、５００Ｖ／ｍ
ｍ以上の高耐電圧強度のものが得られなくなってしま
う。Further, under the above Ba / Ti atomic ratio, S
The same applies when the b / Ti atomic ratio exceeds 0.45%.
Firing at a temperature of 250 ° C. or lower results in a small withstand voltage strength / specific resistance ratio of less than 5, and when firing at a temperature of higher than 1250 ° C., the grain size increases and the grain size increases to 500 V / m.
A high withstand voltage strength of m or more cannot be obtained.
【００１９】Ｂａ／Ｔｉ原子比が、図１中のＢＣ間の直
線境界以上にＴｉの比率が多いと、上記Ｓｂ／Ｔｉ原子
比が０．４５％を越えた場合と同様な問題が生じる。ま
た、Ｂａ／Ｔｉ原子比が、図１中のＡＤ間の直線境界以
上にＢａの比率が多い場合においても、１２５０℃以下
の焼成で、グレイン径が小さくて５００ｖ／ｍｍ以上の
耐圧強度を有するものも得られるが、半導化が不十分で
あり、比抵抗が高くなって、耐圧強度／比抵抗が５未満
となってしまう。When the Ba / Ti atomic ratio is larger than the straight line boundary between BCs in FIG. 1 and the Ti ratio is large, the same problem as when the Sb / Ti atomic ratio exceeds 0.45% occurs. Further, even when the Ba / Ti atomic ratio is higher than the linear boundary between AD in FIG. 1 and the ratio of Ba is large, the grain size is small and the compressive strength is 500 v / mm or more by firing at 1250 ° C. or less. However, the semiconductivity is insufficient, the specific resistance becomes high, and the withstand voltage strength / specific resistance becomes less than 5.
【００２０】Ｓｂ／Ｔｉ原子比とＢａ／Ｔｉ原子比とを
図１のａｂｃｄで囲まれた範囲内にさらに限定したの
は、図１のＡＢＣＤで囲まれた範囲内に限定した場合よ
りも、より優れた特性を有する磁器が得られるためであ
る。すなわち、耐電圧強度が５００Ｖ／ｍｍ以上であ
り、かつ、耐電圧強度／比抵抗が１０以上である特性を
満足する磁器が得られる。The Sb / Ti atomic ratio and the Ba / Ti atomic ratio are further limited within the range surrounded by abcd in FIG. 1 rather than within the range surrounded by ABCD in FIG. This is because a porcelain having more excellent characteristics can be obtained. That is, it is possible to obtain a porcelain satisfying the characteristics that the withstand voltage strength is 500 V / mm or more and the withstand voltage strength / specific resistance is 10 or more.
【００２１】次に、本発明の半導体磁器、特に、本発明
の優れた半導体磁器を得るために必要であるアンチモン
含有チタン酸バリウム粉体の製造方法、について詳細に
説明する。Next, the semiconductor porcelain of the present invention, in particular, the method for producing the antimony-containing barium titanate powder necessary for obtaining the excellent semiconductor porcelain of the present invention will be described in detail.
【００２２】本発明の製造方法において、アンチモンを
含有するチタン化合物の溶液とは、イオンまたは分子単
位で混合された溶液を意味し、たとえば、チタンの塩化
物とアンチモンの水溶性化合物との水溶液や、チタンの
アルコキシドとアンチモンのアルコキシドとの有機溶媒
混合溶液などが適用できる。具体的には、四塩化チタン
もしくは一部水酸基で置換された塩化チタン溶液と塩化
アンチモンとの塩酸水溶液、チタニウムイソプロポキシ
ドとアンチモンイソプロポキシドとのイソプロピルアル
コール溶液などである。In the production method of the present invention, the solution of a titanium compound containing antimony means a solution mixed in units of ions or molecules, for example, an aqueous solution of a chloride of titanium and a water-soluble compound of antimony. An organic solvent mixed solution of titanium alkoxide and antimony alkoxide can be applied. Specifically, it is a hydrochloric acid aqueous solution of titanium tetrachloride or a titanium chloride solution partially substituted with a hydroxyl group and antimony chloride, an isopropyl alcohol solution of titanium isopropoxide and antimony isopropoxide, and the like.
【００２３】また、アンチモンを含有するチタン化合物
のスラリーとは、たとえば、上記アンチモンを含有する
チタン化合物の溶液を加水分解して得られる水酸化物ま
たは酸化物のスラリーを意味する。具体的には、四塩化
チタンもしくは一部水酸基で置換された塩化チタン溶液
と塩化アンチモンとの塩酸水溶液を、アンモニアなどで
中和加水分解して得られるアンチモン含有含水水酸化チ
タンスラリー、チタニウムイソプロポキシドとアンチモ
ンイソプロポキシドとのイソプロピルアルコール溶液に
水を加えて加水分解して得られるスラリーなどである。The antimony-containing titanium compound slurry means, for example, a hydroxide or oxide slurry obtained by hydrolyzing a solution of the antimony-containing titanium compound. Specifically, an antimony-containing hydrous titanium hydroxide slurry obtained by neutralizing and hydrolyzing a hydrochloric acid solution of titanium tetrachloride or a titanium chloride solution partially substituted with a hydroxyl group and antimony chloride with ammonia or the like, titanium isopropoxy Slurry and the like obtained by adding water to an isopropyl alcohol solution of sodium hydroxide and antimony isopropoxide to cause hydrolysis.
【００２４】本発明におけるバリウム化合物とは、バリ
ウムの水酸化物、酸化物、無機塩、アルコキシドなどの
有機バリウム化合物、などを意味する。The barium compound in the present invention means a barium hydroxide, an oxide, an inorganic salt, an organic barium compound such as an alkoxide, and the like.
【００２５】上記アンチモンを含有するチタン化合物の
溶液またはスラリーと、上記バリウム化合物とを湿式反
応させる場合、たとえば、水熱反応法、アルコキシド
法、共沈仮焼法などが適用可能である。When the solution or slurry of the titanium compound containing antimony and the barium compound are subjected to a wet reaction, for example, a hydrothermal reaction method, an alkoxide method, a coprecipitation calcination method or the like can be applied.
【００２６】水熱反応法とは、上述したチタンとアンチ
モンとバリウムの各化合物の混合物を熱加水分解反応し
て、アンチモン含有チタン酸バリウムを得る方法であ
る。この際、チタン塩化物とアンチモンの水溶性化合物
との水溶液に、あらかじめ塩化バリウムなどの水溶性バ
リウム化合物を溶解させた溶液を、水酸化ナトリウムな
どの強アルカリ中で熱加水分解反応しても構わない。The hydrothermal reaction method is a method for obtaining a barium titanate containing antimony by subjecting a mixture of the above-mentioned compounds of titanium, antimony and barium to a thermal hydrolysis reaction. At this time, a solution prepared by previously dissolving a water-soluble barium compound such as barium chloride in an aqueous solution of titanium chloride and a water-soluble compound of antimony may be subjected to thermal hydrolysis reaction in a strong alkali such as sodium hydroxide. Absent.
【００２７】アルコキシド法とは、チタン、アンチモ
ン、バリウムの各アルコキシドを混合溶解した有機溶媒
溶液に加水して、熱を加え反応させる方法である。The alkoxide method is a method in which an alkoxide of titanium, antimony, or barium is mixed and dissolved in an organic solvent solution and heated to react.
【００２８】共沈仮焼法とは、たとえば、チタンの塩化
物やアンチモンの水溶性化合物の水溶液に、あらかじめ
塩化バリウムなど水溶性バリウム化合物を溶解した溶液
を、シュウ酸によって共沈させ、得られる複合シュウ酸
塩を仮焼してアンチモン含有チタン酸バリウムを得る方
法である。The coprecipitation calcination method is obtained, for example, by coprecipitating a solution of a water-soluble barium compound such as barium chloride in an aqueous solution of a water-soluble compound of titanium chloride or antimony with oxalic acid. This is a method of obtaining an antimony-containing barium titanate by calcining a composite oxalate.
【００２９】本発明の製造方法において、上記湿式反応
で得た粉体をさらに均一にする目的で、粒子成長のため
に平均粒子径が０．３μｍを越えてしまわない程度の温
度範囲で、仮焼してもよい。具体的には、仮焼温度範囲
としては７００〜９５０℃が好ましい。In the production method of the present invention, in order to make the powder obtained by the above-mentioned wet reaction more uniform, the temperature is temporarily set within a temperature range in which the average particle size does not exceed 0.3 μm due to particle growth. You may bake. Specifically, the calcining temperature range is preferably 700 to 950 ° C.
【００３０】また、通常Ｔｃシフトの目的で添加される
Ｐｂ，Ｓｒ，Ｃａ，Ｚｒ，Ｓｎなどの元素（シフター剤
と呼ばれる）や、Ｍｎ，Ｃｕ，Ｂ，Ｓｉ，Ｌｉ，Ｎａ，
Ｋ，Ｚｎ，Ｎｉ，Ａｌ，Ｍｇなどの特性改質助剤となる
元素を添加することも、本発明の特性を損なわない範囲
で可能である。Further, elements such as Pb, Sr, Ca, Zr, and Sn (called shifter agents), which are usually added for the purpose of Tc shift, and Mn, Cu, B, Si, Li, Na,
It is also possible to add an element such as K, Zn, Ni, Al, or Mg that serves as a property modifying aid within a range that does not impair the properties of the present invention.
【００３１】以上説明したように、湿式反応工程を用
い、さらにＳｂ／Ｔｉ原子比とＢａ／Ｔｉ原子比とを図
１のＡＢＣＤ好ましくはａｂｃｄで示した範囲内に制御
して得られた、アンチモンを均一に含有するペロブスカ
イト結晶構造を有した平均粒子径０．３μｍ以下のチタ
ン酸バリウム粉体を用いると、１２５０℃以下という従
来にない低温焼成で半導化し、しかも平均グレイン径が
１〜２μｍでかつ最大グレイン径が５μｍ以下という、
グレインが小さくてしかも良くそろった、本発明の特性
を有する磁器が得られる。As described above, antimony obtained by using the wet reaction step and further controlling the Sb / Ti atomic ratio and the Ba / Ti atomic ratio within the range indicated by ABCD, preferably abcd in FIG. When barium titanate powder having a perovskite crystal structure and having an average particle diameter of 0.3 μm or less is uniformly contained, semiconducting is achieved by unprecedented low temperature firing of 1250 ° C. or less, and the average grain diameter is 1 to 2 μm. And the maximum grain diameter is 5 μm or less,
It is possible to obtain a porcelain having the characteristics of the present invention, which has a small grain size and is well aligned.
【００３２】[0032]
【作用】本発明に係る半導体磁器がなぜ、耐電圧強度が
５００ｖ／ｍｍ以上と高いにもかかわらず、比抵抗が低
く、しかも耐電圧強度／比抵抗が５以上さらには１０以
上と、従来にない非常に優れた特性を有しているか明確
でないが、半導化剤であるアンチモンをも湿式合成用試
剤として用いて湿式反応中に添加し、しかも、Ｓｂ／Ｔ
ｉ原子比とＢａ／Ｔｉ原子比とを厳密に制御することに
より、粉体中に均一にアンチモンを分布させた平均粒子
径が０．３μｍ以下のペロブスカイト型結晶構造を有す
るチタン酸バリウムを得ることができたので、上記粉体
を原料として用いることで、１１５０〜１２５０℃とい
う従来にない低温焼成でも、ＳｂがＡＢＯ3 ペロブスカ
イト型結晶構造ＢａＴｉＯ3 （Ａ；Ｂａ、Ｂ；Ｔｉ）中
のＢサイトに均一に置換固溶して半導化し、しかも、平
均径が１〜２μｍと小さくかつ非常に分布の狭いグレイ
ンを形成させることができたためである、と推測され
る。The semiconductor porcelain according to the present invention has a low specific resistance even though the withstand voltage strength is as high as 500 v / mm or more, and the withstand voltage strength / specific resistance is 5 or more or even 10 or more. Although it is not clear that it has very excellent characteristics, antimony, which is a semiconducting agent, is also used as a reagent for wet synthesis during the wet reaction, and Sb / T
Strictly controlling the i atomic ratio and the Ba / Ti atomic ratio to obtain barium titanate having a perovskite crystal structure with an average particle size of 0.3 μm or less in which antimony is uniformly distributed in the powder. Therefore, by using the above-mentioned powder as a raw material, Sb has a B site in the ABO 3 perovskite type crystal structure BaTiO 3 (A; Ba, B; Ti) even at a low temperature of 1150 to 1250 ° C. It is presumed that this is because it was possible to uniformly form a solid solution by substitution so as to be semiconducting and to form grains having a small average diameter of 1 to 2 μm and a very narrow distribution.
【００３３】[0033]
実施例１−１７ 住友シチックス社製の塩化チタン水溶液（Ｔｉとして１
６．５重量％含有）に、あらかじめ塩酸により溶解させ
た五塩化アンチモン溶液を、Ｓｂ／Ｔｉ原子比が表１の
含有量になるようにそれぞれ添加し、攪拌溶解した。攪
拌中、さらに純水を加え、１０倍に希釈した後、５％ア
ンモニア水をｐＨ８となるまで３時間かけて添加混合
し、中和加水分解反応を行った。Example 1-17 Titanium chloride aqueous solution (1 as Ti) manufactured by Sumitomo Sitix
6.5 wt% content), antimony pentachloride solution dissolved in hydrochloric acid in advance was added so that the Sb / Ti atomic ratio was the content shown in Table 1, and dissolved by stirring. While stirring, pure water was further added and diluted 10 times, and then 5% ammonia water was added and mixed for 3 hours until pH 8 was reached to carry out a neutralization hydrolysis reaction.
【００３４】得られたアンチモン含有含水水酸化チタン
スラリーを、ブフナーロートを用いて吸引濾過、水洗を
行い、アンチモン含有含水水酸化チタンケーキを得た
後、該ケーキをＴｉＯ2 換算で０．７ｍｏｌ／ｌの濃度
になるように、純水を加えてスラリー化した。上記スラ
リーを攪拌しながら、反応系を窒素雰囲気にして、Ｂａ
（ＯＨ）2 ・８Ｈ2 Ｏ（林純薬工業社製、試薬特級）を
Ｂａ／Ｔｉ原子比が１．４になるよう添加混合したの
ち、沸騰温度まで約１時間かけて昇温し、１０５℃の温
度で約４時間水熱反応を行った。The obtained antimony-containing hydrous titanium hydroxide slurry is suction filtered using a Buchner funnel and washed with water to obtain an antimony-containing hydrous titanium hydroxide cake, and the cake is converted to TiO 2 in an amount of 0.7 mol / mol. Pure water was added to form a slurry so that the concentration became l. While stirring the above slurry, the reaction system was placed in a nitrogen atmosphere and
(OH) 2 · 8H 2 O ( HayashiJunyaku Kogyo Co., reagent grade) after a Ba / Ti atomic ratio was added and mixed so as to be 1.4, the temperature was raised over a period of about 1 hour to boiling temperature, 105 The hydrothermal reaction was carried out at a temperature of ° C for about 4 hours.
【００３５】その後、室温まで自然冷却したのち、デカ
ンテーションを繰り返し、ブフナーロートを用いて吸引
濾過、水洗を行った。反応後得られたケーキは、ＴｉＯ
2 換算で０．７ｍｏｌ／ｌの濃度になるように純水に再
分散し、スラリー化した。このスラリーを攪拌しながら
６０℃に加温してその温度に保持しながら、Ｂａ／Ｔｉ
原子比調整の目的で、１０％酢酸溶液を加えて各スラリ
ーをｐＨ８〜１０に調整し、その状態を１時間保持し
た。各々のスラリーは、ブフナーロートを用いて吸引濾
過、水洗を行い、乾燥した。Then, after naturally cooling to room temperature, decantation was repeated, and suction filtration using a Buchner funnel and washing with water were performed. The cake obtained after the reaction is TiO 2.
It was redispersed in pure water so as to have a concentration of 0.7 mol / l in terms of 2 and made into a slurry. While stirring this slurry and heating it to 60 ° C. and maintaining it at that temperature, Ba / Ti
For the purpose of adjusting the atomic ratio, each slurry was adjusted to pH 8 to 10 by adding a 10% acetic acid solution, and the state was maintained for 1 hour. Each slurry was suction filtered using a Buchner funnel, washed with water, and dried.
【００３６】得られた粉体は、その粒子径を走査型電子
顕微鏡（日立製作所製 Ｓ−９００）で、結晶形をＸ線
回折装置（リガク電子工業社製 ＲＶ−３００）で、そ
れぞれ測定したところ、いずれの場合においても、平均
粒子径が０．０８μｍの立方晶ペロブスカイト型結晶構
造を有するチタン酸バリウム粉体であった。また、上記
粉体は、蛍光Ｘ線分析装置（日本フィリップス社製 Ｐ
Ｗ１４８０）を用いて組成分析し、Ｂａ／Ｔｉ原子比と
Ｓｂ／Ｔｉ原子比とをそれぞれ定量した。得られた結果
を表１に示す。The particle size of the obtained powder was measured with a scanning electron microscope (S-900 manufactured by Hitachi, Ltd.), and the crystal shape was measured with an X-ray diffractometer (RV-300 manufactured by Rigaku Electronics Co., Ltd.). However, in all cases, the barium titanate powder had a cubic perovskite crystal structure with an average particle diameter of 0.08 μm. In addition, the powder is a fluorescent X-ray analyzer (P manufactured by Nippon Phillips Co., Ltd.
W1480) was used for compositional analysis to determine the Ba / Ti atomic ratio and the Sb / Ti atomic ratio, respectively. The results obtained are shown in Table 1.
【００３７】上記粉体はさらに、各々８００℃で２時間
仮焼し、平均粒子径が０．１μｍのアンチモン含有チタ
ン酸バリウムペロブスカイト結晶微粉体とした。この
際、上記微粉体を蛍光Ｘ線分析装置を用いて再度組成分
析したが、Ｂａ／Ｔｉ原子比およびＳｂ／Ｔｉ原子比
は、いずれも表１に示した値から変化しなかった。Each of the above powders was further calcined at 800 ° C. for 2 hours to obtain antimony-containing barium titanate perovskite crystal fine powder having an average particle diameter of 0.1 μm. At this time, the composition analysis of the fine powder was performed again using a fluorescent X-ray analyzer, and the Ba / Ti atomic ratio and the Sb / Ti atomic ratio did not change from the values shown in Table 1.
【００３８】上記微粉体は、樹脂製のボールとポットと
からなるボールミルを用いてそれぞれ湿式粉砕混合し、
バインダーとしてポリビニルアルコールを粉体に対して
１．０％添加して、スプレードライヤーを用いて造粒
し、造粒粉を得た。The above fine powders are wet pulverized and mixed using a ball mill consisting of resin balls and pots,
Polyvinyl alcohol was added as a binder in an amount of 1.0% to the powder and granulated using a spray dryer to obtain granulated powder.
【００３９】造粒粉は、１トン／ｃｍ2 の圧力で、直径
１５ｍｍ、厚み１ｍｍのペレット状に成形した。この
際、成形体を蛍光Ｘ線分析装置を用いて再度組成分析し
たが、Ｂａ／Ｔｉ原子比およびＳｂ／Ｔｉ原子比は、い
ずれも表１に示した値から変化はなかった。The granulated powder was formed into pellets having a diameter of 15 mm and a thickness of 1 mm at a pressure of 1 ton / cm 2 . At this time, the composition of the molded body was analyzed again using a fluorescent X-ray analyzer, and the Ba / Ti atomic ratio and the Sb / Ti atomic ratio did not change from the values shown in Table 1.
【００４０】上記成形体は、大気中で１１００〜１２５
０℃の間でそれぞれ２５℃刻みの温度幅で焼成温度を設
定して焼成を行った。焼成温度における保持時間は２時
間、昇温は＋３００℃／ｈｒ．、降温は−２００℃／ｈ
ｒ．という条件で、焼成磁器を各々得た。The above-mentioned molded product is 1100 to 125 in air.
Firing was performed by setting the firing temperature in a temperature range of 0 ° C. in 25 ° C. increments. The holding time at the firing temperature is 2 hours, and the temperature rise is + 300 ° C./hr. , The temperature drop is -200 ℃ / h
r. Under the conditions, each firing porcelain was obtained.
【００４１】上記の方法で得た各種組成（Ｂａ／Ｔｉ原
子比、Ｓｂ／Ｔｉ原子比）の焼成磁器の特性を測定し、
表２に示した。The characteristics of the fired porcelain having various compositions (Ba / Ti atomic ratio, Sb / Ti atomic ratio) obtained by the above method were measured,
The results are shown in Table 2.
【００４２】表２における、平均グレイン径や最大グレ
イン径は、走査型電子顕微鏡（以下ＳＥＭと略す）によ
る観察から測定した。平均グレイン径は、ＳＥＭ写真に
一定間隔で直線を引き、該直線にヒットしたグレインの
大きさを０．１μｍ単位で計測し、その個数を計数し
（ただし、グレインが大きく、２度以上ヒットしたもの
はその都度計数する）、全合計個数を約３０００個とし
て、以下の式で計算した。 （グレインの大きさの測定値の合計）／（全合計個数）The average grain diameter and the maximum grain diameter in Table 2 were measured by observation with a scanning electron microscope (hereinafter abbreviated as SEM). For the average grain diameter, a straight line was drawn on the SEM photograph at regular intervals, the size of the grain hitting the straight line was measured in 0.1 μm units, and the number was counted (however, the grain was large and the grain was hit twice or more). The number is calculated each time) and the total number is set to about 3000, and the calculation is performed by the following formula. (Sum of grain size measurements) / (Total number of pieces)
【００４３】比抵抗ρおよび耐電圧強度Ｅは、磁器の両
面にオーミック性銀ペーストを焼き付けて電極とし、こ
れを測定用試料として、２５℃で測定した。耐電圧強度
については、試料に破壊が起こる寸前の最高印加電圧値
を測定し、試料の電極間（厚み：ｍｍ）で割って表した
ものである。The specific resistance ρ and the withstand voltage strength E were measured at 25 ° C. by baking ohmic silver paste on both surfaces of the porcelain to form electrodes, which were used as measurement samples. The withstand voltage strength is represented by measuring the maximum applied voltage value just before the sample is broken and dividing it by the distance between electrodes (thickness: mm) of the sample.
【００４４】焼成温度については、１１００〜１２５０
℃の間で焼成した各磁器の中で、最も良好な耐電圧強度
／比抵抗（Ｅ／ρ）の特性が得られた磁器の焼成温度を
示している。The firing temperature is 1100 to 1250.
The firing temperature of the porcelain having the best characteristics of withstand voltage strength / specific resistance (E / ρ) among the porcelains fired at between ° C is shown.
【００４５】[0045]
【表１】 [Table 1]
【００４６】[0046]
【表２】 [Table 2]
【００４７】比較例１−１１ 実施例と同じ方法を用いて、図１のＡＢＣＤで囲まれた
範囲外であり、Ｂａ／Ｔｉ原子比およびＳｂ／Ｔｉ原子
比が表３に示した値である焼成磁器を作成し、各磁器の
特性を測定して表４に示した。Comparative Example 1-11 Using the same method as in the Example, it is outside the range surrounded by ABCD in FIG. 1, and the Ba / Ti atomic ratio and the Sb / Ti atomic ratio are the values shown in Table 3. A fired porcelain was prepared and the characteristics of each porcelain were measured and shown in Table 4.
【００４８】[0048]
【表３】 [Table 3]
【００４９】[0049]
【表４】 [Table 4]
【００５０】表１および図１から、実施例２〜５、７、
８、１０、１４は図１のａｂｃｄで囲まれた範囲内にあ
り、実施例１、６、９、１１〜１３、１５〜１７は図１
のａｂｃｄで囲まれた範囲内にはないが、ＡＢＣＤで囲
まれた範囲内にあることがわかる。また、表３および図
１から、比較例１〜１１は、図１のＡＢＣＤで囲まれた
範囲内にはないことがわかる。From Table 1 and FIG. 1, Examples 2 to 5, 7,
8, 10 and 14 are within the range surrounded by abcd in FIG. 1, and Examples 1, 6, 9, 11 to 13 and 15 to 17 are shown in FIG.
It can be seen that it is not within the range surrounded by abcd, but is within the range surrounded by ABCD. Further, it can be seen from Table 3 and FIG. 1 that Comparative Examples 1 to 11 are not within the range surrounded by ABCD in FIG.
【００５１】表２から明らかなように、各実施例の平均
グレイン径はいずれにおいても１〜２μｍであり、最大
グレイン径についても５μｍを越えるものは全く見られ
ないことから、本発明の磁器組織においては、グレイン
分布が非常に揃っていることがわかる。As is clear from Table 2, the average grain size of each example is 1 to 2 μm, and the maximum grain size of 5 μm is not observed at all. In, the grain distributions are very uniform.
【００５２】また、表２の実施例と、比較例である表４
とを比較してみると明らかなように、図１のＡＢＣＤで
囲まれた範囲内にある磁器は、比抵抗が低く耐電圧強度
が高いという特性を有し、さらに、図１のａｂｃｄで囲
まれた範囲内にある磁器は、耐電圧強度Ｅ／比抵抗ρが
１０以上と、その中でも非常に優れた特性を有している
ことがわかる。Further, the examples of Table 2 and Table 4 which is a comparative example.
As is clear from the comparison between and, the porcelain in the range surrounded by ABCD in FIG. 1 has a characteristic that the specific resistance is low and the withstand voltage strength is high, and further, it is surrounded by abcd in FIG. It can be seen that the porcelain within the above range has a withstand voltage strength E / specific resistance ρ of 10 or more, and is very excellent among them.
【００５３】比較例１〜８は、本発明である図１のＡＢ
ＣＤで囲まれた範囲に対し、Ｂａ／Ｔｉ原子比が範囲外
のものであるが、上記範囲よりもＴｉ原子比が大きい場
合（比較例１〜４）には、１２５０℃以下の焼成では十
分な特性を有する磁器が得られず、上記範囲よりもＢａ
原子比が大きい場合（比較例５〜８）には、表中の焼成
温度未満の焼成では半導化が不十分となるため比抵抗が
高くなり、表中の焼成温度を越える焼成では耐電圧強度
が低くなってしまい、また、表中に示した最も良い特性
が得られる焼成温度においても、耐電圧強度／比抵抗
（Ｅ／ρ）が５未満となるので、本発明の目的とする特
性が得られない。Comparative Examples 1 to 8 are AB of FIG. 1 according to the present invention.
The Ba / Ti atomic ratio is outside the range surrounded by the CD, but when the Ti atomic ratio is larger than the above range (Comparative Examples 1 to 4), firing at 1250 ° C. or lower is sufficient. It is not possible to obtain a porcelain having excellent characteristics,
When the atomic ratio is large (Comparative Examples 5 to 8), the semiconductivity becomes insufficient in the firing below the firing temperature in the table and the specific resistance increases, and the withstand voltage in the firing above the firing temperature in the table. The strength becomes low, and the withstand voltage strength / specific resistance (E / ρ) is less than 5 even at the firing temperature at which the best characteristics shown in the table are obtained. Can't get
【００５４】比較例９〜１１は、本発明である図１のＡ
ＢＣＤで囲まれた範囲に対し、Ｓｂ／Ｔｉ原子比が本発
明の範囲外（比較例９はアンチモンの含有量が少なく、
比較例１０、１１はアンチモンの含有量が多い場合）の
ものであるが、いずれの場合においても、表中の焼成温
度未満の焼成では半導化が不十分となるため比抵抗が高
くなり、表中の焼成温度を越える焼成では耐電圧強度が
低くなってしまい、また、表中に示した最も良い特性が
得られる焼成温度においても、結果としてＥ／ρが５未
満となるので、本発明の目的とする特性が得られない。Comparative Examples 9 to 11 represent the present invention and are indicated by A in FIG.
In the range surrounded by BCD, the Sb / Ti atomic ratio is outside the range of the present invention (Comparative Example 9 has a low content of antimony,
Comparative Examples 10 and 11 are those in which the content of antimony is high), but in any case, if the firing temperature is lower than the firing temperature in the table, the semiconductivity becomes insufficient, so that the specific resistance becomes high, If the firing temperature exceeds the firing temperature in the table, the withstand voltage strength becomes low. Further, even at the firing temperature at which the best characteristics shown in the table are obtained, as a result, E / ρ becomes less than 5, the present invention The desired characteristics of cannot be obtained.
【００５５】[0055]
【発明の効果】以上のように、湿式反応によって半導化
剤であるアンチモンを均一に含有した微粒の原料粉を用
い、しかも、Ｓｂ／Ｔｉ原子比、Ｂａ／Ｔｉ原子比を厳
密に制御することによって、耐電圧強度が５００Ｖ／ｍ
ｍ以上でかつ耐電圧強度／比抵抗が５以上である従来に
ない特性のＰＴＣ半導体磁器が、さらに、耐電圧強度が
５００Ｖ／ｍｍ以上、耐電圧強度／比抵抗が１０以上と
いう非常に優れたＰＴＣ半導体磁器が得られる。INDUSTRIAL APPLICABILITY As described above, a fine raw material powder uniformly containing antimony as a semiconducting agent is used by a wet reaction, and the Sb / Ti atomic ratio and the Ba / Ti atomic ratio are strictly controlled. Withstand voltage strength of 500V / m
The PTC semiconductor porcelain with unprecedented characteristics of m or more and withstand voltage strength / specific resistance of 5 or more is further excellent in withstand voltage strength of 500 V / mm or more and withstand voltage strength / specific resistance of 10 or more. A PTC semiconductor porcelain is obtained.
【００５６】従って、本発明によれば、従来にまして実
用性に優れたＰＴＣ半導体磁器を提供することが可能で
あり、利用可能範囲の拡大を図ることができる。また、
従来のＰＴＣ半導体磁器を得るためには、通常１３００
℃以上の高温焼成が必要であり、そのため、使用できる
炉体構造としては１４００℃耐用のものが必要となるの
で設備コストが高くなり、しかも、用いるコウバチ、セ
ッタなどの治具の消耗が激しくて維持コストも高くなっ
ていたが、本発明の半導体磁器の製造方法を適用すれ
ば、１２５０℃以下の低温で焼成が可能であるため、上
記コストが低減できる。Therefore, according to the present invention, it is possible to provide a PTC semiconductor porcelain which is more practical than ever, and it is possible to expand the usable range. Also,
To obtain the conventional PTC semiconductor porcelain, it is usually 1300
High temperature firing above ℃ is required, and therefore, the furnace structure that can be used must have a durability of 1400 ℃, so the equipment cost is high, and the consumption of jigs such as wasps and setters is severe. Although the maintenance cost was also high, if the method for manufacturing a semiconductor porcelain of the present invention is applied, firing can be performed at a low temperature of 1250 ° C. or lower, so that the cost can be reduced.
【図１】本発明のチタン酸バリウム系半導体磁器におけ
る、Ｓｂ／Ｔｉ原子比およびＢａ／Ｔｉ原子比の範囲を
示した図である。FIG. 1 is a diagram showing the ranges of Sb / Ti atomic ratio and Ba / Ti atomic ratio in a barium titanate-based semiconductor ceramic of the present invention.
フロントページの続き (72)発明者 坪本 直人 大阪府大阪市大正区船町１丁目３番47号 テイカ株式会社内Front page continuation (72) Inventor Naoto Tsubomoto 1-37 Funamachi, Taisho-ku, Osaka, Osaka
Claims (4)
ロブスカイト型結晶構造を有するチタン酸バリウム半導
体磁器において、Ｓｂ／Ｔｉ原子比およびＢａ／Ｔｉ原
子比とが、図１のＡＢＣＤで囲まれた範囲内にあり、か
つ半導体磁器の平均グレイン径が１〜２μｍであり、か
つ最大グレイン径が５μｍ以下であることを特徴とし、
上記半導体磁器の特性として、耐電圧強度が５００Ｖ／
ｍｍ以上で、かつ耐電圧強度／室温における比抵抗が５
以上であるチタン酸バリウム系半導体磁器。1. In a barium titanate semiconductor ceramic having a perovskite type crystal structure containing antimony as a semiconducting agent, the Sb / Ti atomic ratio and the Ba / Ti atomic ratio are in a range surrounded by ABCD in FIG. And the average grain diameter of the semiconductor porcelain is 1 to 2 μm and the maximum grain diameter is 5 μm or less,
As a characteristic of the above-mentioned semiconductor porcelain, withstand voltage strength is 500 V /
mm or more and withstand voltage strength / specific resistance at room temperature is 5
The above is a barium titanate-based semiconductor porcelain.
ロブスカイト型結晶構造を有するチタン酸バリウム半導
体磁器において、Ｓｂ／Ｔｉ原子比およびＢａ／Ｔｉ原
子比とが、図１のａｂｃｄで囲まれた範囲内にあり、か
つ半導体磁器の平均グレイン径が１〜２μｍであり、か
つ最大グレイン径が５μｍ以下であることを特徴とし、
上記半導体磁器の特性として耐電圧強度が５００Ｖ／ｍ
ｍ以上で、かつ耐電圧強度／室温における比抵抗が１０
以上であるチタン酸バリウム系半導体磁器。2. In a barium titanate semiconductor ceramic having a perovskite type crystal structure containing antimony as a semiconducting agent, the Sb / Ti atomic ratio and the Ba / Ti atomic ratio are in a range surrounded by abcd in FIG. And the average grain diameter of the semiconductor porcelain is 1 to 2 μm and the maximum grain diameter is 5 μm or less,
As a characteristic of the above-mentioned semiconductor porcelain, withstand voltage strength is 500 V / m
m or more and withstand voltage strength / specific resistance at room temperature is 10
The above is a barium titanate-based semiconductor porcelain.
ｂ／Ｔｉ＝０．０５〜０．４５％含有するチタン化合物
の溶液またはスラリーと、バリウム化合物とを湿式反応
させ、必要に応じて仮焼することにより、平均粒子径が
０．３μｍ以下で、かつＳｂ／Ｔｉ原子比およびＢａ／
Ｔｉ原子比が図１のＡＢＣＤで囲まれた範囲にある、ア
ンチモンを均一に含有したペロブスカイト結晶構造を有
したチタン酸バリウム粉体を得、上記粉体を成形したの
ち、該成形体を１１５０〜１２５０℃で焼成することを
特徴とする請求項１記載の半導体磁器の製造方法。3. Antimony as Sb / Ti atomic ratio S
A solution or slurry of a titanium compound containing b / Ti = 0.05 to 0.45% is wet-reacted with a barium compound, and calcined if necessary, so that the average particle diameter is 0.3 μm or less, And Sb / Ti atomic ratio and Ba /
A barium titanate powder having a perovskite crystal structure uniformly containing antimony and having a Ti atomic ratio in a range surrounded by ABCD in FIG. 1 was obtained, and the powder was compacted. The method for manufacturing a semiconductor ceramic according to claim 1, wherein the firing is performed at 1250 ° C.
チタンの塩化物とアンチモンの水溶性化合物との水溶液
を加水分解して得られた、アンチモンを均一に含有した
チタンの含水水酸化物または酸化物であり、バリウム化
合物がバリウムの水酸化物であり、湿式反応が水熱反応
であることを特徴とする請求項３記載の半導体磁器の製
造方法。4. A titanium compound containing antimony,
A hydrous oxide or oxide of titanium uniformly containing antimony, obtained by hydrolyzing an aqueous solution of titanium chloride and a water-soluble compound of antimony, and the barium compound is a hydroxide of barium. The method of manufacturing a semiconductor porcelain according to claim 3, wherein the wet reaction is a hydrothermal reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6036509A JPH08213205A (en) | 1994-02-08 | 1994-02-08 | Barium titanate semiconductor ceramics and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6036509A JPH08213205A (en) | 1994-02-08 | 1994-02-08 | Barium titanate semiconductor ceramics and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08213205A true JPH08213205A (en) | 1996-08-20 |
Family
ID=12471808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6036509A Pending JPH08213205A (en) | 1994-02-08 | 1994-02-08 | Barium titanate semiconductor ceramics and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08213205A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6984355B2 (en) | 1999-11-02 | 2006-01-10 | Murata Manufacturing Co., Ltd. | Semiconducting ceramic material, process for producing the ceramic material, and thermistor |
-
1994
- 1994-02-08 JP JP6036509A patent/JPH08213205A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6984355B2 (en) | 1999-11-02 | 2006-01-10 | Murata Manufacturing Co., Ltd. | Semiconducting ceramic material, process for producing the ceramic material, and thermistor |
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