JPH038765A - Production of voltage-dependent nonlinear resistor porcelain composition and varistor - Google Patents
Production of voltage-dependent nonlinear resistor porcelain composition and varistorInfo
- Publication number
- JPH038765A JPH038765A JP1143727A JP14372789A JPH038765A JP H038765 A JPH038765 A JP H038765A JP 1143727 A JP1143727 A JP 1143727A JP 14372789 A JP14372789 A JP 14372789A JP H038765 A JPH038765 A JP H038765A
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- JP
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- Prior art keywords
- mol
- varistor
- voltage
- component
- sio
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 230000001419 dependent effect Effects 0.000 title claims description 4
- 229910052573 porcelain Inorganic materials 0.000 title 1
- 239000000654 additive Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 150000004706 metal oxides Chemical group 0.000 abstract description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 13
- 239000003990 capacitor Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910019603 Rh2O3 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- -1 5eOx Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910018162 SeO2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910004369 ThO2 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は電気機器、電子機器で発生する異常高電圧、ノ
イズ、静電気などから機器の半導体および回路を保護す
るためのコンデンサ特性とバリスタ特性を有する電圧依
存性非直線抵抗体磁器組成物およびバリスタの製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a voltage having capacitor characteristics and varistor characteristics to protect semiconductors and circuits of equipment from abnormal high voltages, noise, static electricity, etc. generated in electrical equipment and electronic equipment. The present invention relates to a dependent nonlinear resistor ceramic composition and a method for manufacturing a varistor.
従来の技術
従来、各種の電気機器、電子機器における異常高電圧の
吸収、ノイズの除去、火花消去、静電気対策のために電
圧依存性非直線抵抗特性を有するＳｉＣバリスタや、Ｚ
ｎＯ系バリスタなどが使用されている。このようなバリ
スタの電圧−電流特性は近似的に次式のように表すこと
ができる。Conventional technology Conventionally, SiC varistors and Z
nO type varistors are used. The voltage-current characteristics of such a varistor can be approximately expressed as in the following equation.
１＝（Ｖ／Ｃ）α
ここで、Ｉは電流、■は電圧、Ｃはバリスタ固有の定数
、αは電圧−電流非直線指数である。1=(V/C) α Here, I is a current, ■ is a voltage, C is a constant specific to the varistor, and α is a voltage-current nonlinear index.
ＳｉＣバリスタのαは２〜７程度、ＺｎＯ系バリスタで
はαが５０にもおよぶものがある。このようなバリスタ
は比較的高い電圧の吸収には優れた性能を有しているが
、誘電率が低く、固有の静電容量が小さいため、バリス
タ電圧以下の比較的低い電圧の吸収にはほとんど効果を
示さず、また誘電損失ｔａｎδが５〜１０％と大きい。The α of SiC varistors is about 2 to 7, and the α of some ZnO-based varistors is as high as 50. Such varistors have excellent performance in absorbing relatively high voltages, but due to their low dielectric constant and small inherent capacitance, they have little ability to absorb relatively low voltages below the varistor voltage. It has no effect, and the dielectric loss tan δ is as large as 5 to 10%.
一方、これらの低電圧のノイズなどの除去には見かけの
誘電率が５Ｘ１０４程度で、ｔａｎδが１％前後の半導
体コンデンサが利用されている。On the other hand, semiconductor capacitors with an apparent dielectric constant of about 5×10 4 and a tan δ of about 1% are used to remove these low voltage noises.
しかし、このような半導体コンデンサはサージなどによ
りある限度以上の電圧または電流が印加されると、静電
容量が減少したり、破壊されたりしてコンデンサとして
の機能を果たさなくなったりする。However, when a voltage or current exceeding a certain limit is applied to such a semiconductor capacitor due to a surge or the like, the capacitance decreases or the semiconductor capacitor is destroyed, and the capacitor no longer functions as a capacitor.
そこで最近になってＳｒＴｉＯ３を主成分とし、バリス
タ特性とコンデンサ特性の両方の機能を有するものが開
発され、コンピュータなどの電子機器におけるＩＣ，Ｌ
ＳＩなどの半導体素子の保護に利用されている。Therefore, recently, a product that has SrTiO3 as its main component and has both varistor and capacitor properties has been developed, and it
It is used to protect semiconductor devices such as SI.
発明が解決しようとする課題
上記のＳｒＴｉＯ３を主成分とするバリスタとコンデン
サの両方の機能を有する素子は、ＺｎＯ系バリスタに比
べ誘電率が約１０倍と大きいが、αやサージ耐量が小さ
く、バリスタ電圧を低くすると特性が劣化しやすいとい
った欠点を有していた。Problems to be Solved by the Invention The above-mentioned element that has SrTiO3 as a main component and functions as both a varistor and a capacitor has a dielectric constant about 10 times higher than that of a ZnO-based varistor, but its α and surge resistance are small, making it difficult to use as a varistor. It has the disadvantage that the characteristics tend to deteriorate when the voltage is lowered.
そこで本発明では、誘電率が大きく、バリスタ電圧が低
（、αが大きいと共にサージ耐量が大きい電圧依存性非
直線抵抗体磁器組成物およびバリスタの製造方法を提供
することを目的とするものである。Therefore, an object of the present invention is to provide a voltage-dependent nonlinear resistor ceramic composition that has a large dielectric constant, a low varistor voltage (α), and a large surge withstand capacity, and a method for manufacturing the varistor. .
課題を解決するための手段
上記の問題点を解決するために本発明では、Ｓ ｒ ａ
Ｔ ｉ ０３ （０．９５０≦ｈ≦１．０００）
（以下第１成分と呼ぶ）を９０．０００〜９９．９９
８ｍｏ １％、Ｎｂ２Ｏ５，Ｔａ２０５．ＷＯ３，Ｄｙ
２Ｏ３，Ｙ２Ｏ３，Ｌａ２Ｏ３，ＣｅＯ２，Ｓｍ２Ｏ３
，Ｐ ｒ６ＯＮｄ２０３のうち少なくとも１種類以上（
以下第２成分と呼ぶ）を０．００１〜５．０００ｍｏ
１％。Means for Solving the Problems In order to solve the above problems, in the present invention, S r a
T i 03 (0.950≦h≦1.000)
(hereinafter referred to as the first component) from 90.000 to 99.99
8mo 1%, Nb2O5, Ta205. WO3, Dy
2O3, Y2O3, La2O3, CeO2, Sm2O3
, at least one type of Pr6ONd203 (
(hereinafter referred to as the second component) from 0.001 to 5.000 mo
1%.
Ａｌ２０ｚ、５ｂ２０３．Ｂａｄ、ＢｅＯ，Ｐｂ０゜Ｂ
２Ｏ３，Ｃｒ２０ｖ、Ｆｅ２Ｏ：＋、ＣｄＯ，に２０゜
ＣａＯ，Ｃｏ２Ｏ３，Ｃｒ２Ｏ３，Ｆｅ２Ｏ３，ＣｄＯ
，Ｋ２Ｏ，ＣａＯ，Ｃｏ２Ｏ３，ＣｕＯ，Ｃｕ２Ｏ，Ｌ
ｉ２Ｏ。Al20z, 5b203. Bad, BeO, Pb0゜B
2O3, Cr20v, Fe2O:+, CdO, 20°CaO, Co2O3, Cr2O3, Fe2O3, CdO
, K2O, CaO, Co2O3, CuO, Cu2O, L
i2O.
Ｌ ｉ Ｆ、ＭｇＯ，ＭｎＯ２，ＭｎＯ３，Ｎａ２Ｏ。L i F, MgO, MnO2, MnO3, Na2O.
ＮａＦ，ＮｉＯ，Ｒｈ２Ｏ３，５ｅＯｘ、Ａｇ２Ｏ。NaF, NiO, Rh2O3, 5eOx, Ag2O.
ＳｉＯ２，Ｓ ｉ Ｃ，Ｓ ｒｏ、Ｔ １２０３．Ｔｈ
０２゜Ｔ ｉ ０２ 、 Ｖ２Ｏ５，Ｂ １２０３．
Ｚ ｎｏ、ＺｒＯ２゜ＳｎＯ２のうち少なくとも１種類
以上（以下第３成分と呼ぶ）を０．００１〜５．０００
ｍｏ １％含有してなる主成分１００重量部と、ＳｒＴ
ｉＯ３６０．０００〜３２．５００ｍｏ １％，ＳｉＯ
２４０．０００〜６７．５００ｍｏ １％からなる１昆
合物を１２００〜１３００℃で焼成してなる添加物（以
下第４成分と呼ぶ）０．００１〜１０．０００重量部と
からなる電圧依存性非直線抵抗体磁器組成物を得ること
により問題を解決しようとするものである。SiO2, S i C, S ro, T 1203. Th
02°T i 02 , V2O5,B 1203.
At least one or more of Z no, ZrO2゜SnO2 (hereinafter referred to as the third component) from 0.001 to 5.000
100 parts by weight of the main component containing 1% of SrT
iO360.000~32.500mo 1%, SiO
Voltage dependence consisting of 0.001 to 10.000 parts by weight of an additive (hereinafter referred to as the fourth component) made by baking a mixture of 1% of 240.000 to 67.500 mo at 1200 to 1300°C The aim is to solve this problem by obtaining a non-linear resistive ceramic composition.
また、上記組成物を１１００℃以上で焼成するバリスタ
の製造方法、あるいは上記組成物を１１００℃以上で焼
成した後、還元性雰囲気中で１２００℃以上で焼成し、
その後酸化性雰囲気中で９００〜１３００°Ｃで焼成す
るバリスタの製造方法を提案するものである。Further, a method for producing a varistor comprising firing the above composition at 1100°C or higher, or firing the above composition at 1100°C or higher and then firing at 1200°C or higher in a reducing atmosphere,
The present invention proposes a method for manufacturing a varistor in which the varistor is then fired at 900 to 1300°C in an oxidizing atmosphere.
作用
上記の発明において第１成分は主たる成分であり、第２
成分は主に第１成分の半導体化を促進する金属酸化物で
ある。また、第３成分は誘電率。Effect In the above invention, the first component is the main component, and the second component is the main component.
The components are mainly metal oxides that promote semiconducting of the first component. Also, the third component is the dielectric constant.
α、サージ耐量の改善に寄与するものであり、第４成分
はバリスタ電圧の低下、誘電率の改善に有効なものであ
る。特に、第４成分は融点が１２３０〜１２５０℃と比
較的低いため、融点前後の温度で焼成すると液相となり
、その他の成分の反応を促進すると共に粒子の成長を促
進する。そのため粒界部分に第３成分が偏析しやす（な
り、粒界が高抵抗化され易くなり、バリスタ機能および
コンデンサ機能が改善される。また、粒成長が促進され
るためバリスタ電圧が低（なり、粒径の均一性が向上す
るため特性の安定性がよくなり、特にサージ耐量が改善
されることとなる。α contributes to improving the surge resistance, and the fourth component is effective in reducing the varistor voltage and improving the dielectric constant. In particular, since the fourth component has a relatively low melting point of 1230 to 1250° C., when fired at a temperature around the melting point, it turns into a liquid phase, which promotes the reactions of the other components and the growth of particles. As a result, the third component is more likely to segregate at the grain boundaries, making the grain boundaries more likely to have high resistance, improving the varistor and capacitor functions.Also, grain growth is promoted, so the varistor voltage is lower. Since the uniformity of the particle size is improved, the stability of properties is improved, and especially the surge resistance is improved.
実施例 以下に実施例を挙げて本発明を具体的に説明する。Example The present invention will be specifically described below with reference to Examples.
まず、ＳｒＴｉＯ３．５ｉＯｚを下記の第１表に示すよ
うに組成比を種々変えて秤量し、ボールミルなどで２０
８ ｒ混合する。次に、乾燥した後、下記の第１表１こ
示すように温度を種々変えて焼成し、再びボールミルな
どで２０８ ｒ粉砕した後、乾燥し、第４成分とする。First, 3.5 iOz of SrTiO was weighed at various composition ratios as shown in Table 1 below, and 20
8 Mix. Next, after drying, the mixture is calcined at various temperatures as shown in Table 1 below, ground again at 208 r with a ball mill, etc., and dried to obtain the fourth component.
次いで、第１成分、第２成分、第３成分、第４成分を下
記の第１表に示した組成比になるように秤量し、ボール
ミルなどで２４Ｈｒ混合した後、乾燥し、ポリビニルア
ルコールなどの有機バインダーを１０ｗｔ％添加して造
粒した後、１ （ｔ ／ｃｎｆ ）のプレス圧力で１０
φＸｉ”（ｍｍ）の円板状に成形し、１０００℃で１０
Ｈｒ焼成し脱バインダーする。次に、第１表に示したよ
うに温度を種々変えて４Ｈｒ焼成（第１焼成〉し、その
後還元性雰囲気、例えばＮ２ ：Ｈ２＝９：１のガス中
で温度を種々変えて４Ｈｒ焼成（第２焼成）する。さら
にその後、酸化性雰囲気中で温度を種々変えて２ Ｈｒ
焼成（第３焼成）する。Next, the first component, second component, third component, and fourth component were weighed to have the composition ratio shown in Table 1 below, mixed for 24 hours using a ball mill, etc., dried, and mixed with polyvinyl alcohol, etc. After adding 10 wt% of organic binder and granulating it, 10 wt% was added at a press pressure of 1 (t/cnf).
Formed into a disc shape of φXi” (mm) and heated at 1000°C for 10
The binder is removed by Hr firing. Next, as shown in Table 1, the material is fired for 4 hours at various temperatures (first firing), and then fired for 4 hours at various temperatures in a reducing atmosphere, for example, a gas with N2:H2=9:1. After that, the temperature was varied in an oxidizing atmosphere for 2 hours.
Fire (third firing).
こうして得られた第１図および第２図に示す焼結体１の
両平面に外周を残すようにしてＡｇなどの導電性ペース
トをスクリーン印刷などにより塗布し、６００℃、５ｍ
１ｎで焼成し、電極２，３を形成する。次に、半田など
によりリード線を取付け、エポキシなどの樹脂を塗装す
る。このようにして得られた素子の特性を下記の第２表
に示す。A conductive paste such as Ag was applied by screen printing or the like, leaving the outer periphery on both planes of the sintered body 1 shown in FIGS. 1 and 2 obtained in this way.
The electrodes 2 and 3 are formed by firing at 1n. Next, the lead wires are attached using solder or the like, and a resin such as epoxy is applied. The characteristics of the device thus obtained are shown in Table 2 below.
なお、見掛は誘電率はＩＫＨｚでの静電容量から計算し
たものであり、αは
ａ ＝ １ ／ Ｌ ｏ ｇ （Ｖ＋ｏｍＡ／ Ｖ＋ｍ
Ａ ）（ただし、ＶｌｍＡ、ＶｌｏｍＡは１ｍＡ、１０
ｍＡの電流を流した時に素子の両端にかかる電圧である
。）で評価した。また、サージ耐量はパルス性の電流を
印加した後のＶ １ ｍ Ａの変化率が±１０％以内で
ある時の最大のパルス性電流値により評価している。Note that the apparent permittivity is calculated from the capacitance at IKHz, and α is a = 1 / L o g (V + omA / V + m
A) (However, VlmA, VlomA are 1mA, 10
This is the voltage applied across the device when a current of mA flows through it. ) was evaluated. Further, the surge resistance is evaluated based on the maximum pulse current value when the rate of change in V 1 mA after applying the pulse current is within ±10%.
（以 下 余 白 ）
また、第１成分の５ｒａＴｉ０３のａの範囲を規定した
のは、ａが１．０００よりも太き（なると格子欠陥が発
生しに（いため半導体化が促進されず、Ｖ ｍＡが高
くなりすぎて特性が劣化し、方０．９５０より小さくな
るとＴｉ過剰になりすぎてＴｉＯ２の結晶が生成し、組
織が不均一になり特性が劣化するためである。さらに、
第２成分は０．００１ｍｏ １％未満では効果を示さず
、５、０００ｍｏｌ％を越えると粒界に偏析して粒界の
高抵抗化を抑制し、粒界に第２相を形成するため特性が
劣化するものである。また、第３成分はＯ，ＯＯ１ｍｏ
ｌ％未満では効果を示さず、５、０００ｍｏ １％を超
えると粒界に偏析して第２相を形成するため特性が劣化
するものである。(Margin below) Also, the range of a for the first component 5raTi03 was specified because a is thicker than 1.000 (as a result, lattice defects occur (therefore, semiconductor formation is not promoted, and V This is because if the mA becomes too high, the characteristics will deteriorate, and if it becomes less than 0.950, Ti will be too excessive and TiO2 crystals will form, making the structure non-uniform and deteriorating the characteristics.Furthermore,
The second component has no effect if it is less than 0.001mol%, and if it exceeds 5,000mol%, it segregates at the grain boundaries, suppresses the high resistance of the grain boundaries, and forms a second phase at the grain boundaries, so it has characteristics. is deteriorated. Also, the third component is O, OO1mo
If it is less than 1%, it will not be effective, and if it exceeds 5,000mo1%, it will segregate at grain boundaries and form a second phase, resulting in deterioration of properties.
また、第４成分はＳｒＴｉＯ３とＳｉＯ２の２成分系の
相図のなかでＭｇ５ｒＯ３６０．０００〜３２．５００
ｍｏｌ％、５ｉＣｈ ４０．０００〜６７．５００ｍ
ｏｌ％の範囲内のものは最も融点の低い領域の物質であ
り、その範回外では融点が高（なるものである。また、
第４成分の添加量は、０．００１重量部未満では効果を
示さず、１０．０００！量部を越えると粒界の抵抗は高
（なるが粒界の幅が厚くなるため、静電容量が小さくな
ると共にＶｌ ｍＡが高くなり、サージに対して弱（な
るものである。また、第４成分の焼成温度を規定したの
は、低融点の第４成分が合成される温度が１２００℃以
上であるためである。そして、第１焼成の温度を規定し
たのは、第４成分の融点が１２３０〜１２５０℃である
ため、１１００℃以上の温度で焼成すると第４成分が液
相に近い状態になって焼結が促進されるためであり、１
１００℃未満では第４成分の液相焼結効果がないためで
ある。また、第２焼成の温度を規定したのは、１２００
°Ｃ未満では第１焼成後の焼結体が十分に還元されず、
バリスタ特性、コンデンサ特性共に劣化するためである
。さらに、第３焼成の温度を規定したのは、９００℃未
満では粒界の高抵抗化が十分に進まないため、Ｖｌ ｍ
Ａが低くなりすぎバリスタ特性が劣化するためであり、
１３００℃を越えると静電容量が小さくなりすぎコンデ
ンサ特性が劣化するためである。また、第１焼成の雰囲
気は酸化性雰囲気でも還元性雰囲気でも同様の効果があ
ることを確認した。In addition, the fourth component is Mg5rO360.000 to 32.500 in the phase diagram of the two-component system of SrTiO3 and SiO2.
mol%, 5iCh 40.000-67.500m
Those within the range of ol% are substances with the lowest melting point, and those outside that range have high melting points.Also,
If the amount of the fourth component added is less than 0.001 parts by weight, no effect will be shown; If the amount exceeds 50%, the grain boundary resistance becomes high (but the width of the grain boundary becomes thicker, the capacitance becomes smaller and the Vl mA becomes higher, making it weak against surges. The firing temperature of the four components was specified because the temperature at which the fourth component with a low melting point is synthesized is 1200°C or higher.The temperature of the first firing was specified because the temperature of the fourth component with a low melting point was synthesized. is 1,230 to 1,250°C, so if the fourth component is fired at a temperature of 1,100°C or higher, the fourth component becomes close to a liquid phase and sintering is promoted.
This is because the fourth component has no liquid phase sintering effect below 100°C. In addition, the temperature for the second firing was regulated at 1200°C.
If the temperature is below °C, the sintered body after the first firing will not be sufficiently reduced.
This is because both the varistor characteristics and the capacitor characteristics deteriorate. Furthermore, the temperature of the third firing was specified because if it is less than 900°C, the resistance of grain boundaries cannot be sufficiently increased.
This is because A becomes too low and the varistor characteristics deteriorate.
This is because if the temperature exceeds 1300° C., the capacitance becomes too small and the capacitor characteristics deteriorate. Furthermore, it was confirmed that the same effect can be obtained whether the atmosphere for the first firing is an oxidizing atmosphere or a reducing atmosphere.
なお、第２成分としては、上記実施例で挙げた成分以外
にＳｍ２Ｏ３，Ｐ ｒｓｏ＋＋、Ｎｄ２Ｏ５を用いるこ
とができ、かつ２種類以上を組み合せて上記範囲内の添
加量で用いてもよいものである。また、第３成分として
は、上記実施例で挙げた成分以外にＢａｄ、ＰｂＯ，Ｂ
２０３ 、Ｃａｂ。In addition, as the second component, Sm2O3, Prso++, and Nd2O5 can be used in addition to the components listed in the above examples, and two or more types may be combined and used in an amount within the above range. . Further, as the third component, in addition to the components mentioned in the above examples, Bad, PbO, B
203, Cab.
ＣｕＯ，Ｌｉ２０．ＬｉＦ、Ｎａ２０．ＮａＦ。CuO, Li20. LiF, Na20. NaF.
Ｒｈ２Ｏ３、ＳｅＯ２，Ｓ ｉｏ２．Ｓ ｒｏ。Rh2O3, SeO2, Sio2. Sro.
ＴｈＯ２，Ｔｉ０ｚ 、を用いることができ、かつ第２
成分と同様に２種類以上を組合せて上述した範囲内の添
加量で用いてもよいものである。さらに、上記実施例で
はこれら添加物の組合せについては一部のみ示している
が、その他の組合せでも同様の効果が得られることが確
認された。ThO2, Ti0z can be used, and the second
As with the components, two or more types may be combined and used in the amount added within the above-mentioned range. Furthermore, although only some of the combinations of these additives are shown in the above examples, it was confirmed that similar effects can be obtained with other combinations.
発明の効果
以上に示したように本発明によれば、粒子径が大きいた
めバリスタ電圧が低く、誘電率εおよびαが大きく、粒
子径のばらつきが小さいことからサージ電流が素子に均
一に流れるため、サージ耐量が大きくなるという効果が
得られる。Effects of the Invention As shown above, according to the present invention, the varistor voltage is low because the particle size is large, the permittivity ε and α are large, and the variation in particle size is small, so surge current flows uniformly through the element. , the effect of increasing surge resistance can be obtained.
第１図は本発明による素子を示す上面図、第２図は本発
明による素子を示す断面図である。
１・・・・・・焼結体、２，３・・・・・・電極。FIG. 1 is a top view showing an element according to the invention, and FIG. 2 is a sectional view showing the element according to the invention. 1... Sintered body, 2, 3... Electrode.
Claims (1)
０）を９０．０００〜９９．９９８ｍｏｌ％，Ｎｂ＿２
Ｏ＿５，Ｔａ＿２Ｏ＿５，ＷＯ＿３，Ｄｙ＿２Ｏ＿３，
Ｙ＿２Ｏ＿３，Ｌａ＿２Ｏ＿３，ＣｅＯ＿２，Ｓｍ＿２
Ｏ＿３，Ｐｒ＿６Ｏ＿１＿１，Ｎｄ＿２Ｏ＿３のうち少
なくとも１種類以上を０．００１〜５．０００ｍｏｌ％
，Ａｌ＿２Ｏ＿３，Ｓｂ＿２Ｏ＿３，ＢａＯ，ＢｅＯ，
ＰｂＯ，Ｂ＿２Ｏ＿３，Ｃｒ＿２Ｏ＿３，Ｆｅ＿２Ｏ＿
３，ＣｄＯ，Ｋ＿２Ｏ，ＣａＯ，Ｃｏ＿２Ｏ＿３，Ｃｕ
Ｏ，Ｃｕ＿２Ｏ，Ｌｉ＿２Ｏ，ＬｉＦ，ＭｇＯ，ＭｎＯ
＿２，ＭｏＯ＿３，Ｎａ＿２Ｏ，ＮａＦ，ＮｉＯ，Ｒｈ
＿２Ｏ＿３，ＳｅＯ＿２，Ａｇ＿２Ｏ，ＳｉＯ＿２，Ｓ
ｉＣ，ＳｒＯ，Ｔｌ＿２Ｏ＿３，ＴｈＯ＿２，ＴｉＯ＿
２，Ｖ＿２Ｏ＿５，Ｂｉ＿２Ｏ＿３，ＺｎＯ，ＺｒＯ＿
２，ＳｎＯ＿２のうち少なくとも１種類以上を０．００
１〜５．０００ｍｏｌ％含有してなる主成分１００重量
部と、ＳｒＴｉＯ＿３ ６０．０００〜３２．５００ｍｏｌ％，ＳｉＯ＿２４０
．０００〜６７．５００ｍｏｌ％からなる混合物を１２
００℃以上で焼成してなる添加物０．００１〜１０．０
００重量部とからなることを特徴とする電圧依存性非直
線抵抗体磁器組成物。 （２）Ｓｒ＿ａＴｉＯ＿３（０．９５０≦ａ≦１．００
０）を９０．０００〜９９．９９８ｍｏｌ％，Ｎｂ＿２
Ｏ＿５，Ｔａ＿２Ｏ＿５，ＷＯ＿３，Ｄｙ＿２Ｏ＿３，
Ｙ＿２Ｏ＿３，Ｌａ＿２Ｏ＿３，ＣｅＯ＿２，Ｓｍ＿２
Ｏ＿３，Ｐｒ＿６Ｏ＿１＿１，Ｎｄ＿２Ｏ＿３のうち少
なくとも１種類以上を０．００１〜５．０００ｍｏｌ％
，Ａｌ＿２Ｏ＿３，Ｓｂ＿２Ｏ＿３，ＢａＯ，ＢｅＯ，
ＰｂＯ，Ｂ＿２Ｏ＿３，Ｃｒ＿２Ｏ＿３，Ｆｅ＿２Ｏ＿
３，ＣｄＯ，Ｋ＿２Ｏ，ＣａＯ，Ｃｏ＿２Ｏ＿３，Ｃｕ
Ｏ，Ｃｕ＿２Ｏ，Ｌｉ＿２Ｏ，ＬｉＦ，ＭｇＯ，ＭｎＯ
＿２，ＭｏＯ＿３，Ｎａ＿２Ｏ，ＮａＦ，ＮｉＯ，Ｒｈ
＿２Ｏ＿３，ＳｅＯ＿２，Ａｇ＿２Ｏ，ＳｉＯ＿２，Ｓ
ｉＣ，ＳｒＯ，Ｔｌ＿２Ｏ＿３，ＴｈＯ＿２，ＴｉＯ＿
２，Ｖ＿２Ｏ＿５，Ｂｉ＿２Ｏ＿３，ＺｎＯ，ＺｒＯ＿
２，ＳｎＯ＿２のうち少なくとも１種類以上を０．００
１〜５．０００ｍｏｌ％含有してなる主成分１００重量
部と、ＳｒＴｉＯ＿３ ６０．０００〜３２．５００ｍｏｌ％，ＳｉＯ＿２４０
．０００〜６７．５００ｍｏｌ％からなる混合物を１２
００℃以上で焼成してなる添加物０．００１〜１０．０
００重量部とからなる組成物を１１００℃以上で焼成し
たことを特徴とするバリスタの製造方法。 （３）Ｓｒ＿ａＴｉＯ＿３（０．９５０≦ａ≦１．００
０）を９０．０００〜９９．９９８ｍｏｌ％，Ｎｂ＿２
Ｏ＿５，Ｔａ＿２Ｏ＿５，ＷＯ＿３，Ｄｙ＿２Ｏ＿３，
Ｙ＿２Ｏ＿３，Ｌａ＿２Ｏ＿３，ＣｅＯ＿２，Ｓｍ＿２
Ｏ＿３，Ｐｒ＿６Ｏ＿１＿１，Ｎｄ＿２Ｏ＿３のうち少
なくとも１種類以上を０．００１〜５．０００ｍｏｌ％
，Ａｌ＿２Ｏ＿３，Ｓｂ＿２Ｏ＿３，ＢａＯ，ＢｅＯ，
ＰｂＯ，Ｂ＿２Ｏ＿３，Ｃｒ＿２Ｏ＿３，Ｆｅ＿２Ｏ＿
３，ＣｄＯ，Ｋ＿２Ｏ，ＣａＯ，Ｃｏ＿２Ｏ＿３，Ｃｕ
Ｏ，Ｃｕ＿２Ｏ，Ｌｉ＿２Ｏ，ＬｉＦ，ＭｇＯ，ＭｎＯ
＿２，ＭｏＯ＿３，Ｎａ＿２Ｏ，ＮａＦ，ＮｉＯ，Ｒｈ
＿２Ｏ＿３，ＳｅＯ＿２，Ａｇ＿２Ｏ，ＳｉＯ＿２，Ｓ
ｉＣ，ＳｒＯ，Ｔｌ＿２Ｏ＿３，ＴｈＯ＿２，ＴｉＯ＿
２，Ｖ＿２Ｏ＿５，Ｂｉ＿２Ｏ＿３，ＺｎＯ，ＺｒＯ＿
２，ＳｎＯ＿２のうち少なくとも１種類以上を０．００
１〜５．０００ｍｏｌ％含有してなる主成分１００重量
部と、ＳｒＴｉＯ＿３ ６０．０００〜３２．５００ｍｏｌ％，ＳｉＯ＿２４０
．０００〜６７．５００ｍｏｌ％からなる混合物を１２
００℃以上で焼成してなる添加物０．００１〜１０．０
００重量部とからなる組成物を１１００℃以上で焼成し
た後、還元性雰囲気中で１２００℃以上で焼成し、その
後酸化性雰囲気中で９００〜１３００℃で焼成したこと
を特徴とするバリスタの製造方法。[Claims] (1) Sr_aTiO_3 (0.950≦a≦1.00
0) from 90.000 to 99.998 mol%, Nb_2
O_5, Ta_2O_5, WO_3, Dy_2O_3,
Y_2O_3, La_2O_3, CeO_2, Sm_2
0.001 to 5.000 mol% of at least one of O_3, Pr_6O_1_1, Nd_2O_3
, Al_2O_3, Sb_2O_3, BaO, BeO,
PbO, B_2O_3, Cr_2O_3, Fe_2O_
3, CdO, K_2O, CaO, Co_2O_3, Cu
O, Cu_2O, Li_2O, LiF, MgO, MnO
_2, MoO_3, Na_2O, NaF, NiO, Rh
_2O_3, SeO_2, Ag_2O, SiO_2, S
iC, SrO, Tl_2O_3, ThO_2, TiO_
2, V_2O_5, Bi_2O_3, ZnO, ZrO_
2.0.00 of at least one type of SnO_2
100 parts by weight of the main component containing 1 to 5.000 mol%, SrTiO_3 60.000 to 32.500 mol%, SiO_240
．． A mixture consisting of 000 to 67.500 mol%
Additives baked at 00°C or higher 0.001 to 10.0
00 parts by weight of a voltage-dependent nonlinear resistor ceramic composition. (2) Sr_aTiO_3 (0.950≦a≦1.00
0) from 90.000 to 99.998 mol%, Nb_2
O_5, Ta_2O_5, WO_3, Dy_2O_3,
Y_2O_3, La_2O_3, CeO_2, Sm_2
0.001 to 5.000 mol% of at least one of O_3, Pr_6O_1_1, Nd_2O_3
, Al_2O_3, Sb_2O_3, BaO, BeO,
PbO, B_2O_3, Cr_2O_3, Fe_2O_
3, CdO, K_2O, CaO, Co_2O_3, Cu
O, Cu_2O, Li_2O, LiF, MgO, MnO
_2, MoO_3, Na_2O, NaF, NiO, Rh
_2O_3, SeO_2, Ag_2O, SiO_2, S
iC, SrO, Tl_2O_3, ThO_2, TiO_
2, V_2O_5, Bi_2O_3, ZnO, ZrO_
2.0.00 of at least one type of SnO_2
100 parts by weight of the main component containing 1 to 5.000 mol%, SrTiO_3 60.000 to 32.500 mol%, SiO_240
．． A mixture consisting of 000 to 67.500 mol%
Additives baked at 00°C or higher 0.001 to 10.0
A method for manufacturing a varistor, characterized in that a composition comprising 0.00 parts by weight is fired at 1100°C or higher. (3) Sr_aTiO_3 (0.950≦a≦1.00
0) from 90.000 to 99.998 mol%, Nb_2
O_5, Ta_2O_5, WO_3, Dy_2O_3,
Y_2O_3, La_2O_3, CeO_2, Sm_2
0.001 to 5.000 mol% of at least one of O_3, Pr_6O_1_1, Nd_2O_3
, Al_2O_3, Sb_2O_3, BaO, BeO,
PbO, B_2O_3, Cr_2O_3, Fe_2O_
3, CdO, K_2O, CaO, Co_2O_3, Cu
O, Cu_2O, Li_2O, LiF, MgO, MnO
_2, MoO_3, Na_2O, NaF, NiO, Rh
_2O_3, SeO_2, Ag_2O, SiO_2, S
iC, SrO, Tl_2O_3, ThO_2, TiO_
2, V_2O_5, Bi_2O_3, ZnO, ZrO_
2.0.00 of at least one type of SnO_2
100 parts by weight of the main component containing 1 to 5.000 mol%, SrTiO_3 60.000 to 32.500 mol%, SiO_240
．． A mixture consisting of 000 to 67.500 mol%
Additives baked at 00°C or higher 0.001 to 10.0
00 parts by weight is fired at 1100°C or higher, then fired at 1200°C or higher in a reducing atmosphere, and then fired at 900 to 1300°C in an oxidizing atmosphere. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1143727A JPH038765A (en) | 1989-06-06 | 1989-06-06 | Production of voltage-dependent nonlinear resistor porcelain composition and varistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1143727A JPH038765A (en) | 1989-06-06 | 1989-06-06 | Production of voltage-dependent nonlinear resistor porcelain composition and varistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH038765A true JPH038765A (en) | 1991-01-16 |
Family
ID=15345598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1143727A Pending JPH038765A (en) | 1989-06-06 | 1989-06-06 | Production of voltage-dependent nonlinear resistor porcelain composition and varistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH038765A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994029236A1 (en) * | 1993-06-09 | 1994-12-22 | The United States Of America, Represented By The | NOVEL CERAMIC FERROELECTRIC COMPOSITE MATERIAL - BSTO-MgO |
| US5427988A (en) * | 1993-06-09 | 1995-06-27 | The United States Of America As Represented By The Secretary Of The Army | Ceramic ferroelectric composite material - BSTO-MgO |
| US5569632A (en) * | 1994-06-30 | 1996-10-29 | Korea Institute Of Science And Technology | Compositions of high frequency dielectrics |
-
1989
- 1989-06-06 JP JP1143727A patent/JPH038765A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994029236A1 (en) * | 1993-06-09 | 1994-12-22 | The United States Of America, Represented By The | NOVEL CERAMIC FERROELECTRIC COMPOSITE MATERIAL - BSTO-MgO |
| US5427988A (en) * | 1993-06-09 | 1995-06-27 | The United States Of America As Represented By The Secretary Of The Army | Ceramic ferroelectric composite material - BSTO-MgO |
| US5569632A (en) * | 1994-06-30 | 1996-10-29 | Korea Institute Of Science And Technology | Compositions of high frequency dielectrics |
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