JPH04280861A - Composition for barium titanate-based semiconductor porcelain and barium titanate-based semiconductor porcelain using the same composition - Google Patents
Composition for barium titanate-based semiconductor porcelain and barium titanate-based semiconductor porcelain using the same compositionInfo
- Publication number
- JPH04280861A JPH04280861A JP3063741A JP6374191A JPH04280861A JP H04280861 A JPH04280861 A JP H04280861A JP 3063741 A JP3063741 A JP 3063741A JP 6374191 A JP6374191 A JP 6374191A JP H04280861 A JPH04280861 A JP H04280861A
- Authority
- JP
- Japan
- Prior art keywords
- barium titanate
- based semiconductor
- mol
- composition
- semiconductor 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
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 58
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 46
- 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 45
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 12
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 10
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 10
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 235000010216 calcium carbonate Nutrition 0.000 claims abstract description 9
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 8
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims description 21
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910019639 Nb2 O5 Inorganic materials 0.000 description 1
- 229910003781 PbTiO3 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
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
導体磁器用組成物およびそれを用いて得られるチタン酸
バリウム系半導体磁器に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barium titanate semiconductor ceramic composition and a barium titanate semiconductor ceramic composition obtained using the composition.
【0002】0002
【従来の技術】従来、例えば、特公昭63−28324
号公報には、主成分としてBaTiO3 、CaTiO
3 、SrTiO3 およびPbTiO3 と、半導体
化剤としての稀土類元素などと、添加物としてのMnお
よびSiO2 とよりなるチタン酸バリウム系半導体磁
器組成物が開示されている。[Prior Art] Conventionally, for example, Japanese Patent Publication No. 63-28324
The publication contains BaTiO3 and CaTiO as main components.
No. 3, a barium titanate-based semiconductor ceramic composition comprising SrTiO3 and PbTiO3, a rare earth element as a semiconductor agent, and Mn and SiO2 as additives is disclosed.
【0003】また、特開昭58−68903号公報には
、主原料としてのBaCO3 、PbO、CaCO3
、SrCO3 およびTiO2 、半導体化剤としての
Y2 O3 、添加剤としてのMnCO3 、SiO2
およびAl2 O3 を添加してなるチタン酸バリウ
ム系半導体磁器が開示されている。[0003] Furthermore, JP-A No. 58-68903 discloses that BaCO3, PbO, CaCO3 as main raw materials
, SrCO3 and TiO2, Y2 O3 as a semiconducting agent, MnCO3 as an additive, SiO2
A barium titanate-based semiconductor ceramic made by adding Al2O3 and Al2O3 is disclosed.
【0004】特公昭55−42442号公報には、チタ
ン酸バリウムあるいはバリウムの一部をスズまたは鉛で
置換したチタン酸バリウム系固溶体に半導体化元素とし
てNbを添加し、更にMnとSiO2 とを添加してな
るチタン酸バリウム系半導体磁器材料が開示されている
。[0004] Japanese Patent Publication No. 55-42442 discloses that Nb is added as a semiconductor element to barium titanate or a barium titanate solid solution in which a part of the barium is replaced with tin or lead, and further Mn and SiO2 are added. A barium titanate-based semiconductor ceramic material is disclosed.
【0005】[0005]
【発明が解決しようとする課題】チタン酸バリウム系半
導体磁器を、正の抵抗温度特性をもつ半導体として、定
温発熱体などに応用して使用する場合、その正の抵抗温
度特性を維持できる最大使用電圧が充分に高いことが、
安全性の点から重要である。さらに、その正の抵抗温度
特性を維持できる最大使用電圧がより高いチタン酸バリ
ウム系半導体磁器ほど、電気部品としての応用範囲を広
くすることが可能となる。[Problem to be Solved by the Invention] When barium titanate-based semiconductor ceramics is used as a semiconductor with positive resistance-temperature characteristics in a constant-temperature heating element, etc., what is the maximum usage that can maintain its positive resistance-temperature characteristics? Make sure the voltage is high enough
This is important from a safety point of view. Furthermore, barium titanate-based semiconductor porcelain having a higher maximum operating voltage at which it can maintain its positive resistance-temperature characteristics can be used in a wider range of applications as electrical components.
【0006】チタン酸バリウム系半導体磁器に電極を付
け、これに交流電圧を徐々に印加していった時に、その
電気抵抗値が最大になるときの電圧が、正の抵抗温度特
性を維持できる最大使用電圧である。この最大交流電圧
の実効値(Vrms )を電極を挟んだチタン酸バリウ
ム系半導体磁器の厚み(mm)で割った値〔以下単位厚
み当りの最大使用電圧(Vrms /mm)という〕が
より大きいチタン酸バリウム系半導体磁器ほど、より小
型で安全性の高い製品を得ることができる。When an electrode is attached to barium titanate-based semiconductor porcelain and an alternating current voltage is gradually applied to it, the voltage at which the electrical resistance value reaches its maximum is the maximum voltage that can maintain positive resistance-temperature characteristics. This is the voltage used. The value obtained by dividing the effective value of this maximum AC voltage (Vrms) by the thickness (mm) of the barium titanate-based semiconductor porcelain sandwiching the electrodes [hereinafter referred to as the maximum working voltage per unit thickness (Vrms/mm)] is larger for titanium. The barium oxide semiconductor porcelain makes it possible to obtain smaller and safer products.
【0007】従来の技術によるチタン酸バリウム系半導
体磁器においては、この単位厚み当りの最大使用電圧が
、充分には高くなかった。その原因のひとつとして、従
来の技術によるチタン酸バリウム系半導体磁器の結晶組
織が、充分に微細でないことが挙げられる。一方、該半
導体磁器の結晶組織が微細になり過ぎると単位厚み当り
の抵抗が上昇して所期の目的を達し得ない。[0007] In barium titanate semiconductor ceramics according to the prior art, the maximum operating voltage per unit thickness was not sufficiently high. One of the reasons for this is that the crystal structure of barium titanate-based semiconductor ceramics produced by conventional techniques is not sufficiently fine. On the other hand, if the crystal structure of the semiconductor ceramic becomes too fine, the resistance per unit thickness will increase, making it impossible to achieve the intended purpose.
【0008】本発明者らは、斯かる従来技術に残された
課題を解決すべくチタン酸バリウム系半導体磁器用組成
物およびそれを用いて得られるチタン酸バリウム系半導
体磁器について種々検討した結果、主原料、半導体化剤
および添加剤の各成分を特定し、かつ各成分の配合割合
を特定することにより得られるチタン酸バリウム系半導
体磁器用組成物を用いることにより、その実用的な常温
比抵抗を所期の値に維持しつつ、その結晶組織が十分に
微細であって、その単位厚み当りの最大使用電圧が著し
く増大したチタン酸バリウム系半導体機器を得ることに
成功し、茲に提案するものである。[0008] The present inventors have conducted various studies on barium titanate-based semiconductor ceramic compositions and barium titanate-based semiconductor ceramics obtained using the compositions in order to solve the problems remaining in the prior art. By using a barium titanate-based semiconductor porcelain composition obtained by specifying each component of the main raw material, semiconducting agent, and additive, and specifying the blending ratio of each component, its practical room-temperature specific resistance We have succeeded in obtaining a barium titanate-based semiconductor device whose crystal structure is sufficiently fine and whose maximum operating voltage per unit thickness has been significantly increased while maintaining the desired value, and we are now proposing this. It is something.
【0009】本発明は、200℃以上の高温領域で著し
い正の抵抗温度特性を有し、かつ所期の実用的な常温比
抵抗値を維持しつつ、その結晶組織が十分微細であって
単位厚み当りの最大使用電圧が高いチタン酸バリウム系
半導体磁器、およびその製造に用いられるチタン酸バリ
ウム系半導体磁器用組成物を提供することを目的とする
ものである。The present invention has a significantly positive resistance-temperature characteristic in a high temperature region of 200° C. or higher, maintains the desired practical specific resistance value at room temperature, and has a sufficiently fine crystal structure to form a unit The object of the present invention is to provide barium titanate-based semiconductor porcelain having a high maximum operating voltage per thickness, and a composition for barium titanate-based semiconductor porcelain used in its production.
【0010】本発明は、また主として定温発熱体として
用いられるチタン酸バリウム系半導体磁器、およびその
製造に用いられるチタン酸バリウム系半導体磁器用組成
物を提供することを目的とするものである。Another object of the present invention is to provide a barium titanate-based semiconductor porcelain mainly used as a constant-temperature heating element, and a barium titanate-based semiconductor porcelain composition used for the production thereof.
【0011】[0011]
【問題点を解決するための手段】すなわち、本発明は、
主原料としてのBaCO3 、PbO、CaCO3 、
SrCO3 およびTiO2 、半導体化剤としてのN
b2 O5 、添加剤としてのMnCO3 、SiO2
およびAl2 O3 からなるチタン酸バリウム系半
導体磁器用組成物であって、該TiO2 100モル当
り、BaCO3 50〜80モル、PbO20〜40モ
ル、CaCO3 3〜8モル、SrCO3 2〜9モル
、Nb2 O5 0.10〜0.16モル、MnCO3
0.03〜0.07モル、SiO2 2.0〜3.0
モルおよびAl2 O3 0.05〜1.0モルをそれ
ぞれ配合してなる前記チタン酸バリウム系半導体磁器用
組成物;ならびにチタン酸バリウム系半導体磁器用組成
物を湿式微粉砕混合し、脱水・乾燥後、1000〜11
00℃の温度で仮焼し、再び湿式微粉砕混合し、脱水・
乾燥後、バインダーを混ぜて成形し、1250〜130
0℃の温度で0.5〜3時間焼結することによって得ら
れるチタン酸バリウム系半導体磁器を提供するものであ
る。[Means for solving the problems] That is, the present invention has the following features:
BaCO3, PbO, CaCO3 as main raw materials,
SrCO3 and TiO2, N as a semiconducting agent
b2 O5, MnCO3 as additive, SiO2
A barium titanate-based semiconductor ceramic composition comprising: .10-0.16 mol, MnCO3
0.03-0.07 mol, SiO2 2.0-3.0
The above-mentioned barium titanate-based semiconductor porcelain composition comprising 0.05 to 1.0 mol of Al2O3 and the barium titanate-based semiconductor porcelain composition are wet-pulverized and mixed, and after dehydration and drying. , 1000-11
Calcined at a temperature of 00°C, wet pulverized and mixed again, dehydrated and
After drying, mix binder and mold, 1250~130
The present invention provides barium titanate-based semiconductor porcelain obtained by sintering at a temperature of 0° C. for 0.5 to 3 hours.
【0012】本発明のチタン酸バリウム系半導体磁器用
組成物は、主原料としてのBaCO3 、PbO、Ca
CO3 、SrCO3 およびTiO2 、半導体化剤
としてのNb2 O5 、添加剤としてのMnCO3
、SiO2 およびAl2 O3 を所定割合で配合し
てなるものである。The barium titanate-based semiconductor ceramic composition of the present invention contains BaCO3, PbO, Ca as main raw materials.
CO3, SrCO3 and TiO2, Nb2O5 as a semiconducting agent, MnCO3 as an additive
, SiO2 and Al2O3 in a predetermined ratio.
【0013】上記主原料、半導体化剤および添加剤の各
成分の使用量について以下説明する。The amounts of each of the main raw materials, semiconducting agents and additives to be used will be explained below.
【0014】上記主原料としてのBaCO3 の使用量
は、上記TiO2 100モル当り、通常50〜80モ
ルである。該使用量が50モル未満では、半導体化が困
難となり、80モルを超えると200℃以上のスイッチ
ング温度を得ることができない。The amount of BaCO3 used as the main raw material is usually 50 to 80 moles per 100 moles of TiO2. If the amount used is less than 50 moles, it will be difficult to make it into a semiconductor, and if it exceeds 80 moles, it will be impossible to obtain a switching temperature of 200° C. or higher.
【0015】上記主原料としてのPbOの使用量は、上
記TiO2 100モル当り、通常20〜40モルであ
る。該PbOの使用量が20モル未満であれば、200
℃以上のスイッチング温度を得ることができず、40モ
ルを超えると半導体化が困難となる。The amount of PbO used as the main raw material is usually 20 to 40 moles per 100 moles of the TiO2. If the amount of PbO used is less than 20 moles, 200 moles
It is not possible to obtain a switching temperature of .degree. C. or higher, and if the amount exceeds 40 mol, it becomes difficult to make a semiconductor.
【0016】上記主原料としてのCaCO3 の使用量
は、上記TiO2 100モル当り、通常3〜8モルで
ある。該CaCO3 の使用量が3モル未満であれば、
最大使用電圧が低くなり、8モルを超えると半導体化が
困難となる。The amount of CaCO3 used as the main raw material is usually 3 to 8 moles per 100 moles of TiO2. If the amount of CaCO3 used is less than 3 moles,
The maximum working voltage becomes low, and if it exceeds 8 mol, it becomes difficult to make it into a semiconductor.
【0017】上記主原料としてのSrCO3 の使用量
は、上記TiO2 100モル当り、通常2〜9モルで
ある。該SiCO2 の使用量が2モル未満であると、
最大使用電圧が低くなり、9モルを超えると半導体化が
困難となる。The amount of SrCO3 used as the main raw material is usually 2 to 9 moles per 100 moles of TiO2. When the amount of SiCO2 used is less than 2 mol,
The maximum working voltage becomes low, and if it exceeds 9 mol, it becomes difficult to make it into a semiconductor.
【0018】上記半導体化剤としてのNb2 O5 の
使用量は、上記TiO2 100モル当り、通常0.1
0〜0.16、好ましくは0.13〜0.15モルであ
り、該Nb2 O5 の使用量が上記の範囲内にあると
きは、該チタン酸バリウム系半導体磁器の結晶組織が適
度に微細化され、かつ十分に半導体化されるが、上記範
囲から外れると該結晶組織を適度に微細化させることお
よび十分に半導体化させることの両方を同時に実現させ
ることはできなくなる。The amount of Nb2 O5 used as the semiconductor agent is usually 0.1 per 100 moles of TiO2.
0 to 0.16 mol, preferably 0.13 to 0.15 mol, and when the amount of Nb2O5 used is within the above range, the crystal structure of the barium titanate semiconductor ceramic is appropriately refined. However, if the crystal structure is outside the above range, it will not be possible to simultaneously make the crystal structure appropriately finer and to make it sufficiently semiconductive.
【0019】上記添加剤としてのMnCO3 の使用量
は、上記TiO2 100モル当り、通常0.03〜0
.07モル、好ましくは0.04〜0.06モルであり
、該MnCO3 の使用量が0.04モル未満であれば
最大使用電圧が低くなり、0.07モルを超えると半導
体化が困難となる。The amount of MnCO3 used as the additive is usually 0.03 to 0 per 100 moles of TiO2.
.. 07 mol, preferably 0.04 to 0.06 mol. If the amount of MnCO3 used is less than 0.04 mol, the maximum working voltage will be low, and if it exceeds 0.07 mol, it will be difficult to make a semiconductor. .
【0020】上記添加剤としてのSiO2 の使用量は
、上記TiO2 100モル当り、通常2.0〜3.0
モル、好ましくは2.0〜2.8モルであり、該SiO
2 の使用量が2.0モル未満であれば、半導体化が困
難となり、3.0モルを超えると、焼結時の焼結体同士
の融着が激しくなる。The amount of SiO2 used as the additive is usually 2.0 to 3.0 per 100 moles of TiO2.
mol, preferably 2.0 to 2.8 mol, and the SiO
If the amount of 2 used is less than 2.0 moles, it will be difficult to make it into a semiconductor, and if it exceeds 3.0 moles, the sintered bodies will be violently fused together during sintering.
【0021】上記添加剤としてのAl2 O3 の使用
量は、上記TiO2 100モル当り、通常0.05〜
1.0モルであり、、好ましくは0.08〜0.5モル
であり、該Al2 O3 の使用量が0.05モル未満
であれと実用的な比抵抗と高い使用電圧が得られず、1
.0モルを超えると半導体化が困難となる。The amount of Al2O3 used as the additive is usually 0.05 to 100 moles of TiO2.
1.0 mol, preferably 0.08 to 0.5 mol, and if the amount of Al2O3 used is less than 0.05 mol, practical specific resistance and high working voltage cannot be obtained. 1
.. If the amount exceeds 0 mol, it becomes difficult to make a semiconductor.
【0022】本発明のチタン酸バリウム系半導体磁器用
組成物およびチタン酸バリウム系半導体磁器の製造方法
について説明する。The composition for barium titanate-based semiconductor ceramics and the method for producing barium titanate-based semiconductor ceramics of the present invention will be explained.
【0023】主原料、半導体化剤および添加剤の各成分
を所望の組成比で配合してなるチタン酸バリウム系半導
体磁器用組成物と好ましくは純水とを例えば重量比で1
:1の割合でボールミルに装入し、通常10〜40時間
、好ましくは15〜25時間、湿式微粉砕混合し、得ら
れたスラリーを濾過・脱水・乾燥し、ポリビニルアルコ
ール(PVA)、ポリビニルピロリドン(PVP)、メ
チルセルロース(MC)、純水などのバインダーを混ぜ
て成形圧0〜1000kg/cm2 ・ G 好ましく
は100〜500kg/cm2 ・ G で成形し、耐
熱性のさや容器に移し、電気炉を用いて、通常1000
〜1100℃、好ましくは1025〜1075℃の温度
で通常30分〜10時間、好ましくは1〜3時間仮焼し
、次いで重量比1:1の割合で純水を添加し、ボールミ
ル中で通常10〜40時間、好ましくは15〜25時間
湿式微粉砕混合し、得られた混合物を濾過・脱水・乾燥
し、次いでPVAなどの有機溶媒をバインダーとして添
加・混合して、例えば顆粒状に造粒し、成形圧500〜
2500kg/cm2 ・ G 、好ましくは1000
〜2000kg/cm2 ・ G 、でプレス成形し、
次いで耐熱性さや容器に装入し、通常1250〜130
0℃、好ましくは1250〜1280℃で通常0.5〜
3時間、好ましくは1〜2時間焼結し、次いで通常50
〜500℃/hr、好ましくは100〜300℃/hr
の冷却速度で常温まで冷却することにより本発明のチタ
ン酸バリウム系半導体磁器が得られる。[0023] A barium titanate-based semiconductor porcelain composition prepared by blending each component of the main raw material, a semiconducting agent, and an additive in a desired composition ratio and preferably pure water are mixed in a weight ratio of, for example, 1.
: charged into a ball mill at a ratio of 1:1 and wet-pulverized and mixed for usually 10 to 40 hours, preferably 15 to 25 hours, and the resulting slurry is filtered, dehydrated, and dried to dissolve polyvinyl alcohol (PVA) and polyvinylpyrrolidone. (PVP), methylcellulose (MC), pure water, and other binders are mixed and molded at a molding pressure of 0 to 1000 kg/cm2.G, preferably 100 to 500 kg/cm2.G, transferred to a heat-resistant sheath container, and heated in an electric furnace. Usually 1000
Calcinate at a temperature of ~1100°C, preferably 1025~1075°C for usually 30 minutes to 10 hours, preferably 1 to 3 hours, then add pure water at a weight ratio of 1:1 and boil in a ball mill for usually 10 minutes. The mixture is wet-pulverized and mixed for ~40 hours, preferably 15-25 hours, and the resulting mixture is filtered, dehydrated, and dried, and then an organic solvent such as PVA is added and mixed as a binder, and the mixture is granulated, for example, into granules. , molding pressure 500~
2500kg/cm2・G, preferably 1000
Press molded at ~2000kg/cm2・G,
Next, it is charged into a heat-resistant sheath container, and the temperature is usually 1250 to 130
Usually 0.5-1280°C, preferably 1250-1280°C
Sinter for 3 hours, preferably 1-2 hours, then typically 50
~500℃/hr, preferably 100-300℃/hr
The barium titanate semiconductor ceramic of the present invention can be obtained by cooling to room temperature at a cooling rate of .
【0024】[0024]
【発明の効果】本発明によれば、主原料としてのBaC
O3 、PbO、CaCO3 、SrCO3 およびT
iO2 、半導体化剤としてのNb2 O5 、添加剤
としてのMnCO3 、SiO2 およびAl2 O3
をそれぞれ選定し、かつ、その配合割合を特定するこ
とにより、結晶組織が微細で、かつ実用的な常温比抵抗
と、高い最大使用電圧を有し、200℃以上の高温領域
にスイッチング温度を有するチタン酸バリウム系半導体
磁器およびその製造に用いられるチタン酸バリウム系半
導体磁器用組成物が提供される。したがって、本発明の
チタン酸バリウム系半導体磁器は、それを定温発熱体と
して各種ヒーター類への用途に応用した場合、従来より
も高い最大使用電圧、つまり信頼性の高い製品を提供す
ることを可能にし、また従来製品と同等の性能と信頼性
を有する製品を設計する場合は、該半導体磁器の単位厚
み当りの最大使用電圧が高いため、より軽薄な製品とす
ることを可能にするものであって、産業上非常に有用な
ものである。Effects of the Invention According to the present invention, BaC as the main raw material
O3, PbO, CaCO3, SrCO3 and T
iO2, Nb2O5 as a semiconducting agent, MnCO3 as an additive, SiO2 and Al2O3
By selecting each of these and specifying their blending ratio, we have created a product with a fine crystal structure, practical resistivity at room temperature, high maximum operating voltage, and a switching temperature in the high temperature range of 200°C or higher. Provided are barium titanate-based semiconductor porcelain and barium titanate-based semiconductor porcelain compositions used in the production thereof. Therefore, when the barium titanate-based semiconductor porcelain of the present invention is applied to various types of heaters as a constant temperature heating element, it is possible to provide a product with a higher maximum operating voltage than before, that is, a highly reliable product. In addition, when designing a product that has the same performance and reliability as conventional products, it is possible to create a lighter and thinner product because the maximum operating voltage per unit thickness of the semiconductor porcelain is high. Therefore, it is very useful industrially.
【0025】[0025]
【実施例】以下、実施例および比較例により本発明をさ
らに詳細に説明する。EXAMPLES The present invention will now be explained in more detail with reference to Examples and Comparative Examples.
【0026】実施例1.
BaCO3 、PbO、CaCO3 、SrCO3 、
TiO2 、Nb2 O5 、MnCO3 、SiO2
、Al2 O3 の各成分を表1の配合にしたがって
配合してなるチタン酸バリウム系半導体磁器用組成物と
、これと重量比1:1の割合の純水とをナイロン製のボ
ールミルに装入し、20時間、湿式微粉砕混合した後、
得られたスラリーを脱水、乾燥し、PVAバインダーを
混ぜて、成形圧500kg/cm2 ・Gで直径50m
m、厚さ10mmの円板状に成形し、これを電気炉にて
1050℃で2時間仮焼した。仮焼された円板を粗砕し
、次いでこれと重量比1:1の割合で純水を添加し、ナ
イロン製のボールミルにて20時間、湿式微粉砕混合し
た後、得られたスラリーを脱水、乾燥し、PVAバイン
ダーを混ぜて、顆粒状に造粒した。この造粒粉を、成形
圧2000kg/cm2 ・Gで直径16mm、厚さ1
mmの円板状に成形し、電気炉にて1250℃で2時間
焼結させ、その後200℃/hrの冷却速度にて常温ま
で冷却した。これによって得られた焼結体の両面に銀電
極を焼付け、測定用試料を得た。Example 1. BaCO3, PbO, CaCO3, SrCO3,
TiO2, Nb2O5, MnCO3, SiO2
, Al2O3 according to the formulations shown in Table 1, and pure water at a weight ratio of 1:1 were charged into a nylon ball mill. , after wet pulverization and mixing for 20 hours,
The resulting slurry was dehydrated, dried, mixed with a PVA binder, and molded at a diameter of 50 m at a molding pressure of 500 kg/cm2/G.
It was molded into a disk shape with a thickness of 10 mm and was calcined in an electric furnace at 1050° C. for 2 hours. The calcined disks were roughly crushed, then pure water was added thereto at a weight ratio of 1:1, and the slurry was wet-pulverized and mixed for 20 hours in a nylon ball mill, and the resulting slurry was dehydrated. , dried, mixed with a PVA binder, and granulated. This granulated powder was molded to a diameter of 16 mm and a thickness of 1 at a molding pressure of 2000 kg/cm2・G.
It was molded into a disk shape of mm in diameter, sintered in an electric furnace at 1250°C for 2 hours, and then cooled to room temperature at a cooling rate of 200°C/hr. Silver electrodes were baked on both sides of the sintered body thus obtained to obtain a measurement sample.
【0027】この試料について、常温(25℃)におけ
る比抵抗値、スイッチング温度、並びに単位厚み当りの
最大使用電圧を測定し、その値を表2に示した。Regarding this sample, the specific resistance value at room temperature (25° C.), the switching temperature, and the maximum operating voltage per unit thickness were measured, and the values are shown in Table 2.
【0028】上述の各種特性のうち、「スイッチング温
度」は、試料の抵抗値が最小となる値の2倍の抵抗値に
達した時の温度である。「単位厚み当りの最大使用電圧
」は、試料に50hzの交流電圧を印加し、その電圧を
徐々に上昇していった時に、試料の抵抗値が最大になる
ときの電圧の実効値(Vrms )を試料の厚み(mm
)で割った値である。Among the various characteristics described above, the "switching temperature" is the temperature at which the resistance value of the sample reaches a resistance value twice the minimum value. "Maximum operating voltage per unit thickness" is the effective value of the voltage (Vrms) at which the resistance value of the sample reaches its maximum when a 50Hz AC voltage is applied to the sample and the voltage is gradually increased. is the thickness of the sample (mm
) is the value divided by
【0029】また、実施例1で得られた焼結体の表面組
織を、金属顕微鏡で観察した写真を図1に示す。Further, FIG. 1 shows a photograph of the surface structure of the sintered body obtained in Example 1, observed with a metallurgical microscope.
【0030】実施例2〜13および比較例1〜10表1
に示す配合にしたがって、チタン酸バリウム系半導体磁
器用組成物を調製し、実施例1と同様の方法で得られた
チタン酸バリウム系半導体磁器についてそれぞれ実施例
1と同様の特性試験を行った結果を表2に示す。ただし
、実施例2の焼成時間は1時間であり、実施例10の焼
成時間は3時間である。また、比較例9で得られた焼結
体の表面組織を、金属顕微鏡で観察した写真を図2に示
す。Examples 2 to 13 and Comparative Examples 1 to 10 Table 1
A barium titanate-based semiconductor porcelain composition was prepared according to the formulation shown in Example 1, and the barium titanate-based semiconductor porcelain obtained in the same manner as in Example 1 was subjected to the same characteristic tests as in Example 1. are shown in Table 2. However, the firing time of Example 2 was 1 hour, and the firing time of Example 10 was 3 hours. Further, FIG. 2 shows a photograph of the surface structure of the sintered body obtained in Comparative Example 9, which was observed using a metallurgical microscope.
【0031】[0031]
【表1】[Table 1]
【0032】[0032]
【表2】[Table 2]
【図1】本発明のチタン酸バリウム系半導体磁器の表面
組織の1例を示す顕微鏡写真である。FIG. 1 is a micrograph showing an example of the surface structure of barium titanate-based semiconductor ceramic of the present invention.
【図2】比較のためのチタン酸バリウム系半導体磁器の
表面組織の1例を示す顕微鏡写真である。FIG. 2 is a micrograph showing an example of the surface structure of barium titanate-based semiconductor ceramic for comparison.
Claims (2)
、CaCO3、SrCO3 およびTiO2 、半導体
化剤としてのNb2 O5 、添加剤としてのMnCO
3 、SiO2 およびAl2 O3 からなるチタン
酸バリウム系半導体磁器用組成物であって、該TiO2
100モル当り、BaCO3 50〜80モル、Pb
O20〜40モル、CaCO3 3〜8モル、SrCO
3 2〜9モル、Nb2 O5 0.10〜0.16モ
ル、MnCO3 0.03〜0.07モル、SiO2
2.0〜3.0モルおよびAl2 O3 0.05〜1
.0モルをそれぞれ配合してなる前記チタン酸バリウム
系半導体磁器用組成物。Claim 1: BaCO3 and PbO as main raw materials
, CaCO3, SrCO3 and TiO2, Nb2O5 as a semiconducting agent, MnCO as an additive
3. A barium titanate-based semiconductor ceramic composition comprising SiO2 and Al2O3, the TiO2
Per 100 mol, BaCO3 50-80 mol, Pb
O20-40 mol, CaCO3 3-8 mol, SrCO
3 2-9 mol, Nb2O5 0.10-0.16 mol, MnCO3 0.03-0.07 mol, SiO2
2.0-3.0 mol and Al2O3 0.05-1
.. The above-mentioned barium titanate-based composition for semiconductor ceramics, which contains 0 mol of each.
導体磁器用組成物を湿式微粉砕混合し、脱水・乾燥後、
1000〜1100℃の温風で仮焼し、再び湿式微粉砕
混合し、脱水・乾燥後、バインダーを混ぜて成形し、1
250〜1300℃の温度で0.5〜3時間焼結するこ
とによって得られるチタン酸バリウム系半導体磁器。2. The barium titanate-based semiconductor ceramic composition according to claim 1 is wet-pulverized and mixed, and after dehydration and drying,
Calcinate with hot air at 1000-1100℃, wet pulverize and mix again, dehydrate and dry, mix with binder and mold.
Barium titanate-based semiconductor porcelain obtained by sintering at a temperature of 250 to 1300°C for 0.5 to 3 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3063741A JPH04280861A (en) | 1991-03-06 | 1991-03-06 | Composition for barium titanate-based semiconductor porcelain and barium titanate-based semiconductor porcelain using the same composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3063741A JPH04280861A (en) | 1991-03-06 | 1991-03-06 | Composition for barium titanate-based semiconductor porcelain and barium titanate-based semiconductor porcelain using the same composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04280861A true JPH04280861A (en) | 1992-10-06 |
Family
ID=13238140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3063741A Pending JPH04280861A (en) | 1991-03-06 | 1991-03-06 | Composition for barium titanate-based semiconductor porcelain and barium titanate-based semiconductor porcelain using the same composition |
Country Status (1)
Country | Link |
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JP (1) | JPH04280861A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108439975A (en) * | 2018-05-18 | 2018-08-24 | 武汉理工大学 | It is a kind of have stablize strontium titanates calcium base energy storage ceramic of defect sturcture and preparation method thereof |
-
1991
- 1991-03-06 JP JP3063741A patent/JPH04280861A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108439975A (en) * | 2018-05-18 | 2018-08-24 | 武汉理工大学 | It is a kind of have stablize strontium titanates calcium base energy storage ceramic of defect sturcture and preparation method thereof |
CN108439975B (en) * | 2018-05-18 | 2021-04-20 | 武汉理工大学 | Strontium calcium titanate-based energy storage ceramic with stable defect structure and preparation method thereof |
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