JPS62282407A - Manufacture of voltage nonlinear resistance element - Google Patents
Manufacture of voltage nonlinear resistance elementInfo
- Publication number
- JPS62282407A JPS62282407A JP61126072A JP12607286A JPS62282407A JP S62282407 A JPS62282407 A JP S62282407A JP 61126072 A JP61126072 A JP 61126072A JP 12607286 A JP12607286 A JP 12607286A JP S62282407 A JPS62282407 A JP S62282407A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- main component
- mol
- sintered body
- agent containing
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- 239000011787 zinc oxide Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 74
- 239000011701 zinc Substances 0.000 description 9
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
３、発明の詳細な説明
産業上の利用分野
本発明は酸化亜鉛を主成分とし、それ自身が電圧非直線
性を有する焼結体の側面に、高抵抗層を形成した電圧非
直線抵抗体素子の製造方法に関するものである。Detailed Description of the Invention 3. Detailed Description of the Invention Industrial Application Field The present invention forms a high-resistance layer on the side surface of a sintered body containing zinc oxide as a main component and having voltage nonlinearity itself. The present invention relates to a method of manufacturing a voltage nonlinear resistor element.
従来の技術
電圧非直線抵抗体素子は一般にバリスタと呼ばれ、電圧
安定化やサージ吸収素子として用いられている。なかで
も、酸化亜鉛を主成分とし、これに少量のＢｉ、、Ｏ，
、Ｃｏ２Ｏ３，ＭｎＯ，、、５ｂ２０． 、Ｃｒ２Ｏ３
などの金属酸化物を添加した酸化亜鉛バリスタは、その
大きなサージ電流耐量と優れた電圧非直線性から、近年
ギャップレスアレスタ用の素子として従来のシリコンカ
ーバイトバリスタにとって代わり広く利用されている。BACKGROUND ART A voltage nonlinear resistor element is generally called a varistor, and is used as a voltage stabilizing or surge absorbing element. Among them, zinc oxide is the main component, and small amounts of Bi, O,
, Co2O3, MnO, , 5b20. , Cr2O3
Zinc oxide varistors doped with metal oxides have recently been widely used as elements for gapless arresters in place of conventional silicon carbide varistors due to their large surge current withstand capacity and excellent voltage nonlinearity.
酸化亜鉛バリスタをアレスタ素子として用いる場合、極
めて重要な特性要素が２つある。第１は、放電耐量特性
である。これはＪ Ｅ Ｃ−１８７−１９７３に規定さ
れている４×１０μｓの衛撃電流を５分間隔で２回印加
し、素子が耐え得るピーク電流の限界値である。第２に
課電寿命特性で、これは規定の交流電圧を印加した際に
、アレスタ素子が熱暴走に至るまでの時間である。通常
は、周囲温度２１ｏ Ｏ”Ｃ以上、ｎｔＪ （ｖ印加電
圧×１００／ｖ、！ＩＩＡ）を９０％以上に設定し、加
速試験を行う。近年、高放電耐量、長寿命のアレスタ素
子の開発が市場から強く望まれている。When using a zinc oxide varistor as an arrester element, there are two extremely important characteristic factors. The first is discharge endurance characteristics. This is the limit value of the peak current that the device can withstand when a 4×10 μs satellite current specified in JEC-187-1973 is applied twice at 5-minute intervals. The second is the energization life characteristic, which is the time it takes for the arrester element to reach thermal runaway when a specified alternating current voltage is applied. Normally, accelerated tests are performed at an ambient temperature of 21o O"C or higher and ntJ (v applied voltage x 100/v,!IIA) set to 90% or higher. In recent years, arrester elements with high discharge resistance and long life have been developed. is strongly desired by the market.
従来より、電圧非直線抵抗体素子（以下アレスタ素子）
の製造方法として、特開昭５６−６９８０４号公報、特
公昭８Ｑ−１６１２８号公報などが知られている。前者
は、酸化亜鉛形のアレスタ素子（Ｄ成形体マタハ仮焼体
）Ｉｌｌ 面Ｋ、３１０２ 、 Ｚ ｎ ｙ Ｓｂｚ
０，２ 。Conventionally, voltage nonlinear resistor elements (hereinafter referred to as arrester elements)
As a manufacturing method, Japanese Unexamined Patent Publication No. 56-69804, Japanese Patent Publication No. 8Q-16128, etc. are known. The former is a zinc oxide type arrester element (D molded body calcined body) Ill surface K, 3102, Zny Sbz
0,2.
Ｂｉ２Ｏ，などの混合物を塗布した後、焼結し、側面だ
高抵抗層を有するアレスタ素子’ｒＭ造するものである
。後者は、同様の成形体を焼成する際、焼成容器内ＫＳ
ｂ２０． 、 Ｂｉ２Ｏ３，５ｉｎ２すどカラナル混合
物を配置し、気−固相反応により、側面に高抵抗層を有
するアレスタ素子を製造するものである。After coating a mixture of Bi2O, etc., it is sintered to produce an arrester element having a high resistance layer on the side surfaces. When firing a similar molded body, the latter is
b20. , Bi2O3, 5in2 sudocaranal mixture is disposed, and an arrester element having a high resistance layer on the side surface is manufactured by gas-solid phase reaction.
発明が解決しようとする問題点
このような前者の方法では、側面高抵抗層の構造が不安
定で素子と側面剤との密着性が悪く、放電耐量が低いと
いう欠点を有していた。また、後者の方法では、焼成容
器内部に適当に配置した５ｂ２０． 、 Ｂｉ２Ｏ，な
どからなる塗布剤の蒸気と成形体と全反応させるため、
側面高抵抗層の厚みが充分とれず、放電耐量が低いばか
りでなく、同一焼成容器中で焼成可能な素子数が限られ
、量産性に欠けるという欠点を有していた。Problems to be Solved by the Invention The former method has disadvantages in that the structure of the side high resistance layer is unstable, the adhesion between the element and the side surface agent is poor, and the discharge withstand capacity is low. In addition, in the latter method, 5b20. , Bi2O, etc., in order to cause the vapor of the coating agent to react completely with the molded body.
The high-resistance layer on the side surface was not thick enough, resulting in a low discharge withstand capacity, and the number of elements that could be fired in the same firing container was limited, making it difficult to mass-produce.
本発明は、このような開閉点を解決するもので、アレス
タとしての酸化亜鉛バリスタの高性能化、すなわち放電
耐量特性１課電寿命特性の大巾な向上を目的とするもの
である。The present invention solves such switching points and aims to improve the performance of a zinc oxide varistor as an arrester, that is, to significantly improve the discharge withstand characteristics 1 and the charging life characteristics.
問題点を解決するための手段
本発明では、前記の問題点を解決するため、酸化亜鉛を
主成分とするアレスタ素子の成形体または仮焼体の側面
に２種１の成分の異なった側面剤を塗布することにより
、焼結体側面に２層の高抵抗層を形成したものである。Means for Solving the Problems In the present invention, in order to solve the above-mentioned problems, a side surface agent having two types of different components is applied to the side surface of a molded or calcined body of an arrester element containing zinc oxide as a main component. Two high-resistance layers are formed on the side surface of the sintered body by coating the sintered body.
作用
本発明の電圧非直線抵抗体素子の製造方法は、酸化亜鉛
バリスタ素子の成形体または仮焼体の側面に、Ｓｉｎ、
、 ｆ主成分とじＺ ｎ ７ Ｓ ｂ ｚ ０１２を添
加した第１の側面剤を塗布し、その上部にＺｎ２５ｉＯ
４’ｉ主成分としＢｉ２Ｏ，を添加した第２の側面剤を
塗布した後、焼成し、バリスタ素子側面に高抵抗層を形
成するため、高抵抗層下層部にＺ ｎ ｙ Ｓ ｂ ２
０１□。Function The method for manufacturing a voltage nonlinear resistor element of the present invention includes adding a layer of Sin,
, f Main component binding Zn7S b z 012 was added to the first side surface agent, and Zn25iO was applied on top of it.
After applying the second side surface agent containing Bi2O as the main component of 4'i, it is fired to form a high resistance layer on the side surface of the varistor element.
01□.
Ｚｎ２５ｉｎ４の混合相、同上層部にＺｎ２５ｉＯ４相
の安定な２層構造を得ることができる。このことがらバ
リスタ素体−高抵抗層間の密着性が増し放電耐量が向上
し、高抵抗層上部のＺｎ、、 Ｓ工０４のカバーリング
効果にエリバリスタ素体からのＢｉ２Ｏ，飛散を怪減し
、課電寿命特性を大巾に向上させることができる。A stable two-layer structure can be obtained with a mixed phase of Zn25in4 and a Zn25iO4 phase in the upper layer. This increases the adhesion between the varistor body and the high-resistance layer, improves the discharge capacity, and significantly reduces the scattering of Bi2O from the varistor body due to the covering effect of Zn on the top of the high-resistance layer and S-04. , the charging life characteristics can be greatly improved.
実施例
以下、本発明の製造方法およびそれによって得られた電
圧非直線抵抗体素子について実施例に基づき詳細に説明
する。EXAMPLES Hereinafter, the manufacturing method of the present invention and the voltage nonlinear resistor element obtained thereby will be explained in detail based on examples.
まず、ＺｎＯの粉末に、合計量に対しＢｉ２Ｏ，０，５
層ル％ 、 Ｃｏ２０．０．６モル％ 、 ＭｎＯ２０
，５層ル％ 。First, add Bi2O,0,5 to the total amount of ZnO powder.
layer%, Co20.0.6 mol%, MnO20
, 5 layers%.
５ｂ２０５１．０モル％ 、 Ｃｒ２Ｏ，０，６モル％
、Ｎｉ００，６モル％を加え、充分に粉砕、混合した
後、造粒して原料粉を得た。この原料粉を直径４０１１
ＬｌｌＬ、厚さ３０駄の大きさに圧縮成形した。このよ
うにして得られた成形体を９００°Ｃ，２時間焼成し冷
却して仮焼体を得た。5b2051.0 mol%, Cr2O, 0.6 mol%
, 0.6 mol % of Ni were added, thoroughly crushed and mixed, and then granulated to obtain a raw material powder. This raw material powder has a diameter of 4011 mm.
It was compression molded to a size of 30cm thick. The thus obtained molded body was fired at 900°C for 2 hours and cooled to obtain a calcined body.
一方、側面高抵抗層用のペーストは、Ｚｎ７Ｓｂ２Ｏ１
２゜Ｚｎ２５ｉｎ４． Ｂｉ□Ｏ，、Ｓｉｎ□ｆｆｚ適
当な割合−ｃｍ合した原料粉と、エチルセルロース２５
ｗｔ％、プチルカルピトール７５ ｗｔ％からなるバイ
ンダートラ、重量比で１対３の割合で配合し、均一にな
るように混練して作成した。本発明では、この側面高抵
抗層用のペーストは、５ｉｎ２． Ｚｎ、５ｂ２０１□
からなる下層用と、Ｚ ｎ ２ Ｓ ｉＯ４ｆ：主成分
とする上層用の２種類がある。On the other hand, the paste for the side high resistance layer is Zn7Sb2O1
2゜Zn25in4. Bi□O,, Sin□ffz suitable ratio - cm combined raw material powder and ethyl cellulose 25
A binder containing 75 wt% of butylcarpitol was mixed in a weight ratio of 1:3, and kneaded uniformly. In the present invention, the paste for the side high resistance layer is 5in2. Zn, 5b201□
There are two types: one for the lower layer consisting of Zn2SiO4f and the other for the upper layer consisting of Zn2SiO4f as the main component.
前述の仮焼体側面に下層用のペーストラ塗布し、乾燥さ
せてから、上層用のペーストを塗布し、再度乾燥後、空
気中において１２００°Ｃで焼結させた。このようにし
て得られた焼結体の両端面を研磨し、アルミニウムの溶
射電極を形成した。A paste for the lower layer was applied to the side surface of the above-mentioned calcined body, and after drying, a paste for the upper layer was applied, and after drying again, it was sintered at 1200°C in the air. Both end faces of the sintered body thus obtained were polished to form sprayed aluminum electrodes.
第１図は上述したようにして得た電圧非直線抵抗体素子
の断面図であり、１はＺｎＯを主成分とする焼結体、２
はＺｎ７Ｓｂ２Ｏ１２．Ｚｎ２５ｉｏ４相の混在する側
面高抵抗層第１層（下層）、３ばＺｎ２５１０４を主成
分とする側面高抵抗層第２層（上層）、４はアルミニウ
ム溶射により形成された電極である。FIG. 1 is a cross-sectional view of the voltage nonlinear resistor element obtained as described above, in which 1 is a sintered body mainly composed of ZnO, 2 is a sintered body mainly composed of ZnO,
is Zn7Sb2O12. A first layer (lower layer) of a side high resistance layer containing a mixture of Zn25io4 phases, a second layer (upper layer) of a side high resistance layer mainly composed of Zn25104, and 4 are electrodes formed by aluminum spraying.
なお、側面高抵抗層２，３の成分はＸ線回折により確認
された。また、Ｘ線マイクロアナライザーによる分析か
ら、第１層（下層）２にはｕｎ、Ｇｏ。The components of the side high resistance layers 2 and 3 were confirmed by X-ray diffraction. Furthermore, analysis using an X-ray microanalyzer revealed that un and Go were present in the first layer (lower layer) 2.
Ｏｒ などが固溶し、第２層（上層）３には主としてＧ
ｏが固溶していることが確認された。Or etc. are dissolved in solid solution, and the second layer (upper layer) 3 mainly contains G.
It was confirmed that o was dissolved in solid solution.
下記の第１表は、側面高抵抗層第１層お：び第２層用の
側面剤の組成表である。第１層用側面剤はＳｉｎ、、
、 Ｚｎ、５ｂ２０．□からなり、第２層用Ｉ１１ 固
剤はＺｎ２５ｉｎ４． Ｂｉ□Ｏ，からなる。Table 1 below is a composition table of side coating materials for the first and second layers of the side high resistance layer. The side surface agent for the first layer is Sin.
, Zn, 5b20. The solid agent for the second layer is Zn25in4. Consisting of Bi□O.
この側面剤を仮焼体に第１層用側面剤、第２層用側面剤
の順に塗布し、焼結させた後、人！メタリコン電極を付
け、’／４ｍＡ ／Ｂ、 ”／、 、）、／Ｖ、 ｏ、
、Ａ 、外観などを調べた。この結果を下記の第２表に
示すと共に第１層用、第２層用の側面剤の組合せを種々
変えた場合について示している。比較のため従来例１
トＬテＢｉ２Ｏ３，Ｚｎ、５ｂ２Ｏ１２．５ｉｎ２ｉそ
れぞれ１０モルチ、１０モル％、ｓｏモルチ含む側面剤
を含む側面剤を仮焼体に塗布した場合、従来例２とシテ
Ｂ１２Ｏ３，５ｂ２０．ヲそれぞれ１０モル％。This side surface agent was applied to the calcined body in the order of the first layer side surface agent and the second layer side surface agent, and after sintering, the surface layer was sintered. Attach metallicon electrode, '/4mA /B, ''/, , ), /V, o,
, A. We investigated the appearance, etc. The results are shown in Table 2 below, and also show cases in which the combinations of side surfaces for the first layer and the second layer were varied. Conventional example 1 for comparison
When the calcined body was coated with a surfacing agent containing 10 molti, 10 mol%, and so molti of Bi2O3, Zn, 5b2O12.5in2i, respectively, Conventional Example 2 and Bi2O3, 5b20. 10 mol% each.
９０モルチ含む塗布剤を焼成容器内に配置し、気−固相
反応により側面高抵抗層を形成した場合のデータを追記
した。ここで、ｖ１Ｔｎム／Ｂは第２層用側面剤中のＢ
ｉ２Ｏ５濃度が増、＋１０するにつれて低下傾向を示し
、逆にｖｔｍ人／ｖｔｏ□よは向上する傾向がある。し
かし、第２層側面剤中の８１２Ｏ５濃度が３０モル％を
超えると側面剤の流れが発生し、ｖＩ ｍＡ／ ｖ、
ａ ７□えは逆にわずかに上昇する。また、第１層側面
剤中のＺｎ、５ｂ２Ｏ１２＠度が増すにつれ、’Ｉ
／Ｖ は向上している。Data for the case where a coating agent containing 90 molti was placed in a firing container and a side high resistance layer was formed by gas-solid phase reaction was added. Here, v1Tnmu/B is B in the side surface agent for the second layer.
As the i2O5 concentration increases and increases by +10, it shows a decreasing tendency, and conversely, vtm person/vto□yo tends to increase. However, when the 812O5 concentration in the second layer side agent exceeds 30 mol%, flow of the side agent occurs, and vI mA/v,
a7□E, on the contrary, increases slightly. In addition, as the Zn, 5b2O12@ content in the first layer side additive increases, 'I
/V has improved.
１ｍＡ １０／ｊＡ
く第１表〉
単位二モルチ
〈第３人〉
第２図〜第７図に本発明および参考例の製造方法による
電圧非直線抵抗体素子の放電耐量特性、課電寿命特性の
結果を示す。図中の横軸は、第２層側面剤中のＢ１□ｏ
３濃度である。ここで、放電耐量試験はＪＩＣＣ−１８
７−１９７３に規定された４Ｘ１０μｓの衝撃電流を同
一方向に５分間隔で２回印加し、外観異常などをチェッ
クした。また、試験は１０に人毎のステップアップ方式
で行い、図中には黒丸印で示した。そして、２回の衝撃
電流に耐えなかった試料に関しては印加電流から５ＫＡ
ｉ減じて示した。さらに、課電寿命試験は周囲温度１
３０°Ｃ１課電率９５％（６０Ｈ２ＡＣ）の条件で行い
、漏れ電流が１０ｍＡに達した時点で熱暴走と判定し、
それに要した時間を図中に白丸印で示した。上記の第３
表に従来例１お工び２の放電耐量特性、課電寿命特性を
示した。ここで、Ｂｉ２Ｏ，、Ｚｎ、５ｂ２０．２．５
ｉｎ２ 系側固剤塗布方式（従来例１）では、放電耐
量ＳＯＸ人１回、課電寿命２９ 時間、Ｂｉ２Ｏ，、５
ｂ２０３気−固相反応系（従来例２）では、放電耐量５
ＱＫＡ２回、課電寿命３１時間の性能を有していた。1mA 10/jA (Table 1) Unit: 2 molti (3rd person) Figures 2 to 7 show the discharge withstand characteristics and energized life characteristics of voltage nonlinear resistor elements manufactured by the manufacturing methods of the present invention and reference examples. Show the results. The horizontal axis in the figure is B1□o in the second layer side surface agent.
3 concentrations. Here, the discharge withstand test is JICC-18
An impact current of 4×10 μs as specified in 7-1973 was applied twice in the same direction at an interval of 5 minutes, and abnormalities in appearance were checked. Further, the test was conducted in a step-up manner for each person in 10 days, and is indicated by a black circle in the figure. For samples that did not withstand two shock currents, the applied current was increased by 5 KA.
Shown by subtracting i. Furthermore, the energized life test was performed at an ambient temperature of 1
It was conducted under the conditions of 30°C, 95% charge rate (60H2AC), and thermal runaway was determined when the leakage current reached 10mA.
The time required for this is indicated by a white circle in the figure. 3rd above
The table shows the discharge withstand characteristics and energized life characteristics of Conventional Example 1 and Process 2. Here, Bi2O,, Zn, 5b20.2.5
In2 system side solid agent application method (conventional example 1), discharge withstand capacity SOX once, energized life 29 hours, Bi2O, 5
b203 gas-solid phase reaction system (conventional example 2) has a discharge capacity of 5
It had the performance of 2 QKAs and 31 hours of power application life.
第２図から第７図を比較すると、第１層側面剤中のＺｎ
７Ｓｂ２ｏ、２濃度が０．１モルチより低い領域および
３０モルチより高い領域で放電耐量特性、課電寿命特性
とも低レベルにあるが、０．１〜３０モルチの領域では
両特性とも優れていることがわかる。また、第２層側面
剤中の８１２Ｏ．濃度が増加するに従い課電寿命特性は
向上し、２０モル係でピークに達し、３ｏモル％を越え
た場合には再び低下する。これは側面高抵抗層の一部が
焼結反応の過程で、Ｂ１２Ｏ．が過多であることにエリ
流れ落ち、逆にアレスタ素子からのＢ１２ｏ３が飛散し
易くなるためと考えられる。一方、放電耐量特性はＢ１
２Ｏ．濃度が２０〜３０モルチまでは一定で、その後急
激に低下する。これはＢ工、、ｏ、ｍ度が高いため側面
高抵抗層の一部が流れ落ちたり、上層に形成されるｚｎ
２Ｓ１０４相の粒界にＢｉ２Ｏ，が残存するためと考え
られる。そして、第１層側面剤に前記側面剤人５、第２
層側面剤に前記側面剤８３を用いた場合、放電耐量特性
は９０ＫＡ、課電寿命特性は３２６時間の性能を有し、
従来例と比較し著しい高特性が得られることがわかる。Comparing Figures 2 to 7, it can be seen that Zn in the first layer sidewall
7Sb2o, 2 concentration is lower than 0.1 molti and higher than 30 molti, the discharge withstand characteristics and charging life characteristics are at low level, but in the range of 0.1 to 30 molti, both characteristics are excellent. I understand. In addition, 812O. As the concentration increases, the charged life characteristics improve, reaching a peak at 20 mol %, and decrease again when it exceeds 30 mol %. This is due to the process of sintering reaction in which a part of the side high resistance layer is B12O. This is thought to be because too much B12o3 flows down, and conversely, B12o3 from the arrester element becomes more likely to scatter. On the other hand, the discharge withstand characteristic is B1
2O. The concentration remains constant until 20 to 30 molt, and then decreases rapidly. This is due to the high degree of B, o, m, so that part of the side high resistance layer may run off or the Zn formed on the upper layer may run off.
This is thought to be because Bi2O remains at the grain boundaries of the 2S104 phase. Then, the side layer 5 is applied to the first layer side layer, and the second side layer layer is
When the above-mentioned side surface agent 83 is used as the layer side surface agent, the discharge capacity characteristic is 90 KA, the electrification life characteristic is 326 hours,
It can be seen that significantly higher characteristics can be obtained compared to the conventional example.
以上のように、本発明の製造方法による電圧非直線抵抗
体素子が、放電耐量特性、課電寿命特性ともに高性能を
示す理由は、以下のように推定される。すなわち、従来
のＢｉ□Ｏ，、Ｚｎ、５ｂ２Ｏ１２（Ｓｂ２０． ）
、 ５ｉｎ２からなる成分単層側面剤を用いた場合、そ
の生成物は単にＺｎ７Ｓｂ２Ｏ１２とｚｎ２Ｓ１０４の
混在系であるのに対し、２層塗布方式の側面剤を用いた
場合、第１層（下層）にＺｎ７Ｓｂ２Ｏ１２゜Ｚｎ２５
１０４相が生成し、第２層（上層）にＺｎ２５１０４相
が生成して構造が極めて安定となる。この工うにして生
成した下層の特にＺｎ７Ｓｂ２Ｏ１２ 相は高抵抗で
バリスタ素子との密着性が高く放電耐量の向上に寄与し
、上層のＺｎ２５１０４相はバリスタ素子からのＢ１２
Ｏ．飛散を軽減し課電寿命特性の向上に寄与していると
考えられる。As described above, the reason why the voltage nonlinear resistor element manufactured by the manufacturing method of the present invention exhibits high performance in both discharge withstand characteristics and energized life characteristics is presumed as follows. That is, conventional Bi□O,, Zn, 5b2O12 (Sb20.)
, When a single-layer side surface agent consisting of 5in2 is used, the product is simply a mixed system of Zn7Sb2O12 and zn2S104, whereas when a two-layer side surface agent is used, the first layer (lower layer) Zn7Sb2O12゜Zn25
104 phase is generated, and Zn25104 phase is generated in the second layer (upper layer), making the structure extremely stable. The lower layer, especially the Zn7Sb2O12 phase, produced in this way has high resistance and has high adhesion with the varistor element, contributing to improving the discharge withstand capacity, while the upper layer, the Zn25104 phase,
O. It is thought that this reduces scattering and contributes to improving the charging life characteristics.
本実施例においては側面高抵抗層用の２種類の側面剤を
仮焼体に塗布した場合についてのみ記載し次が、第１層
、第２層用側面剤をともに成形体に塗布した場合、また
第１層用側面剤を成形体に、第２層用側面剤を仮焼体に
塗布した場合にも同様の効果があることを確認した。ま
た、本発明においては側面高抵抗層用の材料として５ｉ
ｎ２． Ｚｎ２ＳｉＯ４゜Ｚｎ、５ｂ２Ｏ１２． Ｂｉ
２Ｏ，２用いたが、これらにアレスタ素子の粒界層の構
成要素である成分、すなわちＢｉ Ｏ、Ｃｏ Ｏ、Ｃｒ
２Ｏ，、ＭｎＯ□、 ＮｉＯ，ＭｇＯなどを添加しても
本発明の効果に変わりはないものである。In this example, only the case where two types of side surface agents for the side high resistance layer are applied to the calcined body is described. Next, the case where both the side surface agents for the first layer and the second layer are applied to the molded body, It was also confirmed that similar effects were obtained when the first layer side surface agent was applied to the molded body and the second layer side surface agent was applied to the calcined body. In addition, in the present invention, 5i is used as a material for the side high resistance layer.
n2. Zn2SiO4゜Zn, 5b2O12. Bi
2O,2 was used, but these also contain components that are the constituent elements of the grain boundary layer of the arrester element, namely BiO, CoO, and Cr.
Even if 2O, MnO□, NiO, MgO, etc. are added, the effects of the present invention will not change.
発明の効果
以上のように本発明によれば、酸化亜鉛形バリスタ素子
の成形体または仮焼体の側面に５ｉｎ２゜Ｚｎ７Ｓｂ２
ｏ、２ からなる第１の側面剤を塗布し、その上層に
Ｚｎ２５ｉｎ４． Ｂｉ２Ｏ３ からなる第２の側面
剤を塗布後、焼結させることに工り、放電耐量特性０課
電寿命特性が非常に優れた電圧非直線抵抗体素子を製造
することができる。Effects of the Invention As described above, according to the present invention, a 5in2゜Zn7Sb2
A first side coating consisting of Zn25 in 4. By applying the second side surface agent made of Bi2O3 and then sintering it, it is possible to manufacture a voltage non-linear resistor element having very excellent discharge withstand characteristics and 0-charge life characteristics.
第１図は本発明の製造方法による電圧非直線抵抗体素子
の断面図、第２図〜第７図は本発明お工び参考例の製造
方法による電圧非直線抵抗体素子の放電耐量特性および
課電寿命特性を示す図である。
１・・・・・・酸化亜鉛形バリスタ素子、２・・・・・
・側面高抵抗層第１層（下層）、３・・・・・・側面高
抵抗層第２層（上層）、４・・・・・・電極。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第２
図
ト Ｎ の ＋ Ｎ づ第３図
→８ ｔ ２０ ｓ １ｕ覧（モ）し％ ）第４図
Ｂｉ ２ （ｌｌａ ’ＸｆｉＬ （モルヅ・）第５図
→ ９ｔ２０３ う恵１１ζし代ルプ、）第６図
第７図FIG. 1 is a cross-sectional view of a voltage nonlinear resistor element produced by the manufacturing method of the present invention, and FIGS. 2 to 7 show the discharge withstand characteristics and FIG. 3 is a diagram showing charging life characteristics. 1... Zinc oxide type varistor element, 2...
- Side high resistance layer 1st layer (lower layer), 3... Side high resistance layer 2nd layer (upper layer), 4... Electrode. Name of agent: Patent attorney Toshio Nakao and 1 other person 2nd
Figure N + N Zu Figure 3 → 8 t 20 s 1u View (mo) % ) Figure 4 Bi 2 (lla 'XfiL (Moruzu・) Figure 5 → 9t203 Figure 6 Figure 7
Claims (3)
性を示すよう添加物を加えた成形体を７００〜１１５０
０℃の温度範囲で仮焼し、得られた仮焼体の側面にＳｉ
Ｏ＿２を主成分としＺｎ＿７Ｓｂ＿２Ｏ＿１＿２を０．
１〜３０モル％含む第１の側面剤を塗布し、前記第１の
側面剤の上部にＺｎ＿２ＳｉＯ＿４を主成分としＢｉ＿
２Ｏ＿３を０〜３０モル％含む第２の側面剤を塗布した
後、焼結し、焼結体側面に高抵抗層を形成する電圧非直
線抵抗体素子の製造方法。(1) A molded body containing zinc oxide as the main component and additives added so that the sintered body itself exhibits voltage nonlinearity has a temperature of 700 to 1150
Calcined in a temperature range of 0°C, and Si is placed on the side surface of the calcined body obtained.
The main component is O_2 and Zn_7Sb_2O_1_2 is 0.
A first side agent containing 1 to 30 mol% is applied, and a layer of Zn_2SiO_4 as a main component and Bi_
A method for manufacturing a voltage nonlinear resistor element, which comprises applying a second side surface agent containing 0 to 30 mol% of 2O_3 and then sintering it to form a high resistance layer on the side surface of the sintered body.
性を示すよう添加物を加えた成形体の側面にＳｉＯ＿２
を主成分としＺｎ＿７Ｓｂ＿２Ｏ＿１＿２を０．１〜３
０モル％含む第１の側面剤を塗布し、前記第１の側面剤
の上部にＺｎ＿２ＳｉＯ＿４を主成分としＢｉ＿２Ｏ＿
３を０〜３０モル％含む第２の側面剤を塗布した後、焼
結し、焼結体側面に高抵抗層を形成する電圧非直線抵抗
体素子の製造方法。(2) SiO_2 on the side surface of a molded body whose main component is zinc oxide, with additives added so that the sintered body itself exhibits voltage nonlinearity.
The main component is Zn_7Sb_2O_1_2 from 0.1 to 3
A first side surface agent containing 0 mol% is applied, and a layer containing Zn_2SiO_4 as a main component and Bi_2O_
A method for manufacturing a voltage nonlinear resistor element, which comprises applying a second side surface agent containing 0 to 30 mol% of 3, followed by sintering to form a high resistance layer on the side surface of the sintered body.
性を示すよう添加物を加えた成形体の側面にＳｉＯ＿２
を主成分としＺｎ＿７Ｓｂ＿２Ｏ＿１＿２を０．１〜３
０モル％含む第１の側面剤を塗布し、７００〜１１５０
０℃の温度範囲で仮焼後、仮焼体の側面にＺｎ＿２Ｓｉ
Ｏ＿４を主成分としＢｉ＿２Ｏ＿３を０〜３０モル％含
む第２の側面剤を塗布した後、焼結し、焼結体側面に高
抵抗層を形成する電圧非直線抵抗体素子の製造方法。(3) SiO_2 on the side surface of a molded body containing zinc oxide as the main component and additives added so that the sintered body itself exhibits voltage nonlinearity.
The main component is Zn_7Sb_2O_1_2 from 0.1 to 3
Apply the first side agent containing 0 mol%, and
After calcining in the temperature range of 0℃, Zn_2Si is applied to the side surface of the calcined body.
A method for manufacturing a voltage nonlinear resistor element, which comprises applying a second side surface agent containing O_4 as a main component and 0 to 30 mol% of Bi_2O_3, and then sintering to form a high-resistance layer on the side surface of the sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61126072A JPS62282407A (en) | 1986-05-30 | 1986-05-30 | Manufacture of voltage nonlinear resistance element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61126072A JPS62282407A (en) | 1986-05-30 | 1986-05-30 | Manufacture of voltage nonlinear resistance element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62282407A true JPS62282407A (en) | 1987-12-08 |
Family
ID=14925919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61126072A Pending JPS62282407A (en) | 1986-05-30 | 1986-05-30 | Manufacture of voltage nonlinear resistance element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62282407A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009228709A (en) * | 2008-03-19 | 2009-10-08 | Smc Corp | Solenoid valve drive control apparatus and method for driving solenoid valve |
-
1986
- 1986-05-30 JP JP61126072A patent/JPS62282407A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009228709A (en) * | 2008-03-19 | 2009-10-08 | Smc Corp | Solenoid valve drive control apparatus and method for driving solenoid valve |
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