JPH04120703A - Porcelain composition for voltage nonlinear resistor - Google Patents
Porcelain composition for voltage nonlinear resistorInfo
- Publication number
- JPH04120703A JPH04120703A JP2241560A JP24156090A JPH04120703A JP H04120703 A JPH04120703 A JP H04120703A JP 2241560 A JP2241560 A JP 2241560A JP 24156090 A JP24156090 A JP 24156090A JP H04120703 A JPH04120703 A JP H04120703A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- voltage nonlinear
- nonlinear resistor
- nonlinear
- pbo
- 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 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 6
- 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
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract 2
- 229910010252 TiO3 Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000003795 chemical substances by application 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
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical group [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide 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
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder 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
- 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
- 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、５ｒＴｉ０３、あるいは５ｒｌ−ｘ Ｃａ、Ｔｉ
Ｏ３（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Ｎｂｔ Ｏｓ 、Ｔａ２Ｏ，
。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 5rTi03, 5rl-x Ca, Ti, as disclosed in JP-A-58-16504 and JP-A-58-91602.
The main component is O3 (0°01≦X≦0.5), and NbtOs, Ta2O,
.
ＷＯ３、Ｌａ２ｏ３．ＣａＯ２、Ｎｄｚ Ｏ＊ 、 Ｙ
２０３などの金属酸化物およびサージ劣化防止のための
Ｎａｚ Ｏを含有したものがあった。WO3, La2o3. CaO2, NdzO*, Y
Some contained metal oxides such as 203 and Naz O 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いずれかの
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 either 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、高いバリスタ電
圧、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 a high varistor voltage, a large nonlinear coefficient α, and a high surge resistance. be.
（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 ｒｌ−ｘ−ｙ Ｂ ａＸ Ｃａ、 ） Ｔ ｉ Ｏ
ｓ （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、
Ｎａｇ ０１Ｓｉｎ□およびＰｂＯ（０〈Ｎａ２Ｏ、ｏ
＜ｓ ｉ０２．０＜Ｐｂｏ）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 rl-x-y B aX Ca, ) T i O
s (however, X≦0.30, y≦0.25) is 98
．． 0 to 99.9 mol%, and 0.1 to 2.0 mol% of at least one oxide selected from Nb, W, Ta, In or rare earth elements,
Nag 01Sin□ and PbO (0〈Na2O, o
<s i02.0<Pbo) in total from 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、高いバリスタ電圧、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, it is possible to obtain a ceramic composition for a voltage nonlinear resistor that can obtain a voltage nonlinear resistor having a high varistor voltage, a large nonlinear coefficient α, and a high surge withstand capacity. can.
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１に示す組成比（モル％）となるように、母材料で
あるＳ ｒ ＣＯ３、Ｔ ｉＯ２、Ｃａ Ｃ○３ＢａＣ
Ｏ３、および半導体化剤であるＹ２Ｏ３Ｌａｚ ０３
、Ｎｂｚ Ｏｘ 、ＷＯ３、Ｔａｚ ｏｓＥｒｚ ｏ３
、Ｈｏｚ ｏ３ 、Ｉ ｎｚ 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。(Example) The base materials SrCO3, TiO2, CaC○3BaC were adjusted to have the composition ratios (mol%) shown in Attached Table 1.
O3, and the semiconducting agent Y2O3Laz 03
, Nbz Ox , WO3, Taz osErz o3
, Hoz o3, and Inz 03 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.
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、造粒物を得た。得られ
た造粒粉を１ｔｏｎ／ＣｆＡの圧力で直径１０龍、厚さ
１．５璽璽のベレット状に成形して成形体を得た。Next, the obtained calcined product was pulverized, and 5% by weight of vinyl acetate resin was added thereto and granulated to obtain a granulated product. The obtained granulated powder was molded into a pellet shape with a diameter of 10 mm and a thickness of 1.5 mm under a pressure of 1 ton/CfA to obtain a molded body.
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 ：Ｎｚ ＝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:Nz=1:100 to obtain semiconductor porcelain.
それから、得られた半導体磁器に、Ｎａ２０Ｓｉ０２お
よびｐｂｏの酸化剤を表１に示す割合で添加して、１２
００℃で５時間熱処理を行って、磁器ユニットを得た。Then, oxidizing agents of Na20Si02 and pbo were added to the obtained semiconductor porcelain in the proportions shown in Table 1.
Heat treatment was performed at 00° C. for 5 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向面に銀電極
を形成して電圧非直線抵抗体素子を得た。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バリスタ電圧Ｖ１ｍＡ
（Ｖ） 、非直線係数α、静電容量Ｃ，，（ｎＦ）
、バリスタ電圧の変化率ΔＶＩＭＡ （％）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、バリスタ電圧ＶｌｆｆｉＡ （Ｖ）は、
電圧非直線抵抗体素子に１ｍＡの電流を流したときの値
であり、バリスタ電圧の変化率Δ■１ｍＡ （％）お
よび非直線係数の変化率Δα（％）は、それぞれ、５０
００Ａ／−のサージ電流を印加したときの変化率である
。そして、それらの測定結果を、別表２に示した。Then, the varistor voltage V1mA of the voltage nonlinear resistor element
(V), nonlinear coefficient α, capacitance C,, (nF)
, the rate of change in varistor voltage ΔVIMA (%) and the rate of change in nonlinear coefficient Δα (%), and other electrical characteristics were investigated. In this case, the varistor voltage VlffiA (V) is
This is the value when a current of 1 mA is passed through the voltage nonlinear resistor element, and the rate of change of the varistor voltage Δ■ 1 mA (%) and the rate of change of the nonlinear coefficient Δα (%) are each 50
This is the rate of change when a surge current of 00 A/- is applied. The measurement results are shown in Attached Table 2.
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、／）ＴｉＯ２において、ＢａＯ量すなわち
Ｘを０．３０以下とし、かつＣａＯ量すなわちｙを０．
２５以下とするのは、Ｘおよびｙがそれらの範囲を超え
ると、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
In BaXCa,/)TiO2, the BaO amount, or X, is 0.30 or less, and the CaO amount, or y, is 0.30 or less.
The reason why it is set to 25 or less is because if X and y exceed these ranges, the surge resistance decreases, which is not preferable.
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０．１〜２．０モル％と
するのは、これらの酸化物が０モル％ではバリスタ特性
を示さず、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 semiconducting agent is set to 0.1 to 2.0 mol% is that 0 mol% of these oxides does not affect the varistor properties. This is because if it exceeds 2.0 mol %, the surge resistance will decrease.
さらに、酸化剤としてのＮａ２Ｏ，５ｉＯｚおよびＰ
ｂ Ｏ（０＜ Ｎ ａ ｚ Ｏ、Ｏ＜ Ｓ １０ ｚ
、 Ｏ＜Ｐｂ０）の合計が０．０１モル％未満では非
直線係数が小さくかつサージ耐量が低下し、その合計が
２．０モル％を超えるとサージ耐量が低下する。Furthermore, Na2O, 5iOz and P as oxidizing agents
b O(0< N a z O, O< S 10 z
, O<Pb0) is less than 0.01 mol%, the nonlinear coefficient is small and the surge resistance is reduced, and when the sum exceeds 2.0 mol%, the surge resistance is reduced.
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、高いバリスタ電圧、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, a voltage nonlinear resistor having a high varistor voltage, a large nonlinear coefficient α, and a high surge resistance can be obtained.
上述の実施例では、たとえば、５０００Ａ／ａｌ！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, 5000A/al! Excellent surge resistance after applying a surge voltage, and the nonlinear coefficient α is α
>15, a large voltage nonlinear resistor could be obtained.
また、素体にＢａを添加した場合には、Ｂａを添加しな
い場合より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 element body, 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)
＿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ＰｂＯ（０＜Ｎａ＿２Ｏ、０
＜ＳｉＯ＿２、０＜ＰｂＯ）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 PbO (0<Na_2O, 0
<SiO_2, 0<PbO) in total from 0.01 to 2.
A ceramic composition for a voltage nonlinear resistor containing 0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2241560A JPH04120703A (en) | 1990-09-11 | 1990-09-11 | Porcelain composition for voltage nonlinear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2241560A JPH04120703A (en) | 1990-09-11 | 1990-09-11 | Porcelain composition for voltage nonlinear resistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04120703A true JPH04120703A (en) | 1992-04-21 |
Family
ID=17076166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2241560A Pending JPH04120703A (en) | 1990-09-11 | 1990-09-11 | Porcelain composition for voltage nonlinear resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04120703A (en) |
-
1990
- 1990-09-11 JP JP2241560A patent/JPH04120703A/en active Pending
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