JPH0450165A - Porcelain composition for resistor nonlinear to electric voltage - Google Patents

Porcelain composition for resistor nonlinear to electric voltage

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Publication number
JPH0450165A
JPH0450165A JP2158405A JP15840590A JPH0450165A JP H0450165 A JPH0450165 A JP H0450165A JP 2158405 A JP2158405 A JP 2158405A JP 15840590 A JP15840590 A JP 15840590A JP H0450165 A JPH0450165 A JP H0450165A
Authority
JP
Japan
Prior art keywords
porcelain
resistor
electric voltage
voltage
composition
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
Application number
JP2158405A
Other languages
Japanese (ja)
Inventor
Koji Hattori
康次 服部
Kazuyoshi Nakamura
和敬 中村
Yasunobu Yoneda
康信 米田
Yukio Sakabe
行雄 坂部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
Original Assignee
Murata Manufacturing Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to JP2158405A priority Critical patent/JPH0450165A/en
Publication of JPH0450165A publication Critical patent/JPH0450165A/en
Pending legal-status Critical Current

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  • Compositions Of Oxide Ceramics (AREA)
  • Thermistors And Varistors (AREA)

Abstract

PURPOSE:To obtain a porcelain composition giving a resistor non-linear to electric voltage having a large nonlinear coefficient and a high surge resistance by containing fixed amounts of Na2O, SiO2 and Bi2O3, in a semiconductive porcelain containing a specific composition of strontium titanate-based oxide as a principal component. CONSTITUTION:A semiconductive porcelain composed of 98-99.9mol% oxide having a composition expressed by the formula (x<=0.3; y<=0.25) and 2-0.1mol% an agent making semiconductor (e.g. Y2O3) composed of at least a species of oxide selected from Nb, W, Ta, IN or rare earth elements is produced. Next, total 0.01-2mol% Na2O, SiO2 and Bi2O3 (0<Na2O; 0<SiO2; 0<Bi2O3) is contained in the semiconductive porcelain as an oxidizer to afford the aimed a porcelain composition for a resistor nonlinear to electric voltage. A resistor element non-linear to electric voltage is obtained by forming silver electrodes on opposing faces of a porcelain unit produced from the porcelain composition.

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、特に
、たとえば電子機器で発生する異常電圧、ノイズを吸収
もしくは除去するバリスタとして用いられる電圧非直線
抵抗体を得るための電圧非直線抵抗体用磁器組成物に関
する。
Detailed Description of the Invention (Field of Industrial Application) This invention relates to a ceramic composition for voltage non-linear resistors, and in particular to voltage varistors used as varistors to absorb or remove abnormal voltages and noise generated in electronic equipment. The present invention relates to a ceramic composition for a voltage nonlinear resistor for obtaining a nonlinear resistor.

(従来技術) 従来、この種の磁器組成物からなる電圧非直線抵抗体に
は、粒界酸化型電圧非直線抵抗体と、チタン酸ストロン
チウムを主成分とする電圧非直線抵抗体とがあった。
(Prior art) Conventionally, voltage nonlinear resistors made of this type of ceramic composition include grain boundary oxidation type voltage nonlinear resistors and voltage nonlinear resistors whose main component is strontium titanate. .

粒界酸化型電圧非直線抵抗体では、粒界を酸化すること
によってバリスタ特性を得ている。このように粒界を酸
化する方法としては、空気中で粒界を酸化する方法ある
いはNaz Oなとの酸化剤を粒界に拡散する方法が知
られている。
In a grain boundary oxidation type voltage nonlinear resistor, varistor characteristics are obtained by oxidizing the grain boundaries. As a method for oxidizing grain boundaries in this manner, a method of oxidizing grain boundaries in air or a method of diffusing an oxidizing agent such as Naz O into grain boundaries is known.

また、チタン酸ストロンチウムを主成分とする電圧非直
線抵抗体は、異常電圧、ノイズを吸収するバリスタとし
ての機能のほかにコンデンサとしての機能を有している
。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、SrTiO3あるいはSr+−x CaXTio
3  (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Nb2O5、Taz○62
w03 、Laz 03 、CeO2、Ndz 03 
+ Yz03などの金属酸化物およびサージ劣化防止の
ためのNa20を含有したものがあった。
Furthermore, a voltage nonlinear resistor whose main component is strontium titanate has a function as a capacitor in addition to a function as a varistor that absorbs abnormal voltage and noise. Examples of this type of material include SrTiO3 or Sr+-x CaXTio, as disclosed in JP-A-58-16504 and JP-A-58-91602.
3 (0,01≦X≦0.5) as the main component, and Nb2O5 and Taz○62 as components for semiconductor formation.
w03, Laz 03, CeO2, Ndz 03
+ Some contained metal oxides such as Yz03 and Na20 to prevent surge deterioration.

(発明が解決しようとする課題) しかしながら、粒界酸化型電圧非直線抵抗体において、
空気中で粒界を酸化する前者の方法では、バリスタ特性
が総体的に低く、一方、酸化剤を粒界に拡散する後者の
方法では、静電容量が大きいこと、非直線係数αが大き
いこと、あるいはサージ耐量が大きいことの何れかの特
性を満足させることができても、これらの特性のすべて
を1つの組成物で満足させることができなかった。
(Problem to be solved by the invention) However, in the grain boundary oxidation type voltage nonlinear resistor,
The former method, in which the grain boundaries are oxidized in air, has poor varistor characteristics overall, while the latter method, in which the oxidizing agent is diffused into the grain boundaries, has a large capacitance and a large nonlinear coefficient α. Even if it is possible to satisfy any of the characteristics of , high surge resistance, or high surge resistance, it has not been possible to satisfy all of these characteristics with a single composition.

また、チタン酸ストロンチウムを主成分とする電圧非直
線抵抗体でも、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があった。
In addition, even with a voltage nonlinear resistor whose main component is strontium titanate, although a large nonlinear coefficient α can be obtained, it is difficult to obtain a nonlinear coefficient α and a small deterioration of the varistor voltage even when a surge is applied. was there.

それゆえに、この発明の主たる目的は、任意のバリスタ
電圧を有し、かつ大きい非直線係数αおよび高いサージ
耐量を有する電圧非直線抵抗体を得ることができる、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, which can obtain a voltage nonlinear resistor having an arbitrary varistor voltage, a large nonlinear coefficient α, and a high surge resistance. The goal is to provide the following.

(課題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、(
Srl−x−y BaXCay)Ti03 (ただし、
X≦0.30、y≦0.25)が98.0〜99.9モ
ル%と、Nb、W、Ta、I nあるいは希土類元素の
中から選ばれる少なくとも1種類の酸化物が0,1〜2
.0モル%とからなる半導体磁器に、Na2O,5iO
zおよびBi20(Q<Naz O,,0<S r O
z 、0<B iz O8)を合わせて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 the problem) The ceramic composition for a voltage nonlinear resistor according to the present invention has the following features:
Srl-x-y BaXCay)Ti03 (However,
( ~2
.. Semiconductor porcelain consisting of 0 mol% Na2O, 5iO
z and Bi20 (Q<Naz O,,0<S r O
z, 0<B iz O8) is 0.01 to 2.
This is a ceramic composition for a voltage non-linear resistor, containing 0 mol %.

(発明の効果) この発明によれば、任意のバリスタ電圧を有し、大きい
非直線係数αおよび高いサージ耐量を有する電圧非直線
抵抗体を得ることができる、電圧非直線抵抗体用磁器組
成物を得ることができる。
(Effects of the Invention) According to the present invention, a ceramic composition for a voltage nonlinear resistor is provided, which allows obtaining a voltage nonlinear resistor having an arbitrary varistor voltage, a large nonlinear coefficient α, and a high surge withstand capacity. 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) 別表に示す組成比(モル%)となるように、母材料であ
るSrCO3,TiO2,CaCO3゜BaCO3およ
び半導体化剤であるEr20.。
(Example) The base materials SrCO3, TiO2, CaCO3°BaCO3 and the semiconducting agent Er20. .

Nb2O5,WOi、Ta、Os、In2O3゜Y20
3 、HO20s 、La2O3の各原料粉末を秤量し
て湿式混合し、混合物を得た。得られた混合物を乾燥し
た後、1150℃で2時間仮焼して仮焼物を得た。次い
で、得られた仮焼物を粉砕後、それ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。得られた造
粒粉を1  ton/dの圧力で直径10n、厚さ1.
5鶴のベレット状に成形して成形体を得た。
Nb2O5, WOi, Ta, Os, In2O3゜Y20
3, HO20s, and La2O3 raw material powders were weighed and wet-mixed to obtain a mixture. After drying the obtained mixture, it was calcined at 1150° C. for 2 hours to obtain a calcined product. Next, after pulverizing the obtained calcined product, 5% by weight of vinyl acetate resin was added thereto and granulated to obtain granulated powder. The obtained granulated powder was sized to a diameter of 10 nm and a thickness of 1.5 nm under a pressure of 1 ton/d.
A molded product was obtained by molding into a five-tsuru pellet shape.

そして、この成形体を空気中で1000℃で2時間焼成
した後、体積比でHz  :N2=1 : 100の混
合ガス雰囲気中において1450℃で2時間焼成して半
導体磁器を得た。
Then, this 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 with a volume ratio of Hz:N2=1:100 to obtain semiconductor porcelain.

それから、得られた半導体磁器に、Na2O。Then, Na2O was applied to the obtained semiconductor porcelain.

SiO□およびBi2O3の酸化剤を表に示す割合で添
加して、1200℃で5時間熱処理を行っで、磁器ユニ
ットを得た。このようにして得られた磁器ユニットの対
向面に銀電極を形成して電圧非直線抵抗体素子を得た。
Oxidizing agents of SiO□ and Bi2O3 were added in the proportions shown in the table, and heat treatment was performed at 1200° C. for 5 hours to obtain a ceramic unit. Silver electrodes were formed on the opposing surfaces of the ceramic unit thus obtained to obtain a voltage nonlinear resistor element.

そして、電圧非直線抵抗体素子の静電容量C(nF)、
バリスタ電圧V1...A (■)、非直線係数α、バ
リスタ電圧の変化率ΔV+ff1A (%)および非直
線係数の変化率Δα(%)などの電気的特性を調べた。
And the capacitance C (nF) of the voltage nonlinear resistor element,
Varistor voltage V1. .. .. A (■), nonlinear coefficient α, rate of change in varistor voltage ΔV+ff1A (%), rate of change in nonlinear coefficient Δα (%), and other electrical characteristics were investigated.

この場合、電圧非直線抵抗体素子に1mAの電流を流し
てバリスタ電圧Vl−A  (V)を測定シ、5000
A/cutのサージ電流を印加してバリスタ電圧の変化
率Δ■1□ (%)と非直線係数の変化率Δα(%)と
を測定した。そして、それらの測定結果を表に示した。
In this case, the varistor voltage Vl-A (V) is measured by passing a current of 1 mA through the voltage non-linear resistor element, and after 5000
A surge current of A/cut was applied and the rate of change Δ■1□ (%) of the varistor voltage and the rate of change Δα (%) of the nonlinear coefficient were measured. The measurement results are shown in the table.

なお、表中の試料番号に*印の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
の各成分の組成範囲を限定した理由について説明する。
Next, the reason for limiting the composition range of each component of the ceramic composition for a voltage nonlinear resistor according to the present invention will be explained.

この発明で主成分として用いる(S r +−x−y 
Bax Ca、)TiO:+において、BaO量すなわ
ちXをX≦0.30とし、CaO量すなわちyをy≦0
.25とするのは、Xとyがこれらの範囲を超えると、
試料番号8,15.16のように、サージ耐量が低下し
て好ましくないためである。
Used as the main component in this invention (S r +−x−y
Bax Ca,) TiO:+, the BaO amount, or X, is set to X≦0.30, and the CaO amount, or y, is set to y≦0.
.. 25 is because when X and y exceed these ranges,
This is because, as in sample numbers 8, 15, and 16, the surge resistance decreases, which is undesirable.

また、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の量を0.1〜20モル%とする
のは、試料番号17のようにこれらの酸化物が0モル%
ではバリスタ特性を示さず、試料番号22のように2.
0モル%を超えるとサージ耐量が低下するからである。
Furthermore, the reason why the amount of oxides of Nb, W, Ta, In, or rare earth elements as a semiconductor agent is set to 0.1 to 20 mol% is that these oxides are 0 mol% as in sample number 17.
Sample No. 22 shows no varistor characteristics.
This is because if it exceeds 0 mol%, the surge resistance will decrease.

さらに、試料番号30のように酸化剤としてのNaz 
O,S i O2およびB iz 03  (0<Na
20、  o<s ioz 、  O<B iz Ow
l )の合計が0.01モル%未満では、サージ耐量が
低下するためである。一方、試料番号35,40.44
のように、酸化剤の合計が240モル%を超えると、サ
ージ耐量が低下するためである。
Furthermore, as in sample number 30, Naz as an oxidizing agent
O, S i O2 and B iz 03 (0<Na
20, o<s ioz, O<B iz Ow
This is because if the total amount of l) is less than 0.01 mol%, the surge resistance will decrease. On the other hand, sample number 35, 40.44
This is because, if the total amount of oxidizing agents exceeds 240 mol%, the surge resistance decreases.

また、試料番号31.36のように、酸化剤の中のどれ
かが添加されていない場合、非直線係数が小さくなった
り、サージ耐量が低下するためである。
Further, if any of the oxidizing agents is not added, as in sample number 31.36, the nonlinear coefficient becomes small and the surge resistance decreases.

それムこ対して、この発明にがかる電圧非直線抵抗体用
磁器組成物を用いれば、任意のバリスタ電圧を有し、か
つ大きい非直線係数αおよび高いサージ耐量を有する電
圧非直線抵抗体を得ることができる。
On the other hand, if the ceramic composition for a voltage nonlinear resistor according to the present invention is used, a voltage nonlinear resistor having an arbitrary varistor voltage, a large nonlinear coefficient α, and a high surge resistance can be obtained. be able to.

上述の実施例では、たとえば、5000A/cdのサー
ジ電圧印加後のサージ耐量に優れ、非直線係数αがα〉
15と大きい電圧非直線抵抗体を得ることができた。
In the above embodiment, for example, the surge resistance after application of a surge voltage of 5000 A/cd is excellent, and the nonlinear coefficient α is α>
We were able to obtain a voltage nonlinear resistor with a high voltage of 15.

また、母材料にBaを添加した場合には、Baを添加し
ない場合に比べて静電容量が大きくなり、Baの添加量
によって静電容量をコントロールすることができる。
Furthermore, when Ba is added to the base material, the capacitance becomes larger than when Ba is not added, and the capacitance can be controlled by the amount of Ba added.

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)

【特許請求の範囲】[Claims] (Sr_1_−_x_−_yBa_xCa_y)TiO
_3(ただし、x≦0.30、y≦0.25)が98.
0〜99.9モル%と、Nb,W,Ta,Inあるいは
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
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Bi_2O_3(0<Na_
2O、0<SiO_20<Bi_2O_3)を合わせて
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。
(Sr_1_−_x_−_yBa_xCa_y)TiO
_3 (x≦0.30, y≦0.25) is 98.
0 to 99.9 mol% and 0.1 to 2.0 mol% of at least one type of oxide selected from Nb, W, Ta, In, or rare earth elements.
_2O, SiO_2 and Bi_2O_3 (0<Na_
2O, 0<SiO_20<Bi_2O_3) in a total amount of 0.01 to 2.0 mol%.
JP2158405A 1990-06-15 1990-06-15 Porcelain composition for resistor nonlinear to electric voltage Pending JPH0450165A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2158405A JPH0450165A (en) 1990-06-15 1990-06-15 Porcelain composition for resistor nonlinear to electric voltage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2158405A JPH0450165A (en) 1990-06-15 1990-06-15 Porcelain composition for resistor nonlinear to electric voltage

Publications (1)

Publication Number Publication Date
JPH0450165A true JPH0450165A (en) 1992-02-19

Family

ID=15671034

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2158405A Pending JPH0450165A (en) 1990-06-15 1990-06-15 Porcelain composition for resistor nonlinear to electric voltage

Country Status (1)

Country Link
JP (1) JPH0450165A (en)

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