JPH03139803A - Oxide voltage nonlinear resistor - Google Patents
Oxide voltage nonlinear resistorInfo
- Publication number
- JPH03139803A JPH03139803A JP1277646A JP27764689A JPH03139803A JP H03139803 A JPH03139803 A JP H03139803A JP 1277646 A JP1277646 A JP 1277646A JP 27764689 A JP27764689 A JP 27764689A JP H03139803 A JPH03139803 A JP H03139803A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- mol
- mole
- voltage nonlinear
- weight
- 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 25
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims 3
- 229910052810 boron oxide Inorganic materials 0.000 claims 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052593 corundum Inorganic materials 0.000 abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 5
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract description 5
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007423 decrease Effects 0.000 description 15
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- ZULTYUIALNTCSA-UHFFFAOYSA-N zinc hydride Chemical compound [ZnH2] ZULTYUIALNTCSA-UHFFFAOYSA-N 0.000 description 1
- 229910000051 zinc hydride Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
［従来の技術及び発明が解決しようとする課題］ＺｎＯ
を主成分とした酸化物バリスタとして、ＺｎＯにＢｉ
Ｏ、ＣｏＯ、Ｓｂ２Ｏ３、Ｍｎ０、Ａｌ２Ｏ３等を加
えて成る酸化物バリスタが周知である。この種の酸化物
バリスタはその非直線性が焼結体自体に起因しているた
め対称形の電圧電流特性を示し、その電圧非直線係数が
大きいという長所を持っている。[Detailed description of the invention] [Prior art and problems to be solved by the invention] ZnO
As an oxide varistor whose main component is Bi
Oxide varistors made by adding O, CoO, Sb2O3, Mn0, Al2O3, etc. are well known. This type of oxide varistor exhibits symmetrical voltage-current characteristics because its nonlinearity is caused by the sintered body itself, and has the advantage of having a large voltage nonlinearity coefficient.
ところで、最近の電子機器には、多くの半導体素子が使
用されており、これら半導体素子や機器を異常なサージ
やノイズから保護すること及び回路電圧を安定化するこ
とが重要な課題となっている。この目的のためには、電
圧非直線係数が十分に大きく、課電寿命が十分に長く、
かつサージ耐量に優れたバリスタが要求される。従来も
これらの諸特性が良好なバリスタは製品化されてはいる
が、バリスタに要求される性能は増々高まっており、更
に諸特性を向上させる必要がある。特に、サージ耐量の
一層大きいバリスタが要望されている。By the way, many semiconductor elements are used in recent electronic devices, and protecting these semiconductor elements and devices from abnormal surges and noise and stabilizing circuit voltage have become important issues. . For this purpose, the voltage nonlinearity coefficient is sufficiently large, the energized lifetime is sufficiently long, and
In addition, a varistor with excellent surge resistance is required. Although varistors with good properties have been commercialized in the past, the performance required of varistors is increasing, and there is a need to further improve the properties. In particular, there is a demand for varistors with even greater surge resistance.
そこで、本発明はこのような要求に満足できるバリスタ
を提供することを目的とする。Therefore, an object of the present invention is to provide a varistor that can satisfy such requirements.
［課題を解決するための手段］
上記目的を達成するための本発明は、Ｚｎ（亜鉛）、Ｂ
ｉ （ビスマス）、ｓｂ（アンチモン）、Ｃｏ（コバル
ト）、Ｍｇ（マグネシウム）、Ｍｎ（マンガン）、Ｎｉ
にッケル）をそれぞれ代表的酸化物であるＺｎＯ（Ｈ化
亜鉛）、Ｂ１゜０３（酸化ビスマス）、Ｓｂ２Ｏ３
（酸化アンチモン）、ＣｏＯ （酸化コバルト） 、Ｍ
ｇＯ（酸化マグネシウム） 、ＭｎＯ（酸化マンガン）
、Ｎ１ｐ（酸化ニッケル）に換算して
ＺｎＯ８０，０〜９７．５モル％
Ｂｉ２Ｏ３０，３〜 ３．０Ｔニル％
Ｓｂ２Ｏ３ ０．３〜３．Ｏ：ｅル％ＣｏＯ
Ｏ，３〜 ３．０モル％ＭｇＯ１，ｏ〜 ５．０モル
％
ＭｎＯ０，３〜 ３．０モル％
ＮＩＯ０，３〜 ３．ＯモｔＩ、％
の割合で含む基礎成分１００重量部と、Ｂ（ホウ素）を
その代表的酸化物であるＢ２Ｏ３（酸化ホウ素ンに換算
して０．０１〜０．１重量部と、Ａｌ（アルミニウム）
をその代表的酸化物であるＡ１□０３ （酸化アルミニ
ウム）に換算してｏ、。[Means for Solving the Problems] The present invention for achieving the above object uses Zn (zinc), B
i (bismuth), sb (antimony), Co (cobalt), Mg (magnesium), Mn (manganese), Ni
ZnO (zinc hydride), B1゜03 (bismuth oxide), and Sb2O3, which are typical oxides
(antimony oxide), CoO (cobalt oxide), M
gO (magnesium oxide), MnO (manganese oxide)
, converted to N1p (nickel oxide), ZnO80.0 to 97.5 mol% Bi2O30.3 to 3.0 Tnyl% Sb2O3 0.3 to 3. O:e%CoO
O, 3-3.0 mol% MgO 1, o- 5.0 mol% MnO 0,3-3.0 mol% NIO 0,3-3. 100 parts by weight of the basic component containing B (boron) in the proportion of aluminum)
is converted into its representative oxide A1□03 (aluminum oxide).
０２〜ｏ、ｏｏｓ重量部とを含む焼結体から成る酸化物
電圧非直線抵抗体に係わるものである。The present invention relates to an oxide voltage nonlinear resistor made of a sintered body containing 02 to 02 parts by weight.
［作 用］
上記本発明の酸化物電圧非直線抵抗体は、Ｚｎ、Ｂ１．
５ｂＳＣｏ、Ｍｇ、Ｍｎ、Ｎｉ、Ｂ及びＡｌを上記のよ
うな組成比で含有している。これにより、電圧非直線係
数が大きくがっサージ耐量が優れており、更に課電寿命
特性も良好な酸化物電圧非直線抵抗体が実現できる。[Function] The oxide voltage nonlinear resistor of the present invention has Zn, B1.
5bSCo, Mg, Mn, Ni, B, and Al are contained in the above composition ratio. As a result, it is possible to realize an oxide voltage nonlinear resistor that has a large voltage nonlinear coefficient, has excellent surge resistance, and also has good charging life characteristics.
［実施例コ 次に、本発明の実施例及び比較例を説明する。[Example code] Next, examples and comparative examples of the present invention will be described.
表に示すように、ＺｎＯ，Ｂｉ Ｏ，Ｓｂ２Ｏ３、Ｃ
ｏＯｌＭｇＯｌＭｎＯ，ＮｉＯから成る基礎成分と、Ｂ
Ｏ及びＡｌ２Ｏ３から成る添加成分の組成を種々変え
た試料Ｎ０．１〜４５のバリスタを作製した０表におい
て、基礎成分は総和が１００モル％となるように計量さ
れたＺｎＯ，Ｂｉ２Ｏ３，Ｓｂ２Ｏ３、ＣＯＯｌＭｇＯ
，Ｍｎ０１ＮｉＯの割合がモル％で示されている。但し
、Ｚｎｏは残分として示されている。残分の値は１００
モル％から７口０以外の成分のモル％の和を引いた値に
等しい。添加成分のＢ２Ｏ３、Ａｌ２Ｏ３の添加量は１
００重量部の基礎成分に対する重量部（重量％）で示さ
れている。As shown in the table, ZnO, BiO, Sb2O3, C
A basic component consisting of oOlMgOlMnO, NiO, and B
In Table 0, varistors of samples No. 1 to 45 were prepared with various compositions of additive components consisting of O and Al2O3. In Table 0, the basic components were ZnO, Bi2O3, Sb2O3, COOlMgO, which were weighed so that the total was 100 mol%.
, Mn01NiO is shown in mol%. However, Zno is shown as the remainder. The value of the remainder is 100
It is equal to the value obtained by subtracting the sum of the mole percent of components other than 7-0 from the mole percent. The amount of added components B2O3 and Al2O3 is 1
It is expressed in parts by weight (% by weight) based on 00 parts by weight of the base component.
次に、試料Ｎα１のバリスタの製造方法及び特性測定方
法を説明する。ます、基礎成分としてＺｎＯを９３．２
モル％、
Ｂｉ２Ｏ３を０．３モル％、
Ｓ ｂ ２０３を１．５モル％、
ＣｏＯを１．０モル％、
ＭｇＯを２．５モル％、
ＭｎＯを０，５モル％、
ＮｉＯを１．０モル％
の割合となるように計量し、この基礎成分１００重量部
に対して添加成分としてＢ２Ｏ３をｏ、０５重量部、Ａ
ｌ２Ｏ３を０．００３重量部添加し、これ等の原料粉末
をボールミル等で十分に混合し、これをスプレードライ
ヤで造粒した０次に、造粒して得られた原料を直径１２
．０ｍｍ、厚さ１゜５ｍｍに圧縮成形してディスクに仕
上げ、更にこの成形体を大気中において１２５０℃で１
時間焼成した。これにより、出発原料と実質的に等しい
組成の焼結体が得られた。最後に、この焼結体の両面に
Ａｇペイントの焼付により電極を形成して酸化物バリス
タを完成させた。この酸化物バリスタのバリスタ作用は
導電性微結晶とこれを包囲する高抵抗層に起因すると考
えられる。したがって、材料組成や焼成条件を変えるこ
とによりバリスタのサージ耐量や立上り電圧を制御する
ことができる８以上のようにバリスタ作用は焼結体内部
で生じているので、電極の材料や形成法に特に限定なく
、Ｉｎ、Ａｌ、Ｓｎなどの蒸着による電極あるいはＮｉ
メツキによる電極なども同様の結果が得られている。Next, a method for manufacturing a varistor of sample Nα1 and a method for measuring characteristics will be explained. 93.2% ZnO as the basic component
Mol%, Bi2O3 0.3 mol%, S b 203 1.5 mol%, CoO 1.0 mol%, MgO 2.5 mol%, MnO 0.5 mol%, NiO 1.0 B2O3 was added as an additive component to 100 parts by weight of this basic component, and 0.05 parts by weight of B2O3 and 0.05 parts by weight of A were added.
0.003 parts by weight of l2O3 was added, these raw material powders were thoroughly mixed in a ball mill, etc., and this was granulated in a spray dryer.Next, the raw material obtained by granulation was
．． 0 mm and a thickness of 1° to 5 mm to form a disc, and further heat the molded product in the atmosphere at 1250°C for 15 minutes.
Baked for an hour. As a result, a sintered body having a composition substantially the same as that of the starting material was obtained. Finally, electrodes were formed on both sides of this sintered body by baking Ag paint to complete the oxide varistor. The varistor action of this oxide varistor is thought to be due to the conductive microcrystals and the high resistance layer surrounding them. Therefore, by changing the material composition and firing conditions, the surge resistance and rising voltage of the varistor can be controlled.8 As the varistor action occurs inside the sintered body, the varistor action occurs inside the sintered body, so there is Without limitation, electrodes formed by vapor deposition of In, Al, Sn, etc. or Ni
Similar results have been obtained with plated electrodes.
試料Ｎｏ、 １のバリスタの特性を調べるために、立上
り電圧Ｖ１、電圧非直線係数α、課電寿命特性、サージ
電流耐量を測定したところ、■１は１３９■、αは５０
、課電寿命特性は−２、サージ電流耐量は２５〜３０で
あった。なお、立上り電圧Ｖ１は、バリスタ電流１ｍＡ
におけるバリスタの端子電圧である。電圧非直線係数α
は、バリスタ電流０．１ｍＡにおけるバリスタの端子電
圧■０．１とバリスタ電流１ｍＡにおけるバリスタの端
子電圧■１との比Ｖ１ ／Ｖ０．１である。このαが大
きいバリスタはど非直線性の大きいバリスタといえる。In order to investigate the characteristics of the varistor of sample No. 1, we measured the rising voltage V1, voltage nonlinear coefficient α, energized life characteristics, and surge current withstand capacity.■1 was 139■, and α was 50.
The charging life characteristic was -2, and the surge current withstand capacity was 25 to 30. Note that the rising voltage V1 is a varistor current of 1 mA.
is the terminal voltage of the varistor at . Voltage nonlinear coefficient α
is the ratio V1/V0.1 of the varistor terminal voltage (2)0.1 at a varistor current of 0.1 mA and the varistor terminal voltage (2)1 at a varistor current of 1 mA. A varistor with a large α can be said to have a large nonlinearity.
課電寿命特性は、８５゛Ｃに保たれた恒温槽中で課電率
１００％の直流電圧を２４時間印加した後、室温に戻し
てバリスタ電流０．１ｍＡにおけるバリスタの端子電圧
ＶＯ１１を測定する試験を行い、試験前のバリスタ電流
０．１ｍＡにおけるバリスタの端子電圧に対する変化率
（％）を算出して特性評価を行った。変化率が小さいは
ど課電寿命特性が良いといえる。サージ耐量特性は、Ｊ
ＲＣ（電気学会）規格第２１２番に基づ＜８Ｘ２０μｓ
、２５０ＯＡのサージ電流を３０秒の間隔で５回印加し
、各回終了ごとにバリスタ電流１ｍＡにおける端子電圧
■１を測定してその変化率を算出し、Ｖｌが試験前の値
から１０％低下するまでのサージ電流の印加回数ｎで特
性評価した。印加回数ｎが多いほどサージ耐量特性が優
れているといえる。なお、同−試料量のバリスタを複数
回作製したので、Ｖｌ、α、課電寿命特性は平均値で示
され、サージ電流耐量は最低回数と最高回数とで示され
ている。The energization life characteristics are determined by applying a DC voltage with a 100% energization rate for 24 hours in a constant temperature oven maintained at 85°C, then returning to room temperature and measuring the varistor terminal voltage VO11 at a varistor current of 0.1 mA. A test was conducted, and the characteristics were evaluated by calculating the rate of change (%) with respect to the terminal voltage of the varistor at a varistor current of 0.1 mA before the test. If the rate of change is small, it can be said that the charging life characteristics are good. The surge resistance characteristics are J
Based on RC (Institute of Electrical Engineers of Japan) standard No. 212 <8X20μs
, apply a surge current of 250 OA 5 times at 30 second intervals, measure the terminal voltage 1 at a varistor current of 1 mA after each application, calculate the rate of change, and find that Vl decreases by 10% from the value before the test. Characteristics were evaluated based on the number of times n of surge current was applied. It can be said that the larger the number of applications n is, the better the surge resistance characteristics are. In addition, since the varistor with the same sample amount was produced multiple times, Vl, α, and energized life characteristics are shown as average values, and the surge current withstand capacity is shown as the minimum number of times and the maximum number of times.
試料Ｎｏ、 ２〜４５のバリスタは、組成を変えた以外
は試料Ｎｏ、 １と同一の方法で作製し、同一の方法で
特性を測定した。Varistors of Samples No. 2 to 45 were manufactured in the same manner as Sample No. 1 except that the composition was changed, and their characteristics were measured in the same manner.
表の試料Ｎｏ、 １〜６から明らかなように、ＺｎＯ及
びＢｉ２Ｏ３を除く基礎成分と添加成分とを固定し、Ｂ
ｉ２Ｏ３のモル％を０．１〜５．０モル％の範囲で変化
させ、かつ基礎成分の総和が１００モル％となるように
ＺｎＯを変化させると、サージ電流耐量が表及び第１図
に示すように変化する。Ｂｉ２Ｏ３が３モル％を越える
とサージ電流耐量が低下し、また、Ｂ １２０３が０．
３モル％より少ない範囲においてもサージ電流耐量が低
下する。したがって、優れたサージ電流耐量を得るため
のＢｉ２Ｏ３の好ましい範囲は０．３〜３゜０モル％で
あり、より好ましい範囲は０．５〜２゜０モル％である
。なお、この範囲では、表に示すように、電圧非直線係
数αが大きく得られるし、課電寿命特性も良好である。As is clear from Sample Nos. 1 to 6 in the table, the basic components and additive components except ZnO and Bi2O3 were fixed, and B
When the mol% of i2O3 is varied in the range of 0.1 to 5.0 mol% and the ZnO is varied so that the sum of the basic components is 100 mol%, the surge current withstand capacity is shown in the table and Figure 1. It changes like this. If Bi2O3 exceeds 3 mol%, the surge current withstand capacity decreases, and if B1203 exceeds 3 mol%.
Even in a range of less than 3 mol %, the surge current resistance decreases. Therefore, in order to obtain excellent surge current resistance, the preferred range of Bi2O3 is 0.3 to 3.0 mol%, and the more preferred range is 0.5 to 2.0 mol%. In addition, in this range, as shown in the table, a large voltage nonlinear coefficient α can be obtained, and the charging life characteristics are also good.
試料ＮＧ７〜１２から明らかなように、ＺｎＯ及びＳｂ
２Ｏ３を除く基礎成分と添加成分とを固定し、Ｓｂ２Ｏ
３のモル％を０．１〜５．０モル％の範囲で変化させ、
かつ基礎成分の総和が１００モル％となるようにＺｎＯ
を変化させると、サージ電流耐量が表及び第２図に示す
ように変化する。As is clear from samples NG7 to NG12, ZnO and Sb
The basic components and additive components except 2O3 are fixed, and Sb2O
Varying the mol% of 3 in the range of 0.1 to 5.0 mol%,
and ZnO so that the total of the basic components is 100 mol%.
When , the surge current withstand capacity changes as shown in the table and FIG. 2.
Ｓｂ２Ｏ３が３．０モル％を越えるとサージ電流耐量が
低下し、また、Ｓｂ２Ｏ３が０．３モル％より少ない範
囲においてもサージ電流耐量が低下する。したがって、
優れたサージ電流耐量を得るためのＳｂ２Ｏ３の好まし
い範囲は０．３〜３゜０モル％であり、より好ましい範
囲は０．５〜２０モル％である。なお、この範囲では、
表に示すように、電圧非直線係数αが大きく得られるし
、課電寿命特性も良好である。When Sb2O3 exceeds 3.0 mol%, the surge current withstand capacity decreases, and even in a range where Sb2O3 is less than 0.3 mol%, the surge current withstand capacity decreases. therefore,
The preferable range of Sb2O3 for obtaining excellent surge current resistance is 0.3 to 30 mol%, and the more preferable range is 0.5 to 20 mol%. In addition, in this range,
As shown in the table, a large voltage non-linearity coefficient α can be obtained, and the charging life characteristics are also good.
試料Ｎｏ１３〜１８から明らかなように、ＺｎＯ及びＣ
ｏＯを除く基礎成分と添加成分とを固定し、ＣｏＯのモ
ル％を０．１〜５．０モル％の範囲で変化させ、かつ基
礎成分の総和が１００モル％となるようにＺｎＯを変化
させると、サージ電流耐量が表及び第３図に示すように
変化する。ＣｏＯが３．０モル％を越えるとサージ電流
耐量が低下し、また、ＣｏＯが０，３モル％より少ない
範囲においてもサージ電流耐量が低下する。したがって
、優れたサージ電流耐量を得るためのＣｏＯの好ましい
範囲は０．３〜３．０モル％であり、より好ましい範囲
は０．５〜２．０モル％である。As is clear from samples Nos. 13 to 18, ZnO and C
The basic components and additive components except oO are fixed, the mol% of CoO is varied in the range of 0.1 to 5.0 mol%, and the ZnO is varied so that the sum of the basic components is 100 mol%. Then, the surge current withstand capacity changes as shown in the table and FIG. 3. If the CoO content exceeds 3.0 mol%, the surge current withstand capacity decreases, and even if the CoO content is less than 0.3 mol%, the surge current withstand capacity decreases. Therefore, the preferable range of CoO for obtaining excellent surge current resistance is 0.3 to 3.0 mol%, and the more preferable range is 0.5 to 2.0 mol%.
なお、この範囲では、表に示すように、電圧非直線係数
αが大きく得られるし、課電寿命特性も良好である。In addition, in this range, as shown in the table, a large voltage nonlinear coefficient α can be obtained, and the charging life characteristics are also good.
試料Ｎｏ、 １９〜２３から明らかなように、ＺｎＯ及
びＭｇＯを除く基礎成分と添加成分とを固定し、ＭｇＯ
のモル％を０．５〜１０．０モル％の範囲で変化させ、
かつ基礎成分の総和が１００モル％となるようにＺｎＯ
を変化させると、サージ電流耐量が表及び第４図に示す
ように変化する。ＭｇＯが５．０モル％を越えるとサー
ジ電流耐量が低下し、また、ＭｇＯが１．０モル％より
少ない範囲では電圧非直線係数αが小さくなる。したが
って、優れたサージ電流耐量が得られかつ電圧非直線係
数αが大きく得られるためのＣｏＯの好ましい範囲は１
．０〜５．０モル％であり、より好ましい範囲は２．０
〜４．０モル％である。なお、この範囲では、表のよう
に課電寿命特性も良好に得られる。As is clear from Sample Nos. 19 to 23, the basic components and additive components excluding ZnO and MgO were fixed, and MgO
changing the mol% in the range of 0.5 to 10.0 mol%,
and ZnO so that the total of the basic components is 100 mol%.
When , the surge current withstand capacity changes as shown in the table and FIG. 4. When MgO exceeds 5.0 mol%, the surge current withstand capacity decreases, and when MgO is less than 1.0 mol%, the voltage nonlinear coefficient α becomes small. Therefore, in order to obtain an excellent surge current withstand capacity and a large voltage nonlinear coefficient α, the preferable range of CoO is 1
．． 0 to 5.0 mol%, and the more preferable range is 2.0
~4.0 mol%. In addition, within this range, good charging life characteristics can be obtained as shown in the table.
試料Ｎｏ２４〜２９に示すように、ＺｎＯ及びＭｎＯを
除く基礎成分と添加成分とを固定し、ＭｎＯのモル％を
０．１〜５．０モル％の範囲で変化させ、かつ基礎成分
の総和が１００モル％となるようにＺｎＯを変化させる
と、サージ電流耐量が表及び第５図に示すように変化す
る。第５図から明らかなように、ＭｎＯが３．０モル％
を越えるとサージ電流耐量が低下し、また、ＭｎＯが０
゜３モル％より少ない範囲においてもサージ電流耐１が
低下する。したがって、優れたサージ電流耐量を得るた
めのＭｎＯの好ましい範囲は０．３〜３．０モル％であ
り、より好ましい範囲は０゜４〜１゜０モル％である。As shown in samples Nos. 24 to 29, the base components and additive components except ZnO and MnO were fixed, the mol% of MnO was varied in the range of 0.1 to 5.0 mol%, and the total of the base components was When ZnO is changed to 100 mol %, the surge current withstand capacity changes as shown in the table and FIG. 5. As is clear from Figure 5, MnO is 3.0 mol%
If the MnO exceeds 0, the surge current withstand capacity will decrease
The surge current resistance 1 decreases even in a range of less than 3 mol %. Therefore, in order to obtain excellent surge current resistance, the preferred range of MnO is 0.3 to 3.0 mol%, and the more preferred range is 0.4 to 1.0 mol%.
なお、この範囲では、表のように、電圧非直線係数αが
大きく得られるし、課電寿命特性も良好である。In addition, in this range, as shown in the table, a large voltage nonlinear coefficient α can be obtained, and the charging life characteristics are also good.
試料Ｎｏ３０〜３５に示すように、ＺｎＯ及びＮＩＯを
除く基礎成分と添加成分とを固定し、ＮｉＯのモル％を
０．１〜５．０モル％の範囲で変化させ、かつ基礎成分
の総和が１００モル％となるようにＺｎＯを変化させる
と、サージ電流耐量が表及び第６図に示すように変化す
る。ＮｉＯが３．０モル％を越えると、サージ電流耐量
が低下し、また、ＮｉＯが０．３モル％より少ない範囲
においてもサージ電流耐量が低下する。したがって、優
れたサージ耐量特性を得るためのＮｉＯの好ましい範囲
は０．３〜３．０モル％であり、より好ましい範囲は０
．５〜２．０モル％である。なお、この範囲では、表に
示すように、電圧非直線係数αが大きく得られるし、課
電寿命特性も良好である。As shown in samples Nos. 30 to 35, the basic components and additive components except ZnO and NIO were fixed, the mol% of NiO was varied in the range of 0.1 to 5.0 mol%, and the total of the basic components was When ZnO is changed to 100 mol %, the surge current withstand capacity changes as shown in the table and FIG. 6. If the NiO content exceeds 3.0 mol%, the surge current withstand capacity decreases, and even in a range where the NiO content is less than 0.3 mol%, the surge current withstand capacity decreases. Therefore, the preferable range of NiO to obtain excellent surge resistance characteristics is 0.3 to 3.0 mol%, and the more preferable range is 0.
．． It is 5 to 2.0 mol%. In addition, in this range, as shown in the table, a large voltage nonlinear coefficient α can be obtained, and the charging life characteristics are also good.
試料１１１Ｑ３６〜４０に示すように、基礎成分と、添
加成分のうちＡｌ２Ｏ３を固定し、Ｂ２Ｏ３を１００重
量％の基礎成分に対する重量％を０，００５重量％〜０
．１５％重量％の範囲で変化させると、サージ電流耐量
が表及び第７図に示すように変化する。Ｂ２Ｏ３が０．
１重量％より多くなると、サージ電流耐量が低下し、ま
た、Ｂ２Ｏ３が０．０１重量％より少ない範囲において
もサージ電流耐量は低下する。したがって、優れたサー
ジ耐量特性を得るためのＢ２Ｏ３の好ましい範囲は０．
０１重量％〜０．１重量％であり、より好ましい範囲は
０．０２〜０．０５重量％である。As shown in Samples 111Q36-40, among the base components and additive components, Al2O3 is fixed, and the weight% of B2O3 is 0,005% by weight to 0% relative to the 100% by weight base component.
．． When the amount is changed within the range of 15% by weight, the surge current resistance changes as shown in the table and FIG. 7. B2O3 is 0.
When the content is more than 1% by weight, the surge current withstand capacity decreases, and even in the range where B2O3 is less than 0.01% by weight, the surge current withstand capacity decreases. Therefore, the preferred range of B2O3 to obtain excellent surge resistance characteristics is 0.
The range is from 0.01% to 0.1% by weight, and the more preferred range is from 0.02 to 0.05% by weight.
なお、この範囲では、表に示すように、電圧非直線係数
αが大きく得られるし、課電寿命特性も良好である。In addition, in this range, as shown in the table, a large voltage nonlinear coefficient α can be obtained, and the charging life characteristics are also good.
試料Ｎｏ４１〜４５に示すように、基礎成分と、添加成
分のうちＢ Ｏを固定し、Ａ１□０３を１００重量％の
上記基礎成分に対する重量％を０゜００１重量％〜０．
０１重量％の範囲で変化させると、サージ電流耐量が表
及び第８図に示すように変化する。Ａ ｌ ２０３が０
．００８重量％より多くなるとサージ電流耐量が低下し
、また、Ａｌ２Ｏ３が０．００２重量％より少ない範囲
においては電圧非直線係数が小さくなる。したがって、
優れたサージ電流耐量が得られかつ電圧非直線係数が大
きく得られるためのＡｌ２Ｏ３の好ましい範囲は０．０
０２重量％〜０．００８重量％であり、より好ましい範
囲は０．００３重量％〜０゜００６重量％である。なお
、この範囲では、表のように課電寿命特性も良好に得ら
れる。As shown in samples Nos. 41 to 45, among the basic components and additive components, BO is fixed, and the weight percentage of A1□03 is 0°001% by weight to 0.00% by weight relative to 100% by weight of the above basic components.
When the amount is changed within a range of 0.01% by weight, the surge current resistance changes as shown in the table and FIG. A l 203 is 0
．． When Al2O3 exceeds 0.008% by weight, the surge current withstand capacity decreases, and when Al2O3 is less than 0.002% by weight, the voltage nonlinear coefficient becomes small. therefore,
The preferred range of Al2O3 is 0.0 in order to obtain an excellent surge current withstand capacity and a large voltage nonlinear coefficient.
The range is 0.02% by weight to 0.008% by weight, and a more preferable range is 0.003% by weight to 0.006% by weight. In addition, within this range, good charging life characteristics can be obtained as shown in the table.
［変形例コ
本発明は上述の実施例に限定されるものでなく、例えば
次の変形が可能なものである。[Modifications] The present invention is not limited to the above-described embodiments, and for example, the following modifications are possible.
（１） 各成分の出発原料は酸化物に限られない。例え
ば、Ｃ０１Ｍｇ、ＭｎはそれぞれＣｏＣＯ３、ＭｇＣＯ
３、ＭｎＣＯ３等であってもよい。(1) The starting materials for each component are not limited to oxides. For example, C01Mg and Mn are CoCO3 and MgCO, respectively.
3, MnCO3, etc. may be used.
また、ＢはＨ２Ｂ Ｏ３を原料としてもよい。つまり、
酸化物以外に水酸化物や炭酸塩、フッ化物等でもよい。Further, B may be made from H2B O3. In other words,
In addition to oxides, hydroxides, carbonates, fluorides, etc. may be used.
（２） 各成分の出発原料は複数の成分の化合物であっ
てもよい０例えば、Ｍｇの一部とＡｌとをその化合物で
あるスピネル型のＡ１□Ｍ ｇ Ｏ４として含有させて
もよい、また、Ｃｏの一部とＡｌをその化合物である。(2) The starting material for each component may be a compound of multiple components. For example, a part of Mg and Al may be contained as a spinel-type compound, A1□M g O4, or , a part of Co and Al are its compounds.
スピネル型のＡ Ｉ ２ Ｃ。Spinel type AI2C.
０４として含有させてもよい、上記２つの場合、サージ
電流耐量が更に向上することが確められている。It has been confirmed that in the above two cases, the surge current resistance can be further improved.
（３） 本発明に係わるバリスタの特性を損わない範囲
において別の特性改良のための添加物を混入させてもよ
い。(3) Other additives for improving the characteristics may be mixed in as long as the characteristics of the varistor according to the present invention are not impaired.
［発明の効果］
以上述べたように、本発明によれば、従来の酸化物バリ
スタに比べてサージ耐量が優れており、かつ電圧非直線
係数が大きく、また課電寿命特性も良好である酸化物バ
リスタを提供することができる。このバリスタによれば
、電子機器内で発生する異常電圧や外部からのサージ電
圧を吸収し、半導体素子などの電子部品を保護すること
が可能となり、更にはその大きな電圧非直線係数により
回Ｆ！＠電圧の安定化をはかることができる。[Effects of the Invention] As described above, according to the present invention, an oxide varistor that has superior surge resistance, a larger voltage nonlinear coefficient, and better energized life characteristics than conventional oxide varistors. things barista can provide. According to this varistor, it is possible to protect electronic components such as semiconductor elements by absorbing abnormal voltages generated within electronic devices and surge voltages from the outside, and furthermore, due to its large voltage nonlinear coefficient, it is possible to reduce the number of times F! @Voltage can be stabilized.
第１図、第２図、第３図、第４図、第５図、第６図、第
７図及び第８図は、各成分の量を対数目盛で横軸に示し
、サージ耐量を縦軸に示す図である。Figures 1, 2, 3, 4, 5, 6, 7, and 8 show the amount of each component on a logarithmic scale on the horizontal axis, and the surge resistance on the vertical axis. FIG.
Claims (1)
モン）、Ｃｏ（コバルト）、Ｍｇ（マグネシウム）、Ｍ
ｎ（マンガン）、Ｎｉ（ニッケル）をそれぞれ代表的酸
化物であるＺｎＯ（酸化亜鉛）、Ｂｉ＿２Ｏ＿３（酸化
ビスマス）、Ｓｂ＿２Ｏ＿３（酸化アンチモン）、Ｃｏ
Ｏ（酸化コバルト）、ＭｇＯ（酸化マグネシウム）、Ｍ
ｎＯ（酸化マンガン）、ＮｉＯ（酸化ニッケル）に換算
してＺｎＯ ８０．０〜９７．５モル％ Ｂｉ＿２Ｏ＿３ ０．３〜３．０モル％ Ｓｂ＿２Ｏ＿３ ０．３〜３．０モル％ ＣｏＯ ０．３〜３．０モル％ ＭｇＯ １．０〜５．０モル％ ＭｎＯ ０．３〜３．０モル％ ＮｉＯ ０．３〜３．０モル％ の割合で含む基礎成分１００重量部と、 Ｂ（ホウ素）をその代表的酸化物であるＢ＿２Ｏ＿３（
酸化ホウ素）に換算して０．０１〜０．１重量部と、 Ａｌ（アルミニウム）をその代表的酸化物であるＡｌ＿
２Ｏ＿３（酸化アルミニウム）に換算して０．００２〜
０．００８重量部と を含む焼結体から成る酸化物電圧非直線抵抗体。[Claims] [1] Zn (zinc), Bi (bismuth), Sb (antimony), Co (cobalt), Mg (magnesium), M
n (manganese) and Ni (nickel), respectively, are representative oxides of ZnO (zinc oxide), Bi_2O_3 (bismuth oxide), Sb_2O_3 (antimony oxide), and Co.
O (cobalt oxide), MgO (magnesium oxide), M
In terms of nO (manganese oxide) and NiO (nickel oxide), ZnO 80.0 to 97.5 mol% Bi_2O_3 0.3 to 3.0 mol% Sb_2O_3 0.3 to 3.0 mol% CoO 0.3 to 100 parts by weight of a basic component containing 3.0 mol% MgO 1.0-5.0 mol% MnO 0.3-3.0 mol% NiO 0.3-3.0 mol%, and B (boron) and its representative oxide B_2O_3(
0.01 to 0.1 part by weight (calculated as boron oxide), and Al (aluminum) as its representative oxide, Al_
0.002~ in terms of 2O_3 (aluminum oxide)
An oxide voltage nonlinear resistor comprising a sintered body containing 0.008 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1277646A JPH03139803A (en) | 1989-10-25 | 1989-10-25 | Oxide voltage nonlinear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1277646A JPH03139803A (en) | 1989-10-25 | 1989-10-25 | Oxide voltage nonlinear resistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03139803A true JPH03139803A (en) | 1991-06-14 |
Family
ID=17586329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1277646A Pending JPH03139803A (en) | 1989-10-25 | 1989-10-25 | Oxide voltage nonlinear resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03139803A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006216805A (en) * | 2005-02-04 | 2006-08-17 | Idemitsu Kosan Co Ltd | Zinc system compound oxide and thermoelectric conversion module |
-
1989
- 1989-10-25 JP JP1277646A patent/JPH03139803A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006216805A (en) * | 2005-02-04 | 2006-08-17 | Idemitsu Kosan Co Ltd | Zinc system compound oxide and thermoelectric conversion module |
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