JPH0450163A - Porcelain composition for resistor nonlinear to electric voltage - Google Patents
Porcelain composition for resistor nonlinear to electric voltageInfo
- Publication number
- JPH0450163A JPH0450163A JP2158403A JP15840390A JPH0450163A JP H0450163 A JPH0450163 A JP H0450163A JP 2158403 A JP2158403 A JP 2158403A JP 15840390 A JP15840390 A JP 15840390A JP H0450163 A JPH0450163 A JP H0450163A
- Authority
- JP
- Japan
- Prior art keywords
- porcelain
- voltage
- electric voltage
- composition
- resistor
- 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 20
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical group [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract 3
- 239000000377 silicon dioxide Substances 0.000 abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract 3
- 229910052682 stishovite Inorganic materials 0.000 abstract 3
- 229910052905 tridymite Inorganic materials 0.000 abstract 3
- 230000007423 decrease Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
- Compositions Of Oxide Ceramics (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、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Ｎａ２Ｏなど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 Na2O 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 ＣａＸＴｉｅ、
（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Ｎｂ２０ｓ 、 Ｔａ２ｏ５．Ｗ
Ｏ２、Ｌａｚ ０３ 、Ｃｅ０ｚ 、Ｎａｚｏ３．Ｙ２
０３などの金属酸化物およびサージ劣化防止のためのＮ
ａｚ Ｏ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 CaXTie, as disclosed in JP-A-58-16504 and JP-A-58-91602
(0,01≦X≦0.5) as a main component, and Nb20s, Ta2o5. W
O2, Laz 03, Ce0z, Nazo3. Y2
Metal oxides such as 03 and N to prevent surge deterioration
Some contained azO.
（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、（
Ｓ ｒ １−ｘ−ｙ Ｂａｘ Ｃａｙ） Ｔ ＋０３
（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、Ｎａｚ
ＯｌＳ ｉ Ｏ２およびＭ２Ｏ３（Ｑ＜Ｎａｇ Ｏｌｏ
＜Ｓ ｉ○２．０〈Ｍ２Ｏ３）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:
S r 1-x-y Bax Cay) T +03
(However, X≦0.30, y≦0.25) is 98.0~
99.9 mol% and at least one oxide selected from Nb, W, Ta, In or rare earth elements is 0.
．． Naz
OlS i O2 and M2O3 (Q<Nag Olo
<Si○2.0<M2O3) in total 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５ｒＣＯｘ 、Ｔｉ０ｚ 、ＣａＣＯ３゜Ｂａｃｏ、
および半導体化剤であるＥｒｚＯ，、。(Example) The base materials 5rCOx, TiOz, CaCO3゜Baco,
and ErzO, which is a semiconducting agent.
Ｎｂ２０５ 、ＷＯ３、Ｔａ２ｏｓ 、ｆｒｉｚ ０３
。Nb205, WO3, Ta2os, friz 03
.
Ｙ２０３ 、 Ｈ０２０３、Ｌ ａｚ ０３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１０
ｍ、厚さ１．５＋ｎのベレット状に成形して成形体を得
た。Each raw material powder of Y203, H0203, and L az 03 was 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 mm at a pressure of 1 ton/d.
A molded body was obtained by molding into a pellet shape with a thickness of 1.5 m and a thickness of 1.5+n.
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Ｈ２：Ｉ”Ｊ２＝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 H2:I''J2=1:100 to obtain semiconductor porcelain.
それから、得られた半導体磁器に、Ｎａｇ ０３ｉＯ□
およびＭ ｏ Ｏ３の酸化剤を表に示す割合で添加して
、１２００℃で５時間熱処理を行って、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。Then, the obtained semiconductor porcelain was coated with Nag 03iO□
and M o O3 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Ｖｌ−Ａ （Ｖ） 、非直線係数α、バ
リスタ電圧の変化率ΔＶ１．Ａ （％）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。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ｖ＋−ｓ （Ｖ）を測定し、５０００Ａ
／ｃ＋＋ｔのサージ電流を印加してバリスタ電圧の変化
率ΔＶ、−（％）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。And the capacitance C (nF) of the voltage nonlinear resistor element,
Varistor voltage Vl-A (V), nonlinear coefficient α, rate of change of varistor voltage ΔV1. Electrical properties such as A (%) and the rate of change Δα (%) of the nonlinear coefficient were investigated. In this case, the varistor voltage v+-s (V) is measured by passing a current of 1 mA through the voltage nonlinear resistor element, and the voltage is 5000 A.
A surge current of /c++t was applied to measure the rate of change ΔV, - (%) of the varistor voltage and the rate of change Δα (%) of the nonlinear coefficient. 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 １−ｘ−ｙ
ＢａＸＣａ、）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 1-x-y
BaXCa, )TiO:+, the BaO amount, or X, is set to X≦0.30, and the CaO amount, or y, is set to y≦0.
The reason why it is set to 25 is because if X and y exceed these ranges, the surge resistance decreases, which is not preferable, as in sample number 8, 15.16.
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Ｎ ａ
ｚ Ｏ，Ｓ ｉＯｘおよびＭｏ５ｓ （０＜Ｎａ２Ｏ
，０＜Ｓ ｉｏｚ 、０＜ＭＯＯ３）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２．０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, Na as an oxidizing agent
z O, SiOx and Mo5s (0<Na2O
,0<S ioz ,0<MOO3) is 0°01
This is because if the amount is less than mol%, the surge resistance decreases. On the other hand, if the total amount of oxidizing agents exceeds 2.0 mol %, as in sample number 35.40.44, 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.
それに対して、この発明にか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, by using the ceramic composition for a voltage nonlinear resistor according to the present invention, it is possible to obtain a voltage nonlinear resistor having an arbitrary varistor voltage, a large nonlinear coefficient α, and a high surge resistance. can.
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) Zenhiro
Claims (1)
（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＿２
Ｏ、ＳｉＯ＿２およびＭｏＯ＿３（０＜Ｎａ＿２Ｏ、０
＜ＳｉＯ＿２、０＜ＭｏＯ＿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
(However, x≦0.30, y≦0.25) is 98.0~
99.9 mol% and at least one oxide selected from Nb, W, Ta, In or rare earth elements is 0.
．． 1 to 2.0 mol% of Na_2
O, SiO_2 and MoO_3 (0<Na_2O, 0
<SiO_2, 0<MoO_3) in total 0.01~
A ceramic composition for a voltage nonlinear resistor containing 2.0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2158403A JPH0450163A (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 |
|---|---|---|---|
| JP2158403A JPH0450163A (en) | 1990-06-15 | 1990-06-15 | Porcelain composition for resistor nonlinear to electric voltage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0450163A true JPH0450163A (en) | 1992-02-19 |
Family
ID=15670989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2158403A Pending JPH0450163A (en) | 1990-06-15 | 1990-06-15 | Porcelain composition for resistor nonlinear to electric voltage |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0450163A (en) |
-
1990
- 1990-06-15 JP JP2158403A patent/JPH0450163A/en active Pending
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