JPH02222502A - Grain boundary oxidation type non-linear resistance element - Google Patents
Grain boundary oxidation type non-linear resistance elementInfo
- Publication number
- JPH02222502A JPH02222502A JP1044735A JP4473589A JPH02222502A JP H02222502 A JPH02222502 A JP H02222502A JP 1044735 A JP1044735 A JP 1044735A JP 4473589 A JP4473589 A JP 4473589A JP H02222502 A JPH02222502 A JP H02222502A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- resistance element
- grain boundary
- moo3
- voltage
- 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 description 12
- 238000007254 oxidation reaction Methods 0.000 title claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 229910052573 porcelain Inorganic materials 0.000 abstract description 5
- 239000003990 capacitor Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910010252 TiO3 Inorganic materials 0.000 abstract 2
- 238000000034 method Methods 0.000 abstract 1
- 239000002966 varnish Substances 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 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
- 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
- 238000010304 firing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 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）
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Ｓ ｒ Ｔ ｉ Ｏｓ系の半導体磁器の結晶粒界を空
気中酸化やＮａ、Ｏ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) Conventional grain boundary oxidation type voltage nonlinear resistance elements are made by oxidizing the crystal grain boundaries of SrTiOs semiconductor ceramics in air or with an oxidizing agent such as Na or O, thereby forming crystal grains. There was one in which an insulating layer was formed in the field.
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５ｒＴｉＯ，、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、５ｒＴｉ０３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 5rTiO, semiconductor ceramics, the resistance between the particles constituting the ceramics is large, so the nonlinear coefficient is small. Furthermore, in the case of a device using 5rTi03 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、（Ｓｒ＋−＊ Ｃａｘ ）Ｔｉｅｓ （
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、酸化ナトリウム、酸化チタ
ン、酸化モリブデンがＮａｔ Ｏ，Ｔ ｉ Ｏｘおよび
ＭｏＯ３に換算して（Ｎａ、Ｏ＞０．Ｔｉｅ、＞Ｏ，Ｍ
ｏ５ｓ ＞０）総量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 Problems) This invention provides (Sr+-*Cax)Ties (
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 Sodium oxide, titanium oxide, and molybdenum oxide are converted into Nat O, Ti Ox, and MoO3 (Na, O>0.Tie, >O, M
o5s>0) It is a grain boundary oxidation type voltage nonlinear resistance element containing a total amount 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
０ Ａ／ｃｄ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
Can withstand surges up to 0 A/cd.
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、ＳｒＣＯ３、Ｔｉ１ｔ ＋ ＣａＣ０ｚおよび
Ｎ ｂ ＊ Ｗ、Ｔ ａ 、 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、１１５
０℃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１ｔ
ｏｎ／ａＪの圧力で、直径１０ｍｍ、厚さ１．５ｍのベ
レット状に成形した。この成形体を空気中において１０
００℃で２時間焼成した後、体積比でＨｔ ：Ｎ！
−１： １００の雰囲気中において１４５０℃で２時間
焼成し、半導体磁器を得た。得られた半導体磁器に、別
表に示す割合でＮａ ｔ Ｏ，Ｔ ｌ ０２およびＭＯ
Ｏ，の混合酸化物をフェスとともに塗布し、空気中にお
いて１２００℃で２時間熱処理を行って、磁器ユニット
を得た。(Example) First, oxide powders of SrCO3, Ti1t+CaC0z, 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, 115
The mixture was calcined at 0°C for 2 hours and pulverized. 5% by weight of vinyl acetate resin is added to this pulverized material and granulated, and 1 t of this granulated powder is
It was molded into a pellet shape with a diameter of 10 mm and a thickness of 1.5 m under a pressure of on/aJ. This molded body was placed in air for 10
After baking at 00°C for 2 hours, the volume ratio of Ht:N!
-1: Semiconductor porcelain was obtained by firing at 1450° C. for 2 hours in an atmosphere of 100°C. To the obtained semiconductor porcelain, Na t O, T 1 02 and MO were added in the proportions shown in the attached table.
A mixed oxide of O, was applied together with the face, and a heat treatment was performed in the air at 1200° C. for 2 hours to obtain a ceramic unit.
得られた磁器ユニットの対向面に銀ペーストを塗布し、
８００℃で焼き付けて銀電極を形成し、その電気的特性
を評価した。Apply silver paste to the opposite side of the obtained porcelain unit,
A silver electrode was formed by baking at 800° C., 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ｖｔ−ａ （ｖ）および非直線係数αと５
０００Ａ／−のサージ電流を印加した時のバリスタ電圧
の変化率ΔＶ＋−ａ （％）および非直線係数の変化
率Δα（％）とを測定し、別表に示した。Here, the varistor voltage vt-a (v) and the nonlinear coefficient α and 5
The rate of change in varistor voltage ΔV+-a (%) and the rate of change in nonlinear coefficient Δα (%) when a surge current of 000 A/- was applied were 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、Ｉｎ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, the 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１４のように、ＳｒおよびＣａの原子
数を１としたときのＣａの原子数Ｘが０．２５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 14, when the number of Ca atoms X exceeds 0.25 when the number of Sr and Ca atoms is 1, the varistor voltage decreases and the varistor voltage decreases when a surge current is applied. The voltage change rate and nonlinear coefficient change rate become large.
また、試料番号１５のように、酸化剤の添加量が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 15, the amount of oxidizing agent added 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２１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太き（なる
。Furthermore, as in sample number 21, the amount of oxidizing agent added was 2.
If it exceeds 0 mol%, the varistor voltage change rate and nonlinear coefficient change rate become thicker when a surge current is applied.
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、５０００Ａ／ａＪまでの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。In contrast, the grain boundary oxidation type voltage nonlinear resistance element of the present invention can withstand surge currents of up to 5000 A/aJ 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
、Ｍｏｂ、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。また、静
電容量は、ＭｏＯ３の添加量によってコントロールする
ことができ、粒界酸化型電圧非直線抵抗素子の生産に好
適である。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, when MOB is added, the capacitance can be doubled at maximum compared to the conventional one, and the surge resistance and nonlinear coefficient can be further increased. Further, the capacitance can be controlled by the amount of MoO3 added, and is suitable for producing a grain boundary oxidation type voltage nonlinear resistance element.
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) Zenkei
Claims (1)
ｘ≦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、酸化ナトリウム，酸化チタン，酸化モ
リブデンがＮａ＿２Ｏ，ＴｉＯ＿２およびＭｏＯ＿３に
換算して（Ｎａ＿２Ｏ＞０，ＴｉＯ＿２＞０，ＭｏＯ＿
３＞０）総量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%, Nb,
For an element body consisting of 0.1 to 2.0 mol% of at least one oxide selected from W, Ta, In, and rare earth elements, sodium oxide, titanium oxide, and molybdenum oxide are Na_2O, TiO_2 and in terms of MoO_3 (Na_2O>0, TiO_2>0, MoO_
3>0) containing a total amount of 0.01 to 2.0 mol%,
Grain boundary oxidation type voltage nonlinear resistance element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1044735A JPH02222502A (en) | 1989-02-23 | 1989-02-23 | Grain boundary oxidation type non-linear resistance element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1044735A JPH02222502A (en) | 1989-02-23 | 1989-02-23 | Grain boundary oxidation type non-linear resistance element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02222502A true JPH02222502A (en) | 1990-09-05 |
Family
ID=12699709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1044735A Pending JPH02222502A (en) | 1989-02-23 | 1989-02-23 | Grain boundary oxidation type non-linear resistance element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02222502A (en) |
-
1989
- 1989-02-23 JP JP1044735A patent/JPH02222502A/en active Pending
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