JPH02120277A - Barium titanate semiconductor porcelain material - Google Patents
Barium titanate semiconductor porcelain materialInfo
- Publication number
- JPH02120277A JPH02120277A JP63269542A JP26954288A JPH02120277A JP H02120277 A JPH02120277 A JP H02120277A JP 63269542 A JP63269542 A JP 63269542A JP 26954288 A JP26954288 A JP 26954288A JP H02120277 A JPH02120277 A JP H02120277A
- Authority
- JP
- Japan
- Prior art keywords
- barium titanate
- temperature
- barium
- titanium
- magnetic material
- 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.)
- Granted
Links
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 44
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000004065 semiconductor Substances 0.000 title claims abstract description 35
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 9
- 239000000463 material Substances 0.000 title abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 229910010293 ceramic material Inorganic materials 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052788 barium Inorganic materials 0.000 abstract description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052787 antimony Inorganic materials 0.000 abstract description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000000696 magnetic material Substances 0.000 abstract 4
- 229910009973 Ti2O3 Inorganic materials 0.000 abstract 2
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- DEIVNMVWRDMSMJ-UHFFFAOYSA-N hydrogen peroxide;oxotitanium Chemical compound OO.[Ti]=O DEIVNMVWRDMSMJ-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- XZLXGTUBUCMRCH-UHFFFAOYSA-N tungsten zinc Chemical group [Zn].[W] XZLXGTUBUCMRCH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000016299 Canarium odontophyllum Nutrition 0.000 description 1
- 244000001582 Canarium odontophyllum Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PONGKJLRIGEQCT-UHFFFAOYSA-N [Si]([O-])([O-])([O-])[O-].[Ti+4].[Ba+2] Chemical compound [Si]([O-])([O-])([O-])[O-].[Ti+4].[Ba+2] PONGKJLRIGEQCT-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
- H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
- H01C7/025—Perovskites, e.g. titanates
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は半導体磁器材料に関し、詳しくは常温における
比抵訊が低く、電圧依存性が小さく、さらに比較的大き
い正の抵抗温度特性を有するとともに高温における比抵
抗の低下がない半導体磁器材料に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a semiconductor ceramic material, and more specifically, it has a low resistivity at room temperature, a small voltage dependence, and a relatively large positive resistance temperature characteristic. The present invention relates to a semiconductor ceramic material that does not have a decrease in resistivity at high temperatures.
本発明の半導体磁器材料は、温度制御および電流制御に
利用することができ、また消磁回路に利用することがで
きる。The semiconductor ceramic material of the present invention can be used for temperature control and current control, and can also be used for degaussing circuits.
チタン酸バリウムのセラミックスを、コンデンサ、圧電
体として利用することは従来より広く知られている。It has been widely known that barium titanate ceramics can be used as capacitors and piezoelectric bodies.
チタン酸バリウムに希土類元素を極く少量添加すると、
その比抵祈がｌＯ〜ｌＯΩ・ｃｍの一部の半導体となり
、そのキュリー点に対応する温度において正の抵抗温度
特性（Ｐｏ５ｉｔｉｖｅ ＴｅｍｐｅｒａｔｕｒｅＣｏ
ｅｆｆｉｃｉｅｎｔ （ＰＴＣ特性）〕を示すことは
１９５０年代に発見され、チタン酸バリウム系の半導体
磁器材料が開発されたが、自動制御の発展とともに、微
小電流で作動するデバイス等を使用することが多くなり
、最近では、その弱電化がさらに追んで、常温における
低い抵払値と大きい正の抵＠温度特性を有する半導体の
開発が要望されている。チタン酸バリウムに、イツトリ
ウム（Ｙ）、ｆＮ土類元元素３価の金属元素、およびア
ルカリ金属、タリウム等の１ｏｆＨの金属元素を加え、
焼成して室温付近の温度で大きい正の抵＠温度特性を有
するチタン酸バリウム系の正特性半導体磁器を調音する
方法が提案され（特開昭５８−１０７６０３号公報）、
またチタン酸バリウム系半導体におけるバリウム（Ｂａ
）の一部をストロンチウム（Ｓｒ）で置換することによ
り正の抵抗温度特性（ＰＴＣ特性）を示す温度を低温側
に移動すること、およびそのバリウムの一部を鉛（ｐｂ
）で置換することによりＰＴＣ特性を示す温度を高温側
に移動することは広く知られており、またチタン酸バリ
ウムのバリウム（Ｂａ）の一部をストロンチウム（Ｓｒ
）および鉛（ｐｂ）で置換し、そのチタン酸バリウムに
希土類元素およびビスマス（Ｂｉ）、アンチモン（ｓｂ
）、ニオブ（Ｎｂ）、タンタル（Ｔａ）のうちのｌＮ以
上、マンガン（Ｍｎ）、鉄（Ｆｅ）および飼（Ｃｕ）の
うちの１種以上、およびシリカ（５１０゜）およびアル
ミナ（ＡＩＯ）を添加して焼成したものであって、電圧
依存性が小さく、耐電圧が高い特性を有するチタン酸バ
リウム系半導体磁器が提案されている（特開昭５３−９
８０９５号公報）。When a very small amount of rare earth elements are added to barium titanate,
The resistivity becomes a part of a semiconductor with a range of 1O to 1OΩ・cm, and it exhibits a positive resistance-temperature characteristic (Po5itive TemperatureCo) at the temperature corresponding to its Curie point.
PTC characteristics) was discovered in the 1950s, and barium titanate-based semiconductor porcelain materials were developed, but with the development of automatic control, devices that operate with minute currents are increasingly used. Recently, with the trend towards weaker electrical currents, there has been a demand for the development of semiconductors that have a low resistance value at room temperature and a large positive resistance@temperature characteristic. Adding yttrium (Y), fN earth element trivalent metal element, and 1ofH metal element such as alkali metal and thallium to barium titanate,
A method has been proposed for tuning barium titanate-based positive characteristic semiconductor porcelain which has a large positive resistance@temperature characteristic at a temperature near room temperature by firing (Japanese Patent Application Laid-Open No. 107603/1982).
In addition, barium (Ba) in barium titanate-based semiconductors
) by replacing part of the barium with strontium (Sr) to move the temperature exhibiting positive resistance-temperature characteristics (PTC characteristics) to a lower temperature side, and replacing part of the barium with lead (pb).
) is widely known to shift the temperature exhibiting PTC characteristics to a higher temperature side.
) and lead (pb), and the barium titanate is replaced with rare earth elements, bismuth (Bi), and antimony (sb).
), niobium (Nb), tantalum (Ta), one or more of manganese (Mn), iron (Fe) and copper (Cu), and silica (510°) and alumina (AIO). Barium titanate-based semiconductor porcelain has been proposed, which is made by adding additives and firing, and has characteristics of low voltage dependence and high withstand voltage (Japanese Patent Laid-Open No. 53-9
Publication No. 8095).
またチタン酸バリウム系の正の抵抗温度特性を存する半
導体磁器の製造において、半導体化促進剤としてバリウ
ム−チタニウム−シリケートまたはバリウム−シリケー
ト系化合物を添加し、焼成して正の抵抗温度特性を存す
る比抵抗のバラツキをかさくシ、その比抵抗を低下する
ことが提案されているが（特開昭５７−１０９３０１号
公報）、シリケート成分（Ｓｉｎ）の添加は、バリウム
（Ｂａ）とチタン（Ｔ１）の比率の調整を必要とする。In addition, in the production of barium titanate-based semiconductor porcelain that has positive resistance-temperature characteristics, barium-titanium-silicate or barium-silicate-based compounds are added as a semiconductor accelerator, and the ratio of barium titanate-based ceramics that exhibits positive resistance-temperature characteristics is added by firing. It has been proposed to reduce the variation in resistance and lower the specific resistance (Japanese Patent Application Laid-open No. 109301/1983), but the addition of a silicate component (Sin) is effective against barium (Ba) and titanium (T1). It is necessary to adjust the ratio of
またチタン酸バリウム組成物のチタン（Ｔｉ）の−部を
タングステン−亜鉛（Ｗ−Ｚｎ）またはタングステン−
マグネシウム（Ｗ−Ｍｇ）で置換えたチタン酸バリウム
系半導体磁器が提案されているが（特開昭５６−１６９
３０２号公報）、イオン半径の相違によって固溶体を形
成し難いと考えられる。Alternatively, the negative part of titanium (Ti) in the barium titanate composition may be replaced with tungsten-zinc (W-Zn) or tungsten-zinc (W-Zn).
A barium titanate semiconductor porcelain substituted with magnesium (W-Mg) has been proposed (Japanese Patent Laid-Open No. 56-169).
302), it is thought that it is difficult to form a solid solution due to the difference in ionic radius.
本発明者らは、チタン酸バリウムの圧電性について研究
を続け、−軸方向に配列したチタン酸バリウムを合成樹
脂マトリックスに配列することによって、優れた圧電性
を有するチタン酸バリウム複合圧電素子材料を提案した
が（特願昭６２−９７号）、チタン酸バリウムの電気特
性について研究を砿太し、その研究においてチタン酸バ
リウムにおける酸化チタンの一部を亜酸化チタン（Ｔｔ
ｏ）で置換すると、正の抵抗温度特性（ある温度におい
て比抵抗が急激に増大する特性）に影響を及ぼすことな
く、常温における比抵抗の値が低下することを見出し、
その知見に基づいて本発明に到達した。The present inventors continued research on the piezoelectricity of barium titanate, and created a barium titanate composite piezoelectric element material with excellent piezoelectricity by arranging barium titanate arranged in the -axial direction in a synthetic resin matrix. (Japanese Patent Application No. 1983-1997), but extensive research was conducted into the electrical properties of barium titanate, and in this research, some of the titanium oxide in barium titanate was replaced with titanium suboxide (Tt
It has been discovered that when substituted with o), the value of specific resistance at room temperature decreases without affecting the positive resistance-temperature characteristics (characteristics in which specific resistance rapidly increases at a certain temperature),
Based on this knowledge, we have arrived at the present invention.
本発明の目的は、チタン酸バリウム系半導体磁器材料を
提供することにあり、詳しくは正の抵抗温度特性に影響
を及ぼすことなく、常温における比抵折僅の低下したチ
タン酸バリウム系半導体磁器材料を提供することにある
。An object of the present invention is to provide a barium titanate-based semiconductor ceramic material, and more specifically, a barium titanate-based semiconductor ceramic material that exhibits a slight decrease in specific resistance at room temperature without affecting the positive resistance-temperature characteristics. Our goal is to provide the following.
本発明は、チタン酸バリウムの半導体化添加剤を含むチ
タン酸バリウム系半導体磁器材料において、酸化チタン
成分の一部を亜酸化チタン（Ｔｉｅ 、二三酸化チタ
ン）とし、それによって正の抵＠温度特性に影響を及ぼ
すことなく、常温における比抵択値を低下したことを特
徴とするチタン酸バリウム半導体磁器材料である。The present invention provides a barium titanate-based semiconductor ceramic material containing a barium titanate semiconductor additive, in which a part of the titanium oxide component is titanium suboxide (Tie, titanium ditrioxide), thereby increasing the positive resistance @ temperature. This barium titanate semiconductor ceramic material is characterized by a reduced specific resistance value at room temperature without affecting its properties.
本発明のチタン酸バリウム系半導体磁器材料は、炭酸バ
リウムのバリウム成分、酸化チタンおよび亜酸化チタン
（Ｔｉｅ、二三酸化チタン）のチタニウム成分およびチ
タン酸バリウムの半導体化添加剤の粉末を混合し、成形
して材料混合物の成形体とし、その成形体を焼成するこ
とによって、つくられる。The barium titanate-based semiconductor ceramic material of the present invention is obtained by mixing a barium component of barium carbonate, a titanium component of titanium oxide and titanium suboxide (Tie, titanium ditrioxide), and a semiconductor additive powder of barium titanate, It is produced by molding a material mixture into a molded body and firing the molded body.
本発明のチタン酸バリウム系半導体磁器材器におけるチ
タン酸バリウムの半導体化添加剤は、チタン酸バリウム
に正の抵抗温度特性を付与するものであれだ、これまで
に知られたどのようなものであっても、これを用いるこ
とができるが、希土類元素、マンガン、アンチモン、酸
化ケイ素（ＳｉＯ）を用いることができる。The semiconducting additive for barium titanate in the barium titanate-based semiconductor porcelain material of the present invention may be any known additive that imparts positive resistance-temperature characteristics to barium titanate. If present, this can be used, but rare earth elements, manganese, antimony, and silicon oxide (SiO) can be used.
本発明のチタン酸バリウム系半導体磁器材料において、
材料混合物に、ストロンチウム化合物を加え、それによ
ってチタン酸バリウム系半導体磁器材料の正の抵抗温度
特性（ＰＴＣ特性）を示す温度を低温側に移動し、また
鉛化合物を加え、それによってその正の抵＠温度特性（
ＰＴＣ特性）を示す温度を高温側に移動し、さらにこの
両者の添加量の調整によって、チタン酸バリウム系半導
体磁器材料の正の抵抗温度特性（ＰＴＣ特性）を示す温
度を調整することができる。In the barium titanate-based semiconductor ceramic material of the present invention,
A strontium compound is added to the material mixture, thereby shifting the temperature at which the barium titanate-based semiconductor ceramic material exhibits a positive resistance-temperature characteristic (PTC characteristic) to a lower temperature side, and a lead compound is added, thereby increasing the positive resistance. @Temperature characteristics (
By moving the temperature at which the barium titanate-based semiconductor ceramic material exhibits the positive resistance-temperature characteristic (PTC characteristic) to a higher temperature side and further adjusting the amounts of both, it is possible to adjust the temperature at which the barium titanate-based semiconductor ceramic material exhibits the positive resistance-temperature characteristic (PTC characteristic).
本発明のチタン酸バリウム系半導体磁器材料のＩＩＩ造
において、前記の成形体の焼結における加熱条件は、チ
タン酸バリウムの半導体化を達成しうる温度および時間
のどのような条件であってもよいが、１３００〜１５０
０℃において少なくとも１時間程度であるのが好ましい
。In the third production of the barium titanate-based semiconductor ceramic material of the present invention, the heating conditions for sintering the molded body may be any temperature and time conditions that can achieve the conversion of barium titanate into a semiconductor. But 1300-150
Preferably, the heating time is at least about 1 hour at 0°C.
以下において、本発明を実施例および比較例によりさら
に詳しく説明する。In the following, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１
高純度炭酸バリウム
（口ａｃＯ、堺化学製） ６７９．９４
／ｉ高純度炭酸ストロンチウム
（ＳｒＣＯ、本荘ケミカル社製） ２６．７７．
９酸化チタン
（ＴＩＯ、東邦チタニウム社製） ２８８．３３
／１酸化アンチモン（９９，９％）
（ｓｂｏ、レアメタリック社製１ １．０５７２
／１炭酸マンガン（９９，９％）
（Ｍｎｃｏ 、和光純薬社製） ０．２
０８４９酸化ケイ素（９９，９％）
（ＳｔＯ、レアメタリック社製） １．０８９６
９亜酸化チタン
（ＴＩ３０３、東邦チタニウム社製） ２．６０
７６ Ｆをナイロン製ボールミル用ポット（容量 ：
５７りに入れ、これにイオン交換水３７！を入れ、さら
に鉄心入りナイロンボール（２５朋φ）４０個を入れ、
ボールミル用ポットの蓋を閉ぢて密閉し、ボールミル混
合を２４時間行なった。ボールミルの中味を濾紙により
濾過してペースト状の混合物を取得し、これを蒸発皿に
移し、乾燥器に入れて＋３０’（：において１６時間乾
燥して、乾Ｏ粉末１ｏｏｏ ｇを得た。Example 1 High purity barium carbonate (ACO, manufactured by Sakai Chemical) 679.94
/i High purity strontium carbonate (SrCO, manufactured by Honjo Chemical Co., Ltd.) 26.77.
Titanium 9 oxide (TIO, manufactured by Toho Titanium Co., Ltd.) 288.33
/antimony oxide (99.9%) (sbo, manufactured by Rare Metallic Co., Ltd. 1 1.0572
/1 Manganese carbonate (99.9%) (Mnco, manufactured by Wako Pure Chemical Industries) 0.2
0849 Silicon oxide (99.9%) (StO, manufactured by Rare Metallic) 1.0896
9 Titanium suboxide (TI303, manufactured by Toho Titanium Co., Ltd.) 2.60
76F in a nylon ball mill pot (capacity:
Add 37 liters of ion-exchanged water to this! Then add 40 nylon balls (25 mm φ) with iron core,
The lid of the ball mill pot was closed and airtight, and ball mill mixing was performed for 24 hours. The contents of the ball mill were filtered through a filter paper to obtain a pasty mixture, which was transferred to an evaporating dish and dried in an oven at +30' for 16 hours to obtain 100 g of dry O powder.
乾燥粉末を乳鉢に入れて粉砕し、メツシュ（４２５１Ｊ
ｒｒＬ）を通した。メツシュを通過した乾燥粉末を粉末
成形金型に入れ、３００ Ｋｇ ／ ｃａの加圧の下に
成形して、円盤状の成形体を得た。この成形体を電気炉
に入れ、１１５０℃において２時間熱処理（焼結）を行
なった。Place the dry powder in a mortar, crush it, and use mesh (4251J).
rrL). The dry powder that had passed through the mesh was put into a powder molding mold and molded under a pressure of 300 Kg/ca to obtain a disc-shaped molded body. This molded body was placed in an electric furnace and heat treated (sintered) at 1150°C for 2 hours.
成形体を冷却し、乳鉢において粗粉砕した後、振動ボー
ルミルのナイロンポット０．７１容の容器２個に等分し
て入れ、さらにこれにイオン交換水０．４１を入れ、焼
成物の湿式粉砕を行ない、スラリー状の粉体０．６１を
得た。After cooling the molded body and coarsely pulverizing it in a mortar, it was equally divided into two 0.71-volume nylon pot containers of a vibrating ball mill, and 0.41 ml of ion-exchanged water was added thereto, and the fired product was wet-pulverized. A slurry-like powder of 0.61% was obtained.
このスラリーに１５％ポリビニルアルコール（ゴーセノ
ール、日本合成化学社製品）１４０ｇを加え、その混合
物を撹拌機において混合した後、そのスラリーをスプレ
ードライヤー（アトマイザ−式Ｌ−８型、大川原化工機
社製）により白粉乾燥して、乾Ｑ粒体（数十μｍ）５ｏ
ｏｇを得た。乾燥粒体を成形用金型（１２，５龍（径）
Ｘ２ｍｍ（深さ）〕に入れ、１ ｔｏｎ ／ｃｙｉの加
圧においてプレス成形し、得られた円盤状の成形体（１
２，５ｍｇ（径）×２■（厚さ）〕をアルミナ板上に積
み重ねて、電気炉に入れ、１３６０℃において１．５時
間熱処理（焼結）を行なった。焼結後の円盤状の焼結体
は１０１０１１Ｉ径）Ｘｌ、７朋（厚さ）のサイズのも
のであった。Add 140 g of 15% polyvinyl alcohol (Gohsenol, manufactured by Nippon Gosei Kagaku Co., Ltd.) to this slurry, mix the mixture in a stirrer, and then apply the slurry to a spray dryer (atomizer type L-8 type, manufactured by Okawara Kakoki Co., Ltd.). Dry white powder and dry Q granules (several tens of μm) 50
I got og. A mold for molding the dry granules (12.5 yen (diameter)
x 2 mm (depth)] and press-molded at a pressure of 1 ton/cyi to obtain a disc-shaped molded body (1
2.5 mg (diameter) x 2 mm (thickness)] were stacked on an alumina plate, placed in an electric furnace, and heat-treated (sintered) at 1360° C. for 1.5 hours. The disk-shaped sintered body after sintering had a size of 101011I (diameter) Xl and 7 mm (thickness).
（電気低損の測定）
上記で得た円盤状の焼結体の両面にオーミック電極ペー
スト（デグサー社製）を塗布した後、５００℃において
５分加熱してｆｆ１Ｍを焼付け、その電極上にカバー銀
電極ペースト（デグサー社製）を塗布し、５００℃にお
いてさらに焼付けを行なって測定用サンプルを得た。(Measurement of low electrical loss) After applying ohmic electrode paste (manufactured by Degusr) to both sides of the disc-shaped sintered body obtained above, heat it at 500°C for 5 minutes to bake ff1M, and cover the electrode. A silver electrode paste (manufactured by Degusser) was applied and further baked at 500°C to obtain a measurement sample.
測定用サンプルの両面のｓｈにリード線をハンダ付けし
、その測定用サンプルを、測定用恒温槽（ミニサブゼロ
、ダバイ社製）に入れ、リード線は測定用恒温槽外に引
き出し、電気紙ＶＬ測定器（マルチメーター、ＹＨＰ社
製）に結線した。Solder lead wires to sh on both sides of the measurement sample, place the measurement sample in a thermostatic chamber for measurement (Mini Sub Zero, manufactured by Dabai), pull out the lead wires outside the thermostatic chamber for measurement, and place the electrical paper VL. It was connected to a measuring device (multimeter, manufactured by YHP).
測定用恒温槽の温度を室温から１８０℃まで上昇し、各
測定温度における測定用サンプルの電気抵抗値を読み取
り、次式によって比抵折を算出した。The temperature of the thermostatic chamber for measurement was raised from room temperature to 180° C., the electrical resistance value of the measurement sample at each measurement temperature was read, and the specific resistance was calculated using the following formula.
Ｒ−ρ−
Ｒ：電気抵抗の実測値
ρ ：比抵抗（Ω・ｆｆ１） （算出値）ｔ：測定用
サンプルの厚み（電極間の距離）（朋）Ｓ：電極の面積
（Ｈ）
測定の結果は第１図に示すとおりであった。R-ρ- R: Actual value of electrical resistance ρ: Specific resistance (Ω・ff1) (Calculated value) t: Thickness of measurement sample (distance between electrodes) (B) S: Area of electrode (H) Measurement The results were as shown in Figure 1.
実施例２
実施例１において、円盤状の焼結体の調製における最終
の焼結における焼結の条件を１３６０℃、１時間とした
こと以外は実施例１と同様にして、測定用サンプルを調
製し、さらに実施例１と同様にして、測定用サンプルの
電気抵抗値を測定し、さらに比抵抗（Ω・Ｃｍ）を算出
した。Example 2 A sample for measurement was prepared in the same manner as in Example 1, except that the sintering conditions in the final sintering in the preparation of the disc-shaped sintered body were 1360 ° C. for 1 hour. Furthermore, in the same manner as in Example 1, the electrical resistance value of the measurement sample was measured, and the specific resistance (Ω·Cm) was calculated.
測定の結果は第２図に示すとおりであった。The measurement results were as shown in Figure 2.
比較例１ （従来法）
高Ｊ＠度炭酸バリウム
（ＢａＣＯ、堺化学製） ６８０．７２
ｇ高純度炭酸ストロンチウム
（ＳｒＣＯ、本荘ケミカル社製） ２６．８０７１
酸化チタン
（ＴＩＯＮ東邦チタニウム社製） ２９０．１２９酸
化アンチモン
（ＳｂＯ、レアメタリック社製） １．０５８４１
１炭酸マンガン（９９，９％）
（ＭｎＣＯ、和光純薬社製） ０．２０８７
１酸化ケイ素（９９，９％）
（ＳｉＯ、レアメタリック社製） ＋、０９０８１
！を原料としたこと以外は、実施例１と同様にして、測
定用サンプルを調製し、さらに実施例１と同様にして、
電気抵抗値を測定し、さらに比抵抗を算出した。Comparative Example 1 (Conventional method) High J@degree barium carbonate (BaCO, manufactured by Sakai Chemical) 680.72
gHigh-purity strontium carbonate (SrCO, manufactured by Honjo Chemical Co., Ltd.) 26.8071
Titanium oxide (TION manufactured by Toho Titanium Co., Ltd.) 290.129 Antimony oxide (SbO, manufactured by Rare Metallic Co., Ltd.) 1.05841
Manganese monocarbonate (99.9%) (MnCO, manufactured by Wako Pure Chemical Industries) 0.2087
Silicon monoxide (99.9%) (SiO, manufactured by Rare Metallic) +, 09081
! A sample for measurement was prepared in the same manner as in Example 1, except that the raw material was used, and in the same manner as in Example 1,
The electrical resistance value was measured and the specific resistance was calculated.
測定の結果は第３図に示すとおりであった。The measurement results were as shown in Figure 3.
比較例２
比較例１の原料を使用し、円盤状の焼結体の調製におけ
る最終の焼結の焼結条件を１３６０’（：、 １時間と
したこと以外は、実皿例１と同様にして、測定用サンプ
ルを調製し、さらに実施例１と同様にして、測定用サン
プルの電気抵抗値を測定し、さらに比抵抗（Ω・ｃｍ）
を算出した。Comparative Example 2 The raw material of Comparative Example 1 was used, and the sintering conditions for the final sintering in the preparation of a disk-shaped sintered body were set to 1360' (:, 1 hour), but the same procedure as in Example 1 was carried out. Then, a measurement sample was prepared, and the electrical resistance value of the measurement sample was measured in the same manner as in Example 1, and the specific resistance (Ω cm) was measured.
was calculated.
測定の結果は第４図に示すとおりであった。The measurement results were as shown in FIG.
実施例１および２ （本発明）、ならびに比較例１およ
び２ （従来法）の測定の結果を比較すると、第１表に
示すとおりであった。A comparison of the measurement results of Examples 1 and 2 (invention) and Comparative Examples 1 and 2 (conventional method) was as shown in Table 1.
第１表 実施例および比較例における
〔発朗の効果〕
チタン酸バリウム系の半導体磁器材料のＰＴ（特性に影
響を及ぼすことなく、常温における比抵抗を低下するこ
とができる。Table 1 [Effects of heating] in Examples and Comparative Examples PT of barium titanate-based semiconductor ceramic materials (resistivity at room temperature can be lowered without affecting properties).
第１図は、実施例１のチタン酸バリウム系半導体磁器材
料の抵抗−温度特性図、第２図は実施例２−のチタン酸
バリウム系半導体磁器材料の抵抗−温度特性図、第３図
は、比較例１のチタン酸バリウム系半導体磁器材料の抵
抗−温度特性図、および第４図は比較例２のチタン酸バ
リウム系半導体磁器材料の抵抗−温度特性図である。
ＡＪセ ４ｔ！ こ Ｓ
出願人 積水化成品工業株式会社FIG. 1 is a resistance-temperature characteristic diagram of the barium titanate-based semiconductor ceramic material of Example 1, FIG. 2 is a resistance-temperature characteristic diagram of the barium titanate-based semiconductor ceramic material of Example 2-, and FIG. , a resistance-temperature characteristic diagram of the barium titanate-based semiconductor ceramic material of Comparative Example 1, and FIG. 4 is a resistance-temperature characteristic diagram of the barium titanate-based semiconductor ceramic material of Comparative Example 2. AJ Se 4t! S Applicant Sekisui Plastics Co., Ltd.
Claims (1)
酸バリウム系半導体磁器材料において、酸化チタン成分
の一部が亜酸化チタンであることを特徴とするチタン酸
バリウム系半導体磁器材料。(1) A barium titanate semiconductor ceramic material containing a barium titanate semiconductor additive, characterized in that a part of the titanium oxide component is titanium suboxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63269542A JPH02120277A (en) | 1988-10-27 | 1988-10-27 | Barium titanate semiconductor porcelain material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63269542A JPH02120277A (en) | 1988-10-27 | 1988-10-27 | Barium titanate semiconductor porcelain material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02120277A true JPH02120277A (en) | 1990-05-08 |
| JPH0478579B2 JPH0478579B2 (en) | 1992-12-11 |
Family
ID=17473828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63269542A Granted JPH02120277A (en) | 1988-10-27 | 1988-10-27 | Barium titanate semiconductor porcelain material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02120277A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0538801U (en) * | 1991-10-30 | 1993-05-25 | 株式会社村田製作所 | Positive characteristic thermistor element |
-
1988
- 1988-10-27 JP JP63269542A patent/JPH02120277A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0538801U (en) * | 1991-10-30 | 1993-05-25 | 株式会社村田製作所 | Positive characteristic thermistor element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0478579B2 (en) | 1992-12-11 |
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