JPH03261658A - Porcelain composition for resistor of non-linear to electric voltage - Google Patents
Porcelain composition for resistor of non-linear to electric voltageInfo
- Publication number
- JPH03261658A JPH03261658A JP2061981A JP6198190A JPH03261658A JP H03261658 A JPH03261658 A JP H03261658A JP 2061981 A JP2061981 A JP 2061981A JP 6198190 A JP6198190 A JP 6198190A JP H03261658 A JPH03261658 A JP H03261658A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- resistor
- linear
- ceramic 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 claims abstract description 19
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 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
- 239000000919 ceramic Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 2
- 229910052738 indium Inorganic materials 0.000 abstract description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910008593 TiyO3 Inorganic materials 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 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
- 238000001354 calcination Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 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
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）
この発明は電圧非直線抵抗体用磁器組成物に関し、たと
えば、電子機器で発生する異常電圧、ノイズを吸収もし
くは除去する電圧非直線抵抗体を得るための電圧非直線
抵抗体用磁器ｍ酸物に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a ceramic composition for a voltage nonlinear resistor, and for example, a ceramic composition for a voltage nonlinear resistor that absorbs or removes abnormal voltage and noise generated in electronic equipment. The present invention relates to a ceramic m-oxide for voltage nonlinear resistors.
（従来技術）
従来、この種の電圧非直線抵抗体用磁器組成物には、粒
界酸化型電圧非直線抵抗体用磁器組成物があった。この
粒界酸化型電圧非直線抵抗体用磁器組成物としては、た
とえば５ｒＴｉ０．系の半導体磁器の結晶粒界を空気中
酸化やＮａｚ○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) Conventionally, as this type of ceramic composition for a voltage non-linear resistor, there has been a grain boundary oxidation type ceramic composition for a voltage non-linear resistor. This grain boundary oxidation type ceramic composition for a voltage nonlinear resistor is, for example, 5rTi0. There is one in which the grain boundaries of semiconductor ceramics are oxidized in air or with an oxidizing agent such as Naz○ to form an insulating layer at the grain boundaries.
このような電圧非直線抵抗体用磁器組成物は、その素体
がペロブスカイト結晶構造を有し、強誘電杜を示すため
、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。Such a ceramic composition for a voltage nonlinear resistor has a perovskite crystal structure and exhibits ferroelectricity, and therefore has a function not only as a varistor but also as a capacitor.
したがって、この電圧非直線抵抗体用磁器組成物を用い
た電圧非直線抵抗体では、異常高電圧（サージ）の吸収
や電圧の安定化などを図ることができる。Therefore, in a voltage nonlinear resistor using this ceramic composition for a voltage nonlinear resistor, it is possible to absorb abnormally high voltage (surge) and stabilize the voltage.
（発明が解決しようとする課題）
しかしながら、このような従来の電圧非直線抵抗体用磁
器組成物を用いた電圧非直線抵抗体では、大きな非直線
係数αを得ながら、サージが印加されても非直線係数α
およびバリスタ電圧の劣化の小さいものが得られないと
いう欠点を有していた。(Problem to be Solved by the Invention) However, in a voltage nonlinear resistor using such a conventional ceramic composition for a voltage nonlinear resistor, while obtaining a large nonlinear coefficient α, it is difficult to resist even when a surge is applied. Nonlinear coefficient α
Also, it has the disadvantage that it is not possible to obtain a varistor with small deterioration in voltage.
それゆえに、この発明の主たる目的は、高いバリスタ電
圧を持ち、かつ非直線係数αが大きい値を示し、さらに
、高いサージ耐量の特性を有する電圧非直線抵抗体用磁
器組成物を提供することである。Therefore, the main object of the present invention is to provide a ceramic composition for a voltage nonlinear resistor that has a high varistor voltage, exhibits a large nonlinear coefficient α, and also has high surge resistance characteristics. be.
（課覇を解決するための手段〉
この発明にかかる電圧非直線抵抗体用磁器組成物は、（
Ｓ ｒ、−、Ｃａｗ ）Ｔ ｉｙ Ｏ３（ただし、０≦
ｘ≦０．２５．０．９９６≦ｙ≦１．００３）が９８．
０〜９９．９モル％と、Ｎｂ、Ｗ、Ｔａ、Ｉｎあるいは
希土類元素の酸化物が０．１〜２．０モル％とからなる
半導体磁器に、Ｎａ２Ｏ．５ｉ０２とＣｏ ｚ ０３
（ただし、０＜Ｎａ、０くＳｉ、Ｑ＜Ｃｏ）とをあわ
せて０．０１〜２．０モル％含有されてなる、電圧非直
線抵抗体用磁器組成物である。(Means for solving problems) The ceramic composition for a voltage nonlinear resistor according to the present invention has (
S r, -, Caw ) T iy O3 (however, 0≦
x≦0.25.0.996≦y≦1.003) is 98.
Na2O. 5i02 and Coz 03
(However, 0<Na, 0<Si, and Q<Co) are contained in a total of 0.01 to 2.0 mol % in a ceramic composition for a voltage nonlinear resistor.
（発明の効果）
この発明によれば、高いバリスタ電圧を有し、サージ耐
量にすくれ、かつ大きい非直線係数αを有する電圧非直
線抵抗体用磁器組成物が得られる。(Effects of the Invention) According to the present invention, a ceramic composition for a voltage nonlinear resistor having a high varistor voltage, a low surge resistance, and a large nonlinear coefficient α can be obtained.
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、母材料である、５ｒＣＯｚ 、Ｔｉｅ、。(Example) First, the base material is 5rCOz, Tie.
ＣａＣＯ３の粉末と、’ｒａｚｏｓおよび希土類元素の
酸化物であるＹ２Ｏ３．Ｌａｚ Ｏｚ 、ＥｒｚＯ３お
よび ＨＯ２Ｏ３の粉末とを準備し、これらの各原料粉
末を、表に示す組成比の電圧非直線抵抗体用磁器組成物
が得られるように杆量して湿式混合し、混合物を得た。CaCO3 powder, 'razos and rare earth element oxide Y2O3. Laz Oz, ErzO3, and HO2O3 powders were prepared, and each of these raw material powders was weighed and wet-mixed to obtain a ceramic composition for a voltage nonlinear resistor having the composition ratio shown in the table. Obtained.
そして、得られた混合物を乾燥後、１１５０℃で２時間
仮焼して粉砕し、わ）砕物を得た。After drying, the resulting mixture was calcined at 1150° C. for 2 hours and ground to obtain a) crushed product.
次いで、得られたわ）砕物に酢酸ビニル系樹脂を５重量
％添加して造粒し、造粒粉を得た。さらに、得られた造
粒粉を１Ｌｏｎ／ｃｏｔの圧力で直径ｌＯ關＋ Ｉ’Ｘ
さ１，５ｍｍのペレット状に成形して成形体を得た。Next, 5% by weight of vinyl acetate resin was added to the obtained crushed material and granulated to obtain a granulated powder. Furthermore, the obtained granulated powder was heated at a pressure of 1 Lon/cot to
A molded product was obtained by molding into a pellet having a diameter of 1.5 mm.
そして、この成形体を空気中で１０００℃で２時間仮焼
した後、体積比でＨ，：Ｎｚ、＝１ ： １００の混合
ガス雰囲気中において、■４５０℃で２時間焼成して半
導体磁器を得た。After calcining this molded body in air at 1000°C for 2 hours, it was fired at 450°C for 2 hours in a mixed gas atmosphere with a volume ratio of H,:Nz, = 1:100 to produce semiconductor porcelain. Obtained.
さらに、得られた半導体６ｉ器に、Ｎａ２０．ＳｉＯ２
およびＣｏ、０３からなる酸化剤を表に示す割合で添加
して、空気中で１２Ｏ０°Ｃで２時間熱処理を施して磁
器ユニットを得た。Furthermore, Na20. SiO2
An oxidizing agent consisting of Co, Co, and O3 was added in the proportions shown in the table, and heat treatment was performed at 1200°C in air for 2 hours to obtain a ceramic unit.
このようにして得られた磁器ユニットの対抗面に銀電極
を形成して電圧非直線抵抗素子を得た。A voltage nonlinear resistance element was obtained by forming a silver electrode on the opposing surface of the ceramic unit thus obtained.
そして、この電圧非直ｖＡ抵抗素子の電気的特性を評価
した。Then, the electrical characteristics of this voltage non-direct vA resistance element were evaluated.
この場合、得られた電圧非直線抵抗素子にｌ ｍＡの電
流を流したときのバリスタ電圧Ｖｌ−Ａ （Ｖ）、非
直線係数αおよび５０００ Ａ ／ ｃｔＡのサージ電
流を印加したときのバリスタ電圧ＶｌｆｉＡの変化率Δ
ＶｌｌｈＡと非直線係数αの変化率Δαとを測定し、表
に示した。In this case, the resulting voltage is the varistor voltage Vl-A (V) when a current of l mA is passed through the non-linear resistance element, the non-linear coefficient α and the varistor voltage VlfiA when a surge current of 5000 A/ctA is applied. rate of change Δ
VllhA and the rate of change Δα of the nonlinear coefficient α were measured and shown in the table.
なお、表中の試料番号に＊印を付したものは、この発明
の範囲外である。Note that sample numbers marked with * in the table are outside the scope of this invention.
次に、この発明にかかる電圧非直線抵抗体用磁器組成物
の各成分のＭｉ威範囲を限定した理由について説明する
。Next, the reason why the Mi range of each component of the ceramic composition for a voltage nonlinear resistor according to the present invention is limited will be explained.
試料番号３に示すように、半導体化剤としてのＮｂ、Ｗ
、Ｔａ、Ｉｎあるいは希土類元素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はできなか
った。As shown in sample number 3, Nb and W as semiconducting agents
, Ta, In, or rare earth element oxides, the electrical properties could not be measured.
また、試ネ４番号７に示すように、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
スタ電圧の変化率ΔＶ１ｍＡおよび非直線係数の変化率
Δαが大きくなる。In addition, as shown in test number 4, number 7, the semiconducting agent was 2.0
If it exceeds mol%, the rate of change ΔV1mA of the varistor voltage and the rate of change Δα of the nonlinear coefficient when a surge current is applied become large.
さらに、試料番号９に示すように、（Ｓｒ、−９ＣａＸ
）Ｔ゛ｉ、ＯｙのＸが０．２５を超えた場合、バリスタ
電圧Ｖ １ｍＡ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の変化率ΔＶＩＩＩＩＩＡお
よび非直線係数の変化率Δαが大きくなる。Furthermore, as shown in sample number 9, (Sr, -9CaX
) When X of T゛i and Oy exceeds 0.25, the varistor voltage V 1mA becomes smaller and the rate of change ΔVIIIA of the varistor voltage and the rate of change Δα of the nonlinear coefficient when a surge current is applied becomes larger. .
さらにまた、試料番号１０に示すように、酸化剤の添加
量が０．０１モル％より少ない場合、バリスタ電圧Ｖｌ
＋ａＡおよび非直線係数αが小さくなる。Furthermore, as shown in sample number 10, when the amount of oxidizing agent added is less than 0.01 mol%, the varistor voltage Vl
+aA and the nonlinear coefficient α become smaller.
試料番号１１および１２のように、酸化剤が０．２モル
％添加されているものの３つの酸化剤の全てが添加され
ない場合、サージ電流を印加したときのバリスタ電圧の
変化率ΔＶｌ＠６が大きくなったり、非直線係数の変化
率Δαが大きくなったりする。As in sample numbers 11 and 12, when 0.2 mol% of oxidizing agent is added but all three oxidizing agents are not added, the rate of change in varistor voltage ΔVl@6 when a surge current is applied is large. or the rate of change Δα of the nonlinear coefficient becomes large.
また、試料番号１４に示すように、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
バリスタ電圧の変化率ΔＶＩＩＩＡおよび非直線係数の
変化率Δαが大きくなる。In addition, as shown in sample number 14, the amount of oxidizing agent added was 2
．． If it exceeds 0 mol %, the rate of change ΔVIIIA of the varistor voltage and the rate of change Δα of the nonlinear coefficient when a surge current is applied become large.
さらに、試料番号１５に示すように、ｙが０゜９９６よ
り小さい場合は、非直線係数αが小さくなり、試料番号
１８に示すように、ｙが１．００３より大きい場合は、
サージ電流を印加したときのバリスタ電圧の変化率ΔＶ
１ｍＡおよび非直線係数の変化率Δαが大きくなる。Furthermore, as shown in sample number 15, when y is smaller than 0°996, the nonlinear coefficient α becomes small, and as shown in sample number 18, when y is larger than 1.003,
Varistor voltage change rate ΔV when applying surge current
1 mA and the rate of change Δα of the nonlinear coefficient become larger.
それに対して、この発明の電圧非直線抵抗体用磁器Ｍ１
底物を用いれば、高いバリスタ電圧を有し、サージ電流
が印加されても特性が変わりにくく、かつ大きい非直線
係数を有する電圧非直線抵抗体を得ることができる。On the other hand, the porcelain M1 for voltage nonlinear resistor of this invention
By using the base material, it is possible to obtain a voltage nonlinear resistor having a high varistor voltage, whose characteristics do not easily change even when a surge current is applied, and a large nonlinear coefficient.
Claims (1)
、０≦ｘ≦０．２５、０．９９６≦ｙ≦１．００３）が
９８．０〜９９．９モル％と、Ｎｂ、Ｗ、Ｔａ、Ｉｎあ
るいは希土類元素の酸化物が０．１〜２．０モル％とか
らなる半導体磁器に、 Ｎａ＿２Ｏ、ＳｉＯ＿２およびＣｏ＿２Ｏ＿３（ただし
、０＜Ｎａ、０＜Ｓｉ、０＜Ｃｏ）をあわせて０．０１
〜２．０モル％含有されてなる、電圧非直線抵抗体用磁
器組成物。[Claims] (Sr_1_-_xCa_x)Ti_yO_3 (0≦x≦0.25, 0.996≦y≦1.003) is 98.0 to 99.9 mol%, Nb, W, Ta , In or rare earth element oxides in a total amount of 0.1 to 2.0 mol %, Na_2O, SiO_2 and Co_2O_3 (0<Na, 0<Si, 0<Co) in a total of 0. 01
A ceramic composition for a voltage nonlinear resistor containing ~2.0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2061981A JPH03261658A (en) | 1990-03-12 | 1990-03-12 | Porcelain composition for resistor of non-linear to electric voltage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2061981A JPH03261658A (en) | 1990-03-12 | 1990-03-12 | Porcelain composition for resistor of non-linear to electric voltage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03261658A true JPH03261658A (en) | 1991-11-21 |
Family
ID=13186867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2061981A Pending JPH03261658A (en) | 1990-03-12 | 1990-03-12 | Porcelain composition for resistor of non-linear to electric voltage |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03261658A (en) |
-
1990
- 1990-03-12 JP JP2061981A patent/JPH03261658A/en active Pending
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