JPH02184567A - Porcelain composition for voltage-nonlinear resistance element - Google Patents
Porcelain composition for voltage-nonlinear resistance elementInfo
- Publication number
- JPH02184567A JPH02184567A JP1001658A JP165889A JPH02184567A JP H02184567 A JPH02184567 A JP H02184567A JP 1001658 A JP1001658 A JP 1001658A JP 165889 A JP165889 A JP 165889A JP H02184567 A JPH02184567 A JP H02184567A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- resistance
- porcelain
- porcelain composition
- nonlinear
- 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
- 239000000203 mixture Substances 0.000 title abstract description 14
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 229910003077 Ti−O Inorganic materials 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910003080 TiO4 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 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
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical group [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-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〉
この発明は（Ｓｒ＋−ｘＣａｘ） Ｔｉｙ Ｏｓを主成
分とする電圧非直線抵抗体を得るための磁器組成物に関
するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a ceramic composition for obtaining a voltage nonlinear resistor containing (Sr+-xCax)TiyOs as a main component.
〈従来の技術とその課題〉
電子機器で発生する異常電圧、ノイズ等を吸収もしくは
除去するために種々のバリスタが使用されている。<Prior art and its problems> Various varistors are used to absorb or remove abnormal voltages, noise, etc. generated in electronic devices.
チタン酸ストロンチウムを主成分とする電圧非直線性抵
抗体は異常電圧、ノイズを吸収するバリスタとしての機
能のほか、コンデンサとしての機能を有している。A voltage nonlinear resistor whose main component is strontium titanate functions not only as a varistor that absorbs abnormal voltage and noise, but also as a capacitor.
この種の材料としては、特開昭５８−１６５０４号公報
、特開昭５８−９１６０２号公報に開示されているよう
に、５ｒＴｉＯｓ、あるいは５ｒｌ−ｘＣａＸＴｉＯｓ
（０，０１≦ｘ≦０．５）を主成分とし、これに半導
体化のための成分としてＮｂ１Ｏｓ 、 Ｔａ１ｌｓ
、 ＷＯｓ、Ｌａ１ｅｓ 、Ｃｅｎｔ、ＮｄｚＯｓ 、
ＹｚＯｓなどの金属酸化物およびサージ劣化防止のため
のＮａ、Ｏを含有したものからなっている。Examples of this type of material include 5rTiOs or 5rl-xCaXTiOs, as disclosed in Japanese Patent Application Laid-open No. 58-16504 and Japanese Patent Application Laid-open No. 58-91602.
(0,01≦x≦0.5) as the main component, and Nb1Os and Ta1ls as components for semiconductor formation.
, WOs, La1es, Cent, NdzOs,
It is made of metal oxide such as YzOs and contains Na and O to prevent surge deterioration.
しかしながら、これら従来の組成物はアルカリ金属酸化
物であるＮａｔＯを粒界に拡散させていることによって
非直線係数（α）やサージ耐量等のバリスタ特性を向上
させることが可能であるが、反面このために耐湿性、特
に高湿度雰囲気中での特性の経時変化が大きいという欠
点がみられるのである。However, in these conventional compositions, it is possible to improve varistor properties such as nonlinear coefficient (α) and surge resistance by diffusing an alkali metal oxide, NatO, into the grain boundaries; Therefore, it has the disadvantage that its moisture resistance, especially in a high-humidity atmosphere, changes significantly over time.
これはアルカリ金属がイオン化傾向太き（、このため高
湿度雰囲気中で外部電極あるいは電極中のガラスフリッ
トと反応して電極を腐食させたり、または腐食によって
抵抗数が発生して特性が変化していくためである。This is because alkali metals have a strong tendency to ionize (because of this, they may react with the external electrode or the glass frit in the electrode in a high humidity atmosphere, corroding the electrode, or corrosion may generate resistance and change its characteristics. It's to go.
〈発明の目的〉
この発明は上記に鑑みて高い電圧非直線係数（α）とサ
ージ耐量を持ち、高湿度中での耐湿性にすぐれた電圧非
直線抵抗体用の磁器組成物を提供することを目的とする
ものである。<Object of the invention> In view of the above, the present invention provides a ceramic composition for a voltage nonlinear resistor that has a high voltage nonlinear coefficient (α) and surge resistance, and has excellent moisture resistance in high humidity. The purpose is to
〈課題を解決するための手段〉
即ち、この発明は上記した問題点を解決するためになさ
れたものであって、
（Ｓｒ＋−ｘＣａｘ） Ｔｉｙ ０３ （但し、０≦ｘ
≦０．２５．０、９９６≦ｙ≦１．００３ ＞が９８．
０〜９９．９モル％と、Ｎｂ％Ｗ％Ｔａ、 Ｉｎ、 Ｙ
あるいは希土類元素の酸化物０．１〜２．０モル％とか
らなる半導体磁器にＮａｘＴｉｙＯｚ （但し、ｘ
＝２ｎ、 ｙ＝ ｎ’ 、 ｚ ＝ ｎ＋２ｎ’であっ
て、ｎ 、 ｎ’は自然数）
が０．０１〜１．０重量％含有されてなる電圧非直線抵
抗体用磁器組成物を提供するものである。<Means for Solving the Problems> That is, this invention was made to solve the above problems, and (Sr+-xCax) Tiy 03 (However, 0≦x
≦0.25.0, 996≦y≦1.003 >98.
0 to 99.9 mol% and Nb%W%Ta, In, Y
Alternatively, NaxTiyOz (however, x
=2n, y=n', z=n+2n', where n and n' are natural numbers). It is.
く作用〉
この発明で主成分として用いる（Ｓｒ＋−ｘｃａＸ）Ｔ
ｔｙＯ８において、ｙの量を０．９９６〜１．００３の
範囲とするのは、ｙがｉ、ｏｏｏ未満〜０．９９６の範
囲ではサージ耐量が改善され、一方ｙが１．０００〜１
．００３の範囲では特性が安定し、バラツキが小さくな
るという効果が得られるからである。(Sr+-xcaX)T used as the main component in this invention
In tyO8, the reason why the amount of y is set in the range of 0.996 to 1.003 is that when y is in the range of less than i,ooo to 0.996, the surge resistance is improved, whereas when y is in the range of 1.000 to 1.
．． This is because in the range of 003, the characteristics are stable and the variation is reduced.
また、（Ｓｒ＋−ｘＣａｘ） Ｔｉｙ Ｏａにおいて、
Ｘを０≦ｘ≦０．２５とするのはＣａ量が０．２５を越
えると、サージ耐量が低下して好ましくないためであり
、半導体化剤としてのＮｂ、 Ｗ、 Ｔａ、 Ｉｎ、
Ｙあるいは希土類元素の酸化物の量を０．１〜２．０モ
ル％とするのはこれらの酸化物が０モル％ではバリタス
特性を示さず、２．０モル％を越えるとサージ耐量が低
下する。Also, in (Sr+-xCax) Tiy Oa,
The reason why X is set to 0≦x≦0.25 is because if the amount of Ca exceeds 0.25, the surge resistance decreases, which is undesirable.
The reason for setting the amount of Y or rare earth element oxides to 0.1 to 2.0 mol% is that if these oxides are 0 mol%, they do not exhibit baritas characteristics, and if they exceed 2.0 mol%, the surge resistance decreases. do.
また酸化剤として用いるＮａｘＴｉｙＯｚで表わされる
化合物の量が０．０１重量％未溝になると、バリスタ電
圧および非直線係数が小さくなり、１．０重量％を越え
る場合はサージ耐量が低下する。Further, if the amount of the compound represented by NaxTiyOz used as an oxidizing agent is 0.01% by weight, the varistor voltage and nonlinear coefficient become small, and if it exceeds 1.0% by weight, the surge resistance decreases.
〈実施例〉 以下この発明を実施例により詳細に説明する。<Example> The present invention will be explained in detail below with reference to Examples.
第１表に示す組成比（モル％）となるように母材料と半
導体化剤として５ｒＣＯａ 、Ｔｉ０ｉ、ＣａＯｌＬａ
ｇ’ｓ 、ＹｔＯｓ、Ｅｒａ’ｓの各原料粉末を秤量、
配合し、湿式で混合して乾燥した後、１１５０℃で２時
間仮焼した。5rCOa, TiOi, CaOlLa were used as the base material and the semiconducting agent so that the composition ratio (mol%) shown in Table 1 was achieved.
Weigh the raw material powders of g's, YtOs, and Era's,
After blending, wet mixing and drying, the mixture was calcined at 1150° C. for 2 hours.
次いで粉砕後、酢酸ビニル系樹脂を５重量％添加して得
られた造粒物を１ｔｏｎ／ ｃｍ”の圧力で直径１０ｍ
ｍφ、１．５ｍｍ厚のベレット状に成形した。After pulverization, the granules obtained by adding 5% by weight of vinyl acetate resin were pulverized to a diameter of 10 m at a pressure of 1 ton/cm.
It was molded into a pellet shape with mφ and 1.5 mm thickness.
得られた成形体を空気中で１０００℃、２時間焼成した
後、Ｈ２／ Ｎｚ＝ １／１００ （ｖｏｌ比）の混
合ガス雰囲気中で１４５０℃、２時間焼成して半導体磁
器を得た。The obtained molded body was fired in air at 1000°C for 2 hours, and then fired at 1450°C for 2 hours in a mixed gas atmosphere of H2/Nz=1/100 (vol ratio) to obtain semiconductor porcelain.
一方、ＮａｘＯとＴｉＯ□を一定比で溶融させてＮａ１
ＴｉＯｓ 、ＮａｇＴｉｔＯｓ％Ｎａ＋ＴｉＯ４などの
化合物を得、これらをそれぞれ＃４００以下の微粉に粉
砕した。On the other hand, Na1
Compounds such as TiOs and NagTitOs%Na+TiO4 were obtained, and each of these was ground into fine powder of #400 or less.
上記で得た半導体磁器と化合物粉末を混合し、１２００
℃で２時間熱処理を行なった。Mix the semiconductor porcelain obtained above and the compound powder,
Heat treatment was performed at ℃ for 2 hours.
かくして得られた磁器ユニットの対向面に銀電極を設け
て電圧非直線性抵抗体素子を得、該素子のバリスタ電圧
Ｖ１、非直線係数α、サージ電圧印加によるｖｌおよび
αの変化率ΔＶ１、Δα等の電気的特性を調べたところ
第１表に示す結果が得られた。Silver electrodes are provided on the facing surfaces of the ceramic unit thus obtained to obtain a voltage nonlinear resistor element, and the varistor voltage V1 of the element, the nonlinear coefficient α, and the rate of change of vl and α due to surge voltage application ΔV1, Δα The results shown in Table 1 were obtained.
なお、表中の試料ＮＯ，に＊印を付したものはこの発明
の請求範囲外である。Note that the sample numbers marked with * in the table are outside the scope of the claims of this invention.
また、第１表中の試料Ｎａ、 ２で得られたこの発明の
電圧非直線抵抗素子とＳｒｏ、 ａｏｃａｏ、 ＊ａＴ
ＬＯｓ、９９．０モル％、Ｙ、０．０．５モル％、Ｎａ
ｚｏ ０．５モル％からなる従来の電圧非直線抵抗素子
とを６０℃、相対湿度（Ｒ１（） ９５％中に放置し、
湿中での誘電損失の経時変化を調べたところ、第１図の
結果が得られ、この発明の磁器組成物によるものが高温
高温中での耐湿性において非常に優れていることが認め
られた。In addition, the voltage nonlinear resistance element of the present invention obtained with samples Na and 2 in Table 1 and Sro, aocao, *aT
LOs, 99.0 mol%, Y, 0.0.5 mol%, Na
A conventional voltage non-linear resistance element consisting of 0.5 mol% of
When the change in dielectric loss over time in humidity was investigated, the results shown in Figure 1 were obtained, and it was recognized that the porcelain composition of the present invention has excellent moisture resistance in high temperature environments. .
〈発明の効果〉
以上説明したように、この発明によれば５０００Ａ／ｃ
ｍ”のサージ電圧印加後のサージ耐量にすぐれ、非直線
係数（α）がα〉１５と高い値が得られ、かつ高温高温
中における誘電損失の経時変化が小さい、即ち耐湿特性
にすぐれた電圧非直線抵抗体用の磁器組成物が得られる
のである。<Effects of the Invention> As explained above, according to this invention, 5000A/c
A voltage with excellent surge resistance after application of a surge voltage of m'', a high non-linear coefficient (α) of α>15, and a small change in dielectric loss over time in high temperatures, that is, excellent moisture resistance. A ceramic composition for a non-linear resistor is obtained.
第１図はこの発明の磁器組成物を用いた電圧非直線抵抗
体の高温高温中での誘電損失の経時変化を示す線図であ
る。FIG. 1 is a diagram showing the change over time in dielectric loss of a voltage nonlinear resistor using the ceramic composition of the present invention at high temperatures.
Claims (1)
０≦ｘ≦０．２５、０．９９６≦ｙ≦１．００３）が９
８．０〜９９．９モル％と、Ｎｂ、Ｗ、Ｔａ、Ｉｎ、Ｙ
あるいは希土類元素の酸化物０．１〜２．０モル％とか
らなる半導体磁器にＮａ＿ｘＴｉ＿ｙＯ＿ｚ（但し、ｘ
＝２ｎ、ｙ＝ｎ’、ｚ＝ｎ＋２ｎ’であって、ｎ、ｎ’
は自然数）が０．０１〜１．０重量％含有されてなる電
圧非直線抵抗体用磁器組成物。(Sr_1_-_xCa_x)Ti_yO_3 (However,
0≦x≦0.25, 0.996≦y≦1.003) is 9
8.0 to 99.9 mol%, Nb, W, Ta, In, Y
Alternatively, Na_xTi_yO_z (however, x
=2n, y=n', z=n+2n', where n, n'
is a natural number) in an amount of 0.01 to 1.0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1001658A JPH02184567A (en) | 1989-01-06 | 1989-01-06 | Porcelain composition for voltage-nonlinear resistance element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1001658A JPH02184567A (en) | 1989-01-06 | 1989-01-06 | Porcelain composition for voltage-nonlinear resistance element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02184567A true JPH02184567A (en) | 1990-07-19 |
Family
ID=11507619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1001658A Pending JPH02184567A (en) | 1989-01-06 | 1989-01-06 | Porcelain composition for voltage-nonlinear resistance element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02184567A (en) |
-
1989
- 1989-01-06 JP JP1001658A patent/JPH02184567A/en active Pending
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