JPH0417303A - Manufacture of barium titanate porcelain semiconductor - Google Patents
Manufacture of barium titanate porcelain semiconductorInfo
- Publication number
- JPH0417303A JPH0417303A JP12146990A JP12146990A JPH0417303A JP H0417303 A JPH0417303 A JP H0417303A JP 12146990 A JP12146990 A JP 12146990A JP 12146990 A JP12146990 A JP 12146990A JP H0417303 A JPH0417303 A JP H0417303A
- Authority
- JP
- Japan
- Prior art keywords
- barium titanate
- semiconductor
- mixture
- dried
- temperature
- 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
- 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 38
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 38
- 239000004065 semiconductor Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 235000006748 manganese carbonate Nutrition 0.000 abstract description 6
- 239000011656 manganese carbonate Substances 0.000 abstract description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 4
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011363 dried mixture Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 8
- 229910000410 antimony oxide Inorganic materials 0.000 description 7
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 7
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 description 6
- 229940093474 manganese carbonate Drugs 0.000 description 5
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229910010252 TiO3 Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 239000004568 cement Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
Landscapes
- 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、キュリー点以上の温度において正の抵抗温度
係数を有し、室温抵抗率が非常に小さいことによる優れ
たＰＴＣ特性を有するチタン酸バリウム系磁器半導体の
製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides titanic acid which has a positive temperature coefficient of resistance at temperatures above the Curie point and has excellent PTC properties due to very low room temperature resistivity. The present invention relates to a method for manufacturing a barium-based ceramic semiconductor.
ランタン、タンタル、セリウム、イツトリウム、ビスマ
ス、タングステン、銀、サマリウム、ディスプロシウム
等の酸化物をチタン酸バリウム系磁器に添加することに
よって、正の抵抗温度係数（ＰＴＣ特性）を有する磁器
半導体を得ることは、従来から広く知られている。また
、希土類元素、タンタル、ニオブ、またはアンチモンを
含有するチタン酸バリウム系磁器半導体組成物に二酸化
ケイ素を添加し、酸素の存在下で焼成することによって
磁器半導体組成物の電気特性を向上させることも提案さ
れている（特開昭５３−５９８８８号公報参照）。By adding oxides such as lanthanum, tantalum, cerium, yttrium, bismuth, tungsten, silver, samarium, dysprosium, etc. to barium titanate ceramic, a ceramic semiconductor having a positive temperature coefficient of resistance (PTC characteristic) is obtained. This has been widely known for a long time. Additionally, the electrical properties of the ceramic semiconductor composition can be improved by adding silicon dioxide to a barium titanate ceramic semiconductor composition containing a rare earth element, tantalum, niobium, or antimony and firing it in the presence of oxygen. It has been proposed (see Japanese Patent Laid-Open No. 53-59888).
ところが、上記従来のチタン酸バリウム磁器半導体の製
造方法では、キュリー点以上の温度において正の抵抗温
度係数を有し、かつ室温において抵抗率の非常に小さい
素子を得るのは難しいという問題点を有している。However, the conventional method for manufacturing barium titanate ceramic semiconductors described above has the problem that it is difficult to obtain an element that has a positive temperature coefficient of resistance at temperatures above the Curie point and has a very low resistivity at room temperature. are doing.
本発明に係るチタン酸バリウム磁器半導体の製造方法は
、上記課題を解決するために、キュリー点移動物質を含
むチタン酸バリウム基体組成物に半導体化剤を加えて焼
成してなるチタン酸バリウム磁器半導体の製造方法にお
いて、半導体化剤として、チタン酸バリウム基体組成物
に対してＳｂ２Ｏ３を使用することを特徴としている。In order to solve the above-mentioned problems, a barium titanate porcelain semiconductor according to the present invention is produced by adding a semiconducting agent to a barium titanate base composition containing a Curie point transfer substance and firing the mixture. The manufacturing method is characterized in that Sb2O3 is used as a semiconducting agent for a barium titanate base composition.
なお、５ｂ２０．の添加量は、好ましくは０．０７５モ
ル％〜０．１４モル％の範囲である。In addition, 5b20. The amount added is preferably in the range of 0.075 mol% to 0.14 mol%.
上記の構成によれば、半導体化剤として添加した０、０
７５モル％〜０．１４モル％の５ｂｚＯ３によって、半
導体化が容易に行え、しかも室温での抵抗率をより小さ
（設定することができるので、電流容量の小さい回路中
に対応することができる汎用性に優れた低抵抗ＰＣＴ素
子を製造することができる。According to the above configuration, 0, 0 added as a semiconducting agent
With 75 mol% to 0.14 mol% of 5bzO3, it can be easily made into a semiconductor, and the resistivity at room temperature can be set to a lower value, so it is a general-purpose product that can be used in circuits with small current capacity. A low resistance PCT element with excellent properties can be manufactured.
本発明の一実施例を第１図に基づいて説明すれば、以下
のとおりである。An embodiment of the present invention will be described below based on FIG.
本実施例は、キュリー点移動物質を含むチタン酸バリウ
ム基体組成物に半導体化剤を加えて焼成することからな
るチタン酸バリウム磁器半導体の製造方法において、半
導体化剤として、チタン酸バリウム基体組成物に対して
０．０７０モル％〜０．１８０モル％の酸化アンチモン
（５ｂｚＯ＋ ）を使用した時に、５ｂｚｏ、の添加量
によって室温における抵抗率がどのように変化し、その
結果、チタン酸バリウム磁器半導体の製造に対して好ま
しい５ｂ２ｏ、の添加量の範囲を限定することを開示し
ている。This example describes a method for producing a barium titanate ceramic semiconductor, which comprises adding a semiconducting agent to a barium titanate base composition containing a Curie point transfer substance and firing the mixture. When antimony oxide (5bzO+) is used in an amount of 0.070 mol% to 0.180 mol% relative to barium titanate ceramic semiconductor, how does the resistivity at room temperature change depending on the amount of 5bzo added? It is disclosed that the range of the amount of 5b2o added is preferably limited for the production of 5b2o.
本実施例においては、炭酸ストロンチウム（ＳｒＣＯｌ
）等のキュリー点移動物質を含むチタン酸バリウム基体
組成物に対して０．０７０モル％〜０．１５０モル％の
酸化アンチモン（５ｂｚＯｚ ）を配合するが、その際
、この配合物に鉱化剤として炭酸マンガン（ＭｎＣ０３
）を、また電圧依存性安定荊として二酸化ケイ素（５ｉ
Ｏｚ ）等を配合している。In this example, strontium carbonate (SrCOl
0.070 mol% to 0.150 mol% of antimony oxide (5bzOz) is blended into a barium titanate base composition containing a Curie point transfer substance such as as manganese carbonate (MnC03
), and silicon dioxide (5i
Oz) etc. are blended.
この配合物を自動乳鉢において１時間〜２４時間、エタ
ノール（特級試薬）の存在下で湿式混合し、乾燥した後
、１０００’Ｃ〜１４００°Ｃにおいて１時間〜３時間
仮焼する。仮焼した配合物は、粉砕し、自動乳鉢におい
てＰＶＡ（ポリビニルアルコール）２ｗｔ％〜８ｗｔ％
の水溶液を加えて１時間〜６時間混合し、乾燥した後に
十分粉砕する。このようにしてできた粉末を円盤状成形
器において成形した後、その成形物を１３００°Ｃ〜１
４００°Ｃにおいて０時間〜１０時間保持し、焼成して
チタン酸バリウム磁器半導体が得られる。The formulation is wet mixed in an automatic mortar for 1 to 24 hours in the presence of ethanol (special grade reagent), dried, and then calcined at 1000'C to 1400C for 1 to 3 hours. The calcined compound is crushed and mixed with PVA (polyvinyl alcohol) 2wt% to 8wt% in an automatic mortar.
Add an aqueous solution of , mix for 1 to 6 hours, dry, and then thoroughly pulverize. After molding the powder thus produced in a disc molding machine, the molded product was heated to 1300°C to 1
The barium titanate ceramic semiconductor is obtained by holding at 400°C for 0 to 10 hours and firing.
以下において本発明を〔実施例工〕ないし〔実施例４〕
に基づいて、さらに詳細に説明する。The present invention will be described below with reference to [Example Work] to [Example 4].
This will be explained in more detail based on the following.
〔実施例１〕
無水炭酸バリウム（ＢａＣＯｚ 、日本化学工業製高純
度品） ６８．０７ ｇ、高純度二酸化チタン（ＴｉＯ
□、東邦チタニウム社製） ２９．０１ ｇ、無水炭酸
ストロンチウム（ＳｒＣＯ，、本荘ケミカル社製）２．
６８ｇ、炭酸マンガン（Ｍｎｃｏ３、和光純薬社製９９
．９％）０゜０２０９ ｇ、二酸化ケイ素（ＳｉＯｚ、
東芝セラミックス製 ｕｓ−８５） ０．１０９１ｇ、
酸化アンチモン（ＳｂＪ：＋、レアメタリック社製 ９
９．９９％試薬） ０．１０５８ｇを内径２００ＩＩＩ
Ｉｌのアルミナ乳鉢に入れ、自動乳鉢において３時間エ
タノール（特級試薬）の存在下で湿式混合した後、その
混合物を１３０℃において乾燥した。その乾燥混合物を
９０ｍｍＸ９０ｍｍのアルミナルツボ（三菱鉱業セメン
ト類、ＤＦＡ−ＰＳ９９）に入れ、これを電気炉に入れ
て１８０°Ｃ／ｈの昇温速度で加熱し、１１５０°Ｃで
２時間仮焼した。[Example 1] 68.07 g of anhydrous barium carbonate (BaCOz, high-purity product manufactured by Nihon Kagaku Kogyo), high-purity titanium dioxide (TiO
□, manufactured by Toho Titanium Co., Ltd.) 29.01 g, anhydrous strontium carbonate (SrCO, manufactured by Honjo Chemical Co., Ltd.)2.
68g, manganese carbonate (Mnco3, manufactured by Wako Pure Chemical Industries, Ltd. 99
．． 9%) 0°0209 g, silicon dioxide (SiOz,
Toshiba Ceramics us-85) 0.1091g,
Antimony oxide (SbJ:+, manufactured by Rare Metallic Co., Ltd. 9
9.99% reagent) 0.1058g to inner diameter 200III
After wet mixing in an automatic mortar for 3 hours in the presence of ethanol (special grade reagent), the mixture was dried at 130°C. The dry mixture was placed in a 90 mm x 90 mm aluminum crucible (Mitsubishi Mining Cement, DFA-PS99), placed in an electric furnace, heated at a temperature increase rate of 180°C/h, and calcined at 1150°C for 2 hours. .
その仮焼物を乳鉢で粉砕した後、自動乳鉢においてＰＶ
Ａ（ポリビニルアルコール）２−ｔ％水溶液を約１００
ｃｃとともに３時間部合し、１３０″Ｃで乾燥した。After crushing the calcined product in a mortar, PV
About 100% A (polyvinyl alcohol) 2-t% aqueous solution
cc for 3 hours and dried at 130''C.
このようにして得られた乾燥物を乳鉢でよく粉砕し、Ｐ
ＶＡ配合の粉末を成形用成形器（１２，５ｍｍ（径）
Ｘ３５ａｍ （高さ）］に入れ、１ ｔｏｎ ／ｃｒｌ
の加圧下に成形し、その成形物を次の条件において焼成
した。Thoroughly crush the dried product thus obtained in a mortar, and
A molding machine (12.5 mm (diameter)) for molding powder containing VA
x35am (height)], 1 ton/crl
The molded product was then fired under the following conditions.
温度範囲 昇温または降温の条件室温 〜８０
０°Ｃ１４５°ｃ／ｈの昇温８００°Ｃ２時間保持
８００°Ｃ〜１３６０°Ｃ１５０°Ｃ／ｈの昇温１３６
０″ＣＩ５分間保持
１３６０″Ｃ−１０００″Ｃ３６０℃／ｈの降温１００
０°Ｃ〜５５０°Ｃ２４５°Ｃ／ｈの降温５５０°Ｃ温
度コントロールの終了
室温に冷却した後、錠剤状成形物の円盤面にオーミック
性の銀電極（デグサ社製）を塗布し、５８０゛Ｃにおい
て５分間焼付けて電極を形成し、その電極上にカバー電
極（デグサ社製）を塗布し、さらに５６０℃において５
分間焼付けを行って、チタン酸バリウム磁器半導体の試
料を得た。Temperature range: Conditions for heating or cooling Room temperature ~80
Temperature increase at 0°C 145°C/h 800°C Hold for 2 hours 800°C - 1360°C Temperature increase at 150°C/h 136
0″CI held for 5 minutes 1360″C-1000″C 360°C/h temperature drop 100
0°C to 550°C 245°C/h temperature drop 550°C End of temperature control After cooling to room temperature, an ohmic silver electrode (manufactured by Degussa) was applied to the disk surface of the tablet-shaped molded product, and the temperature was lowered to 580°C. Baking for 5 minutes at 560°C to form an electrode, coating the electrode with a cover electrode (manufactured by Degussa), and baking at 560°C for 5 minutes.
Baking was performed for a minute to obtain a sample of barium titanate porcelain semiconductor.
このチタン酸バリウム磁器半導体の原料の配合組成は次
のとおりであった。The composition of the raw materials for this barium titanate ceramic semiconductor was as follows.
（Ｂａ、、、 ｑｓＳｒｏ、 ｏｓ ） ＴｉＯ３＋
Ｏ，ＯＯ０５ＭｎＯｚ ＋０．００５ＳｉＯｚ＋０．０
０１０ｓｂ、ｏ３
この試料の抵抗の温度変化を測定した結果、正の抵抗温
度係数を示す領域が生じる温度（キュリー点）は１０３
°Ｃであり、抵抗の立ち上がり幅は４．２桁であった。(Ba,..., qsSro, os) TiO3+
O,OO05MnOz +0.005SiOz+0.0
010sb, o3 As a result of measuring the temperature change of the resistance of this sample, the temperature (Curie point) at which a region exhibiting a positive temperature coefficient of resistance occurs is 103
°C, and the rise width of the resistance was 4.2 digits.
このとき室温での抵抗率は１４．００Ω・ｌであった。At this time, the resistivity at room temperature was 14.00 Ω·l.
〔実施例２〕
無水炭酸バリウム（ＢａＣ０ｚ ） ６８．０５ ｇ、
高純度二酸化チタン（ＴｉＯ□） ２９．００ ｇ、無
水炭酸ストロンチウム（５ｒＣＯｚ） ２．６８ｇ、炭
酸マンガン（ＭｎｃＯ：＋ ）０．０２０９ ｇ、二酸
化ケイ素（５ｉＯｚ ） ０．１０９０８、酸化７７＋
モア（５ｂＺＯ３） ０．１３７５ｇｔ−使用したこと
以外は上記実施例１と同様にしてチタン酸バリウム磁器
半導体の試料を得た。[Example 2] Anhydrous barium carbonate (BaC0z) 68.05 g,
High purity titanium dioxide (TiO□) 29.00 g, anhydrous strontium carbonate (5rCOz) 2.68g, manganese carbonate (MncO:+) 0.0209 g, silicon dioxide (5iOz) 0.10908, oxidation 77+
A barium titanate ceramic semiconductor sample was obtained in the same manner as in Example 1 above, except that 0.1375 gt of Moa (5bZO3) was used.
このチタン酸バリウム磁器半導体の原料の配合組成は次
のとおりである。The composition of the raw materials for this barium titanate ceramic semiconductor is as follows.
（Ｂａａ、 ｑｓｓｒｏ、 ａｓ ） ＴｉＯ３＋０．
０００５ＭｎＯ２＋０．００５ＳｉＯ２十０．００１３
ＳｂｚＯ３
この試料の抵抗の温度変化を測定した結果、正の抵抗温
度係数を示す領域が生じる温度（キュリー点）は１０５
℃であり、抵抗の立ち上がり幅は３．５桁であった。こ
のとき室温での抵抗率は４．９４Ω・１であった。(Baa, qssro, as) TiO3+0.
0005MnO2 + 0.005SiO2 0.0013
SbzO3 As a result of measuring temperature changes in the resistance of this sample, the temperature at which a region exhibiting a positive temperature coefficient of resistance occurs (Curie point) is 105
℃, and the resistance rise width was 3.5 digits. At this time, the resistivity at room temperature was 4.94Ω·1.
〔実施例３〕
無水炭酸バリウム（ＢａＣＯｘ ） ６９．００ ｇ、
高純度二酸化チタン（ＴｉＯ□） ２９．０２ ｇ、無
水炭酸ストロンチウム（５ｒＣＯ：＋ ） ２．６８ｇ
、炭酸マンガン（ＭｎｃＯｓ ）０．０２０９ ｇ、二
酸化ケイ素（５ｉＯｚ ） ０．１０９１ｇ、酸化アン
チモン（ｓｂ、ｏ、 ） ０．０７４１ ｇを使用した
こと以外は上記実施例１と同様にしてチタン酸バリウム
磁器の試料を得た。[Example 3] Anhydrous barium carbonate (BaCOx) 69.00 g,
High purity titanium dioxide (TiO□) 29.02 g, anhydrous strontium carbonate (5rCO:+) 2.68 g
Barium titanate porcelain was prepared in the same manner as in Example 1 above, except that 0.0209 g of manganese carbonate (MncOs), 0.1091 g of silicon dioxide (5iOz), and 0.0741 g of antimony oxide (SB, O, ) were used. samples were obtained.
このチタン酸バリウム磁器の原料の配合組成は次のとお
りである。The composition of the raw materials for this barium titanate porcelain is as follows.
（Ｂａｏ、 ｑｓＳｒｏ、 ａｓ ） ＴｉＯ：＋ ＋
Ｏ，ＯＯ０５ＭｎＯｚ ＋〇、 ００５ＳｉＯｚ＋Ｏ
，０Ｏ０７Ｓｂ２０２
この試料の室温での抵抗率は、３．４ ＸＩＯ’Ω・ｌ
であったが、半導体とならず、上記諸特性の測定は不可
能であった。(Bao, qsSro, as) TiO: + +
O, OO05MnOz +〇, 005SiOz+O
,0O07Sb202 The resistivity of this sample at room temperature is 3.4 XIO'Ω・l
However, it did not become a semiconductor, and it was impossible to measure the above characteristics.
〔実施例４］
無水炭酸バリウム（ＢａＣ０３） ６８．０４ ｇ、高
純度二酸化チタン（Ｔｉ０ｚ ） ２９．００ ｇ、無
水炭酸ストロンチウム（ＳｒＣＯ３） ２．６８ｇ、炭
酸マンガン（ＭｎｃＯｚ ）０．０２０９ ｇ、二酸化
ケイ素（５ｉＯｚ ） ０．１０９０ｇ、酸化アンチモ
ン（５ｂ２ｏ、 ） ０．１５８７ｇを使用したこと以
外は上記実施例１と同様にしてチタン酸バリウム磁器の
試料を得た。[Example 4] Anhydrous barium carbonate (BaC03) 68.04 g, high purity titanium dioxide (Ti0z) 29.00 g, anhydrous strontium carbonate (SrCO3) 2.68 g, manganese carbonate (MncOz) 0.0209 g, silicon dioxide A sample of barium titanate porcelain was obtained in the same manner as in Example 1 above, except that 0.1090 g of (5 iOz) and 0.1587 g of antimony oxide (5b2O, ) were used.
このチタン酸バリウム磁器の原料の配合組成は次のとお
りである。The composition of the raw materials for this barium titanate porcelain is as follows.
（Ｂａａ、 ９ＳｓｒＯ，ｏｓ） ＴｉＯ３＋ ０．０
００５ＭｎＯｚ ＋ ０．００５ＳｉＯｚ＋０．００１
５ＳｂｚＯ＋
この試料は絶縁体化して半導体とならず、上記諸特性の
測定は不可能であった。(Baa, 9SsrO,os) TiO3+ 0.0
005MnOz + 0.005SiOz+0.001
5SbzO+ This sample became an insulator and did not become a semiconductor, so it was impossible to measure the above characteristics.
以上より、〔実施例１〕ないし〔実施例４］の結果を整
理すると、第１表に示すようになる。第１表から明らか
なように、半導体化剤として、チタン酸バリウム基体組
成物に対して酸化アンチモン（５ｂｚＯｓ’）を使用す
ることによって、室温における抵抗率を非常に小さくす
ることができる。また、上記チタン酸バリウム磁器半導
体の５ｂ２０ａ添加量依存性（〔実施例１］ないし〔実
施例３〕の各試料の特性に対応する）は、第１図に示す
ようになる。即ち、第１図に示すように、チタン酸バリ
ウム磁器半導体の５ｂｚＯｚ添加量が０．０７５モル％
よりも小さいか、または０．１４モル％よりも大きい場
合、室温における抵抗率（比抵抗）は大きくなってしま
う。よって、５ｂｚＯｚの添加量は、好ましくは、０．
０７５モル％〜０．１４モル％の範囲であることがわか
る。From the above, the results of [Example 1] to [Example 4] are summarized as shown in Table 1. As is clear from Table 1, by using antimony oxide (5bzOs') as a semiconducting agent for the barium titanate base composition, the resistivity at room temperature can be made very low. Further, the dependence of the 5b20a addition amount of the barium titanate ceramic semiconductor (corresponding to the characteristics of each sample of [Example 1] to [Example 3]) is shown in FIG. That is, as shown in FIG. 1, the amount of 5bzOz added to the barium titanate ceramic semiconductor is 0.075 mol%.
or greater than 0.14 mol%, the resistivity (specific resistance) at room temperature will become large. Therefore, the amount of 5bzOz added is preferably 0.
It can be seen that the content ranges from 0.075 mol% to 0.14 mol%.
二こで、原料の配合組成の異なる上記各種チタン酸バリ
ウム磁器半導体の試料の諸物性の測定方法を以下に説明
する。Now, methods for measuring various physical properties of samples of the above-mentioned barium titanate ceramic semiconductors having different compositions of raw materials will be explained below.
（１）キュリー点の測定
チタン酸バリウム磁器半導体の試料を測定用の試料ホル
ダーに取り付け、測定槽（ＭＩＮＩ−５ＩＩＢＺＥＲＯ
にＣ−８１０Ｐ タバイ ニスペック■製）内に装着
して、−５０°Ｃから１９０℃までの温度変化に対する
試料の電気抵抗の変化を直流抵抗計（マルチメーター３
４７８Ａ Ｙ ＨＰ製）を用いて測定した。(1) Measurement of Curie point Attach the barium titanate porcelain semiconductor sample to the measurement sample holder, and place it in the measurement tank (MINI-5IIBZERO
C-810P (manufactured by Nisspec ■) in a DC resistance meter (Multimeter 3
478A (manufactured by HP).
測定により得られた電気抵抗−温度のプロットより、抵
抗値が室温における抵抗値の２倍になるときの温度をキ
ュリー点とした。From the electrical resistance-temperature plot obtained by measurement, the temperature at which the resistance value becomes twice the resistance value at room temperature was defined as the Curie point.
（２）室温抵抗率の測定
チタン酸バリウム磁器半導体の試料を２５°Ｃの測定槽
において、直流抵抗計（マルチメーター３４７８ＡＹＨ
Ｐ製）を用いて電気抵抗値を測定した。(2) Measurement of room temperature resistivity A barium titanate porcelain semiconductor sample was placed in a measurement tank at 25°C using a DC resistance meter (multimeter 3478AYH).
The electrical resistance value was measured using a commercially available product (manufactured by P.P.).
チタン酸バリウム磁器半導体の試料の調製において、電
極塗布前に試料の大きさ（径および厚さ）を測定してお
き、次式により比抵抗（ρ）を算出し、これを抵抗率と
した。In preparing a barium titanate porcelain semiconductor sample, the size (diameter and thickness) of the sample was measured before applying the electrode, and the specific resistance (ρ) was calculated using the following formula, and this was taken as the resistivity.
ρ＝Ｒ−Ｓ／ｌ
ρ： 比抵抗（抵抗率） 〔Ω・１〕Ｒ： 電気抵抗
の測定値 〔Ω〕
Ｓ： 電極の面積 （ｃ４）
ｔ： 試料の厚さ 〔Ω〕
（３）抵抗率の立ち上がり幅の測定
キュリー点の測定の温度変化（−５０℃から１９０”ｃ
＞に対する試料の電気抵抗の変化の測定を、さらに２
００℃を超える温度まで続行し、その抵抗率−温度プロ
ットにおいて、キュリー点における電気抵抗の急激な立
ち上がりのときの抵抗率と、２００°Ｃにおける抵抗率
とを比較して、その桁数の対数比を抵抗率の立ち上がり
幅とした。ρ=R-S/l ρ: Specific resistance (resistivity) [Ω・1] R: Measured value of electrical resistance [Ω] S: Area of electrode (c4) t: Thickness of sample [Ω] (3) Measurement of rise width of resistivity Temperature change for measurement of Curie point (from -50℃ to 190"C)
＞The change in electrical resistance of the sample was measured for 2 more times.
Continue until the temperature exceeds 00°C, and in the resistivity-temperature plot, compare the resistivity at the sudden rise in electrical resistance at the Curie point with the resistivity at 200°C, and calculate the logarithm of the number of digits. The ratio was taken as the rise width of resistivity.
なお、本発明に係るチタン酸バリウム磁器半導体は、室
温において抵抗率が小さいので、電流容量の小さい回路
における低抵抗ＰＴＣ素子として使用することができ、
例えば温度ヒユーズスイッチング電源のコンパレータと
しても使用することができる。本発明に係るチタン酸バ
リウム磁器半導体は、上記以外に、電解コンデンサーの
保護回路、カラーＴＶ自動消磁装置、自動車等のモータ
起動装置、電子機器の過熱防止装置、遅延素子、タイマ
、液面計、無接点スイッチ、リレー接点保護装置などに
利用することができる。In addition, since the barium titanate ceramic semiconductor according to the present invention has a low resistivity at room temperature, it can be used as a low resistance PTC element in a circuit with a small current capacity.
For example, it can also be used as a comparator for a temperature fuse switching power supply. In addition to the above, the barium titanate ceramic semiconductor according to the present invention can be applied to electrolytic capacitor protection circuits, color TV automatic degaussing devices, motor starting devices for automobiles, overheat prevention devices for electronic equipment, delay elements, timers, liquid level gauges, etc. Can be used for non-contact switches, relay contact protection devices, etc.
（以下余白）
第１表
（以下余日）
［発明の効果］
本発明に係るチタン酸バリウム磁器半導体の製造方法は
、半導体化剤として、チタン酸バリウム基体組成物に対
して０．０７５モル％〜０．１４モル％の５ｂｚＯ３を
使用する構成をなしている。(Hereinafter in the margins) Table 1 (hereinafter in the remaining days) [Effects of the invention] The method for producing a barium titanate ceramic semiconductor according to the present invention uses 0.075 mol% of the barium titanate base composition as a semiconducting agent. The composition uses ~0.14 mol% of 5bzO3.
それゆえ、半導体化がより容易に行え、しかもキュリー
点以上の温度において正の抵抗温度係数を有すると共に
、室温での抵抗率をより小さく設定することができるの
で、電流容量の小さい回路中に対応することができる汎
用性に優れた低抵抗ＰＴＣ素子を製造できるという効果
を奏する。Therefore, it can be made into a semiconductor more easily, has a positive temperature coefficient of resistance at temperatures above the Curie point, and can be set to a smaller resistivity at room temperature, making it suitable for use in circuits with small current capacity. It is possible to manufacture a low-resistance PTC element with excellent versatility.
第１図は本発明の一実施例を示すものであり、本発明に
係るチタン酸バリウム磁器半導体の比抵抗の酸化アンチ
モン（ＳｂｚＯｘ ）添加量依存性を示す説明図である
。
特許出願人 積水化成品工業株式会社代理人
弁理士 原 謙FIG. 1 shows an embodiment of the present invention, and is an explanatory diagram showing the dependence of the resistivity of a barium titanate ceramic semiconductor according to the present invention on the amount of antimony oxide (SbzOx) added. Patent applicant Sekisui Plastics Co., Ltd. Agent
Patent attorney Ken Hara
Claims (1)
成物に半導体化剤を加えて焼成してなるチタン酸バリウ
ム磁器半導体の製造方法において、半導体化剤として、
チタン酸バリウム基体組成物に対して０．０７５モル％
〜０．１４モル％のＳｂ＿２Ｏ＿３を使用することを特
徴とするチタン酸バリウム磁器半導体の製造方法。1. In a method for producing a barium titanate ceramic semiconductor by adding a semiconducting agent to a barium titanate base composition containing a Curie point transfer substance and firing the mixture, as the semiconducting agent,
0.075 mol% based on barium titanate base composition
A method for producing a barium titanate ceramic semiconductor, characterized in that ~0.14 mol% of Sb_2O_3 is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2121469A JP2839932B2 (en) | 1990-05-10 | 1990-05-10 | Method for producing barium titanate porcelain semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2121469A JP2839932B2 (en) | 1990-05-10 | 1990-05-10 | Method for producing barium titanate porcelain semiconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0417303A true JPH0417303A (en) | 1992-01-22 |
| JP2839932B2 JP2839932B2 (en) | 1998-12-24 |
Family
ID=14811923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2121469A Expired - Fee Related JP2839932B2 (en) | 1990-05-10 | 1990-05-10 | Method for producing barium titanate porcelain semiconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2839932B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147292A (en) * | 1974-10-18 | 1976-04-22 | Matsushita Electric Ind Co Ltd | |
| JPS5595673A (en) * | 1978-12-27 | 1980-07-21 | Matsushita Electric Ind Co Ltd | Semiconductive ceramic material and production thereof |
| JPS58147004A (en) * | 1982-02-25 | 1983-09-01 | 松下冷機株式会社 | Method of producing semiconductor porcelain material |
-
1990
- 1990-05-10 JP JP2121469A patent/JP2839932B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147292A (en) * | 1974-10-18 | 1976-04-22 | Matsushita Electric Ind Co Ltd | |
| JPS5595673A (en) * | 1978-12-27 | 1980-07-21 | Matsushita Electric Ind Co Ltd | Semiconductive ceramic material and production thereof |
| JPS58147004A (en) * | 1982-02-25 | 1983-09-01 | 松下冷機株式会社 | Method of producing semiconductor porcelain material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2839932B2 (en) | 1998-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6071842A (en) | Barium titanate-based semiconductor ceramic | |
| JP5988388B2 (en) | Semiconductor porcelain composition and method for producing the same | |
| JP4058140B2 (en) | Barium titanate semiconductor porcelain | |
| JPH0417303A (en) | Manufacture of barium titanate porcelain semiconductor | |
| JP2613327B2 (en) | Barium titanate-based porcelain semiconductor | |
| JP2690597B2 (en) | Method for producing barium titanate porcelain semiconductor | |
| JP4217337B2 (en) | Manufacturing method of semiconductor porcelain | |
| JPH01143202A (en) | Positive temperature coefficient(ptc) thermister for moderate high temperature | |
| JP2000264726A (en) | Semiconductor porcelain | |
| JP2595385B2 (en) | Method for producing barium titanate-based porcelain semiconductor | |
| JPS6243522B2 (en) | ||
| JP6075877B2 (en) | Semiconductor porcelain composition and method for producing the same | |
| JPH07297009A (en) | Positive temperature coefficient thermistor and manufacturing method thereof | |
| JP2705019B2 (en) | Porcelain semiconductor composition and method for producing the same | |
| JPH0822773B2 (en) | Method for manufacturing barium titanate porcelain semiconductor | |
| JPH07118061A (en) | Barium titanate-based semiconductor porcelain composition | |
| JP2566335B2 (en) | Method for manufacturing barium titanate porcelain semiconductor | |
| JPH03218966A (en) | Production of barium titanate-based porcelain semiconductor | |
| JP2511561B2 (en) | Method for manufacturing barium titanate porcelain semiconductor | |
| JP2613323B2 (en) | Barium titanate-based porcelain semiconductor | |
| JPH02283665A (en) | Production of barium titanate porcelain semiconductor | |
| JPH04144201A (en) | Positive temperature coefficient thermistor and manufacture thereof | |
| JPS5948521B2 (en) | Method for manufacturing positive characteristic semiconductor porcelain | |
| JPH04238860A (en) | Production of barium titanate-based porcelain semiconductor | |
| JPS63280401A (en) | Semiconductor porcelain composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |