JPH02265216A - Grain-boundary oxidation type voltage nonlinear resistance element - Google Patents
Grain-boundary oxidation type voltage nonlinear resistance elementInfo
- Publication number
- JPH02265216A JPH02265216A JP1087564A JP8756489A JPH02265216A JP H02265216 A JPH02265216 A JP H02265216A JP 1087564 A JP1087564 A JP 1087564A JP 8756489 A JP8756489 A JP 8756489A JP H02265216 A JPH02265216 A JP H02265216A
- Authority
- JP
- Japan
- Prior art keywords
- resistance element
- boundary oxidation
- oxidation type
- grain
- nonlinear resistance
- 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
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 239000003990 capacitor Substances 0.000 abstract description 4
- 229910052738 indium Inorganic materials 0.000 abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 2
- 229910010252 TiO3 Inorganic materials 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
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は粒界酸化型電圧非直線抵抗素子に関し、特に
たとえば電子機器や電気機器で発生する異常電圧、ノイ
ズおよび静電気などを吸収または除去するためなどに用
いられるバリスタなどのような、粒界酸化型電圧非直線
抵抗素子に関する。[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a grain boundary oxidation type voltage nonlinear resistance element, and in particular, to absorb or remove abnormal voltage, noise, static electricity, etc. generated in electronic equipment or electrical equipment. The present invention relates to grain boundary oxidation type voltage nonlinear resistance elements, such as varistors used for various purposes.
（従来技術）
従来の粒界酸化型電圧非直線抵抗素子としては、たとえ
ば５ｒＴｉＯ＋系の半導体磁器の結晶粒界を空気中酸化
やＮａ２ｏなどの酸化剤によって酸化し、結晶粒界に絶
縁層を形成したものがあった。(Prior art) As a conventional grain boundary oxidation type voltage nonlinear resistance element, for example, the grain boundaries of 5rTiO+ semiconductor ceramics are oxidized in air or with an oxidizing agent such as Na2O to form an insulating layer at the grain boundaries. There was something I did.
このような電圧非直線抵抗素子は、その素体がペロブス
カイト結晶構造を有し、強誘電性を示すため、単にバリ
スタとしての機能のみでなく、コンデンサとしての機能
も有する。したがって、この電圧非直線抵抗素子を用い
て、異常高電圧（サージ）の吸収や電圧の安定化などを
行うことができるという利点がある。Since such a voltage nonlinear resistance element has a perovskite crystal structure and exhibits ferroelectricity, it functions not only as a varistor but also as a capacitor. Therefore, there is an advantage that this voltage nonlinear resistance element can be used to absorb abnormally high voltage (surge), stabilize voltage, and the like.
（発明が解決しようとする課題）
しかしながら、従来の５ｒＴｉ○３系半導体磁器を用い
たものでは、磁器を構成する粒子間の抵抗が大きいため
、その非直線係数が小さい。また、５ｒＴｉＯ：ｌ系半
導体磁器を用いたものでは、パルス電圧が印加されるこ
とによってその電気的特性が劣化してしまう。(Problems to be Solved by the Invention) However, in those using conventional 5rTi○3 semiconductor ceramics, the resistance between particles constituting the ceramics is large, so the nonlinear coefficient is small. Furthermore, in the case of a device using 5rTiO:l semiconductor ceramic, the electrical characteristics deteriorate when a pulse voltage is applied.
それゆえに、この発明の主たる目的は、バリスタ特性と
コンデンサ特性の両方を備え、大きなバリスタ電圧と大
きな非直線係数を有し、かつ大きなサージ耐量を有する
、粒界酸化型電圧非直線抵抗素子を提供することである
。Therefore, the main object of the present invention is to provide a grain boundary oxidation type voltage nonlinear resistance element that has both varistor characteristics and capacitor characteristics, has a large varistor voltage, a large nonlinear coefficient, and has a large surge withstand capacity. It is to be.
（課題を解決するための手段）
この発明は、（Ｓｒｌ−ｘ Ｃａ、 ）Ｔｉ０３ （
ただし、Ｘ≦０．２５）を９８．０〜９９．９モル％と
、Ｎｂ、Ｗ、Ｔａ、Ｉ ｎおよび希土類元素の中から選
ばれる少なくとも１種類の酸化物を０゜１〜２．０モル
％とからなる素体に対して、ＣｕＯ，ＰｂＯ，Ｂ ｉｚ
Ｏ：ｌ 、Ｓｂｚ ０３ 、Ｖｚ ＯｓＭｏｂｆｆの
中から選ばれる少なくとも１種類とＮａ２ｏ、Ｔ ｉ０
２’ （Ｎａｚ Ｑ＞ｏ、Ｔ ｉ ０２ ＞０）とを合
わせて０．０１〜２．０モル％含有されてなる、粒界酸
化型電圧非直線抵抗素子である。(Means for solving the problem) The present invention provides (Srl-x Ca, )Ti03 (
However, X≦0.25) is 98.0 to 99.9 mol%, and at least one oxide selected from Nb, W, Ta, In, and rare earth elements is CuO, PbO, B iz
At least one type selected from O:l, Sbz 03, Vz OsMobff, Na2o, Ti0
2' (Naz Q>o, T i 02 >0) in a total content of 0.01 to 2.0 mol%.
（発明の効果）
この発明によれば、バリスタ特性とコンデンサ特性の両
方を備えた粒界酸化型電圧非直線抵抗素子を得ることが
できる。さらに、この粒界酸化型電圧非直線抵抗素子は
、１００〜３００Ｖ程度の大きなバリスタ電圧を得るこ
とができ、さらに１５以上の大きな非直線係数を得るこ
とができる。(Effects of the Invention) According to the present invention, a grain boundary oxidation type voltage nonlinear resistance element having both varistor characteristics and capacitor characteristics can be obtained. Furthermore, this grain boundary oxidation type voltage nonlinear resistance element can obtain a large varistor voltage of about 100 to 300 V, and can also obtain a large nonlinear coefficient of 15 or more.
また、この粒界酸化型電圧非直線抵抗素子では、５００
０Ａ／ｃｎ！までのサージに耐えることができる。Moreover, in this grain boundary oxidation type voltage nonlinear resistance element, 500
0A/cn! Can withstand up to surges.
この発明の上述の目的、その他の目的、特徴および利点
は、以下の実施例の詳細な説明から一層明らかとなろう
。The above objects, other objects, features and advantages of the present invention will become more apparent from the detailed description of the following embodiments.
（実施例）
まず、Ｓ ｒ ＣＯ３、Ｔ ｉ ０２ 、 Ｃａ Ｃ
ＯａおよびＮｂ、Ｗ、Ｔａ、Ｉ ｎ、希土類元素の酸化
物粉末を別表に示す組成比のものが得られるように秤量
して湿式混合した。この混合物を乾燥後、１１５０℃で
２時間仮焼し、粉砕した。この粉砕物に酢酸ビニル系樹
脂を５重量％添加して造粒し、この造粒粉を１． ｔｏ
ｎ ／ ｃ＋＋ｔの圧力で、直径１０龍２厚さ１．５鰭
のベレット状に成形した。この成形体を空気中において
１ｏｏｏ℃で２時間焼成した後、体積比でＨ２：ＮＺ
＝１ ： １００の雰囲気中において１４５０°Ｃで２
時間焼成し、半導体磁器を得た。得られた半導体ｌａ器
に、別表に示す割合で酸化剤を加え、１２００℃で２時
間熱処理を行って、磁器ユニットを得た。得られた磁器
ユニットの対向面に銀電極を形成し、その電気的特性を
評価した。(Example) First, S r CO3, T i 02 , Ca C
Oxide powders of Oa, Nb, W, Ta, In, and rare earth elements were weighed and wet-mixed to obtain composition ratios shown in the attached table. After drying this mixture, it was calcined at 1150° C. for 2 hours and pulverized. 5% by weight of vinyl acetate resin was added to this pulverized product and granulated, and the granulated powder was mixed with 1. to
It was molded into a pellet shape with a diameter of 10 dragons and a thickness of 1.5 fins using a pressure of n/c++t. After firing this molded body in air at 100°C for 2 hours, the volume ratio of H2:NZ
=1: 2 at 1450°C in an atmosphere of 100°C
After firing for several hours, semiconductor porcelain was obtained. An oxidizing agent was added to the obtained semiconductor ceramic in the proportion shown in the attached table, and heat treatment was performed at 1200° C. for 2 hours to obtain a ceramic unit. A silver electrode was formed on the opposing surface of the obtained ceramic unit, and its electrical characteristics were evaluated.
ここでは、磁器ユニットに１ｍＡの電流を流した時のバ
リスタ電圧Ｖ、□ （Ｖ）および非直線係数αと５００
０Ａ／ｃＩＩｔのサージ電流を印加した時のバリスタ電
圧の変化率Δｖ１、（％）および非直線係数の変化率Δ
α（％）とを測定し、別表に示した。Here, the varistor voltage V, □ (V) and nonlinear coefficient α when a current of 1 mA is passed through the ceramic unit, and 500
Varistor voltage change rate Δv1, (%) and nonlinear coefficient change rate Δ when applying a surge current of 0 A/cIIt
α (%) was measured and shown in the attached table.
表の試料番号３のように、半導体化剤としてのＮｂ、Ｗ
、Ｔａ、Ｉ ｎおよび希土類元素などの酸化物が添加さ
れていない場合、その電気的特性を測定することができ
なかった。As shown in sample number 3 in the table, Nb and W as semiconducting agents
If oxides such as , Ta, In and rare earth elements were not added, its electrical properties could not be measured.
また、試料番号７のように、半導体化剤が２゜０モル％
を超えた場合、サージ電流を印加したときのバリスタ電
圧変化率および非直線係数変化率が大きくなる。In addition, as in sample number 7, the semiconducting agent was 2°0 mol%.
If it exceeds , the rate of change in varistor voltage and the rate of change in nonlinear coefficient will increase when a surge current is applied.
さらに、試料番号１２のように、ＳｒおよびＣａの原子
数を１としたときのＣａの原子Ｄｘが０２５を超えた場
合、バリスタ電圧が小さくなるとともに、サージ電流を
印加したときのバリスタ電圧変化率および非直線係数変
化率が大きくなる。Furthermore, as in sample number 12, when the number of atoms of Sr and Ca is 1, the Ca atom Dx exceeds 025, the varistor voltage decreases, and the rate of change in varistor voltage when a surge current is applied. and the nonlinear coefficient change rate increases.
また、試料番号１３のように、酸化剤の添加■が０．０
１モル％より少ない場合、バリスタ電圧および非直線係
数が小さくなる。In addition, as in sample number 13, the addition of oxidizing agent ■ is 0.0
When it is less than 1 mol%, the varistor voltage and nonlinear coefficient become small.
さらに、試料番号１４．１５．１６のように酸化剤がＮ
ａｚ ＱかＴ ｉ Ｏ□のいずれが工種の場合には、バ
リスタ電圧および非直線係数（α）がともに小さくなる
。Furthermore, as in sample number 14.15.16, the oxidizing agent
When either az Q or T i O□ is the type of work, both the varistor voltage and the nonlinear coefficient (α) become small.
さらに、試料番号１９および試料番号２７のように、酸
化剤の添加量が２．０モル％を超えた場合、サージ電流
を印加したときのバリスタ電圧変化率および非直線係数
変化率が大きくなる。Furthermore, as in Sample No. 19 and Sample No. 27, when the amount of oxidizing agent added exceeds 2.0 mol %, the varistor voltage change rate and nonlinear coefficient change rate when a surge current is applied become large.
それに対して、この発明の粒界酸化型電圧非直線抵抗素
子では、５０００ Ａ ／ ｃｉまテノサージ電流に耐
えることができ、かつ非直線係数αが１５以上と大きい
。On the other hand, the grain boundary oxidation type voltage nonlinear resistance element of the present invention can withstand a tenosurge current of up to 5000 A/ci and has a large nonlinear coefficient α of 15 or more.
また、酸化剤として、ＮａおよびＴｉの酸化物を用いた
場合、サージ耐量および非直線係数が従来のものの１．
５倍程度になり、安定性にも優れたものとなる。さらに
、Ｃｕ Ｏ，Ｐ ｂ Ｏ，Ｂ ｉ ｚＯｌ、 Ｓ ｂ
ｚ Ｏ：ｌ’、 Ｖ２ Ｏ５、Ｍ ｏ ０３の中から
選ばれる少なくとも１種類を加えた場合、静電容量が従
来のものに比べて最大２倍にすることができるとともに
、サージ耐量や非直線係数をさらに大きくすることがで
きる。Furthermore, when oxides of Na and Ti are used as oxidizers, the surge resistance and nonlinear coefficient are 1.
It becomes about 5 times as large and has excellent stability. Furthermore, CuO, PbO, BizOl, Sb
When at least one type selected from z O:l', V2 O5, and M o 03 is added, the capacitance can be up to twice that of conventional ones, and the surge resistance and non-linearity can be increased. The coefficient can be made even larger.
特許出願人 株式会社 村田製作所 代理人 弁理士 岡 １） 全 啓Patent applicant Murata Manufacturing Co., Ltd. Agent: Patent Attorney Oka 1) Zenhiro
Claims (1)
≦０．２５）を９８．０〜９９．９モル％と、Ｎｂ，Ｗ
，Ｔａ，Ｉｎおよび希土類元素の中から選ばれる少なく
とも１種類の酸化物を０．１〜２．０モル％とからなる
素体に対して、ＣｕＯ，ＰｂＯ，Ｂｉ＿２Ｏ＿３，Ｓｂ
＿２Ｏ＿３，Ｖ＿２Ｏ＿５，ＭｏＯ＿３の中から選ばれ
る少なくとも１種類とＮａ＿２Ｏ，ＴｉＯ＿２（Ｎａ＿
２Ｏ＞０，ＴｉＯ＿２＞０）とを合わせて０．０１〜２
．０モル％含有されてなる、粒界酸化型電圧非直線抵抗
素子。(SR_1_-_xCa_x)TiO_3 (however, x
≦0.25) from 98.0 to 99.9 mol%, and Nb, W
CuO, PbO, Bi_2O_3, Sb
At least one type selected from _2O_3, V_2O_5, MoO_3 and Na_2O, TiO_2 (Na_
2O>0, TiO_2>0) and 0.01 to 2
．． A grain boundary oxidation type voltage nonlinear resistance element containing 0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087564A JPH02265216A (en) | 1989-04-05 | 1989-04-05 | Grain-boundary oxidation type voltage nonlinear resistance element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087564A JPH02265216A (en) | 1989-04-05 | 1989-04-05 | Grain-boundary oxidation type voltage nonlinear resistance element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02265216A true JPH02265216A (en) | 1990-10-30 |
Family
ID=13918488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1087564A Pending JPH02265216A (en) | 1989-04-05 | 1989-04-05 | Grain-boundary oxidation type voltage nonlinear resistance element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02265216A (en) |
-
1989
- 1989-04-05 JP JP1087564A patent/JPH02265216A/en active Pending
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