JPH0448703A - Manufacture of voltage nonlinear resistor - Google Patents
Manufacture of voltage nonlinear resistorInfo
- Publication number
- JPH0448703A JPH0448703A JP2157268A JP15726890A JPH0448703A JP H0448703 A JPH0448703 A JP H0448703A JP 2157268 A JP2157268 A JP 2157268A JP 15726890 A JP15726890 A JP 15726890A JP H0448703 A JPH0448703 A JP H0448703A
- Authority
- JP
- Japan
- Prior art keywords
- mole
- oxide
- zno
- added
- raw material
- 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 abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940105296 zinc peroxide Drugs 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 47
- 239000011787 zinc oxide Substances 0.000 claims description 23
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010304 firing Methods 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide 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】
〔産業上の利用分野〕
本願発明は、酸化亜鉛系の電圧非直線抵抗体の製造方法
に関し、特に、耐サージ性を改善した電圧非直線抵抗体
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a zinc oxide-based voltage nonlinear resistor, and particularly to a method for manufacturing a voltage nonlinear resistor with improved surge resistance.
電気機器あるいは回路を、スイッチ開閉やソレノイド遮
断、あるいは雷等に伴って発生する衝撃電流から保護す
るサージ保護素子として用いる電圧非直線抵抗体には、
基本特性として、所定電圧において瞬間的にこのような
小電流から大電流に渡る電流を吸収できる電流−電圧特
性が必要であり、従って衝撃電流耐量が大きく、繰返し
衝撃電流の負荷即ち繰返しサージに対する変化量が少な
く、定格電流即ち常時課電電圧に対して漏洩電流が少な
い、即ち、電圧非直線抵抗体の負担が少なく、寿命の長
いことが必要とされている。Voltage nonlinear resistors used as surge protection elements to protect electrical equipment or circuits from shock currents generated by switching on/off, solenoid shutoff, or lightning strikes, etc.
As a basic characteristic, current-voltage characteristics are required that can momentarily absorb currents ranging from small to large currents at a given voltage, and therefore have a large impact current withstand capacity, and are resistant to changes in response to repeated impact current loads, that is, repeated surges. It is required that the leakage current is small with respect to the rated current, that is, the constantly applied voltage, that is, the load on the voltage nonlinear resistor is small, and the life is long.
このような電圧非直線抵抗体としては、従来ＳｉＣ系バ
リスタ、Ｓｅ系バリスタ″等が使用されてきたが、近年
、前記のように瞬間的に大電流を流すことのできる２、
畦立上がり特性を有し、衝撃電流耐量が大きい等バリス
タ特性に優れた酸化亜鉛系の電圧非直線抵抗体が開発さ
れ、広範に使用されるようになってきている。Conventionally, SiC-based varistors, Se-based varistors, etc. have been used as such voltage nonlinear resistors, but in recent years, as mentioned above, 2, which can instantaneously flow large currents,
Zinc oxide-based voltage nonlinear resistors with excellent varistor characteristics, such as ridge rising characteristics and high impact current resistance, have been developed and have come to be widely used.
このような電圧非直線抵抗体は、酸化亜鉛（ＺｎＯ）を
成形し、１０００℃以上の温度で焼成してつくることが
できるが、この焼結体をなすＺｎＯは、ウルツ鉱型の結
晶構造をなし、通常、この亜鉛と酸素とは化学ｆ論的な
組成比からは僅かにずれて亜鉛が過剰に含まれている。Such a voltage nonlinear resistor can be made by molding zinc oxide (ZnO) and firing it at a temperature of 1000°C or higher, but the ZnO that makes up this sintered body has a wurtzite crystal structure. Normally, the composition ratio of zinc and oxygen is slightly deviated from the stoichiometric composition, and zinc is contained in excess.
この過剰亜鉛原子は、結晶格子間に侵入しており、結晶
粒子内は半導体特性を示しているが、結晶粒界は焼成時
に、雰囲気酸素による選択酸化により、亜鉛と酸素との
組成比が略１となり、絶縁層を形成している。しかし、
このような雰囲気酸素のみによって亜鉛結晶粒界におけ
る十分な酸化絶縁層を形成させるのは実質的に困難であ
って、原料を成形焼結する過程で必要なバリスタ特性を
確保するために、さらに、ＺｎＯ微結晶の周囲を取り囲
む酸化ビスマス（Ｂ ｉ ｚ ０３）または酸化プラセ
オジム（Ｐ ｒ。These excess zinc atoms penetrate between the crystal lattices, and the inside of the crystal grains exhibits semiconducting properties. However, during firing, the grain boundaries are selectively oxidized by atmospheric oxygen, so that the composition ratio of zinc to oxygen decreases. 1, forming an insulating layer. but,
It is practically difficult to form a sufficient oxide insulating layer at the zinc grain boundaries using only oxygen in this atmosphere. ZnO microcrystals are surrounded by bismuth oxide (B i z 03) or praseodymium oxide (P r.
０ＩＩ）などの副成分を主体とした網目状の粒界層とそ
の付近の粒界域に存在するスピネル相とからなる高抵抗
層を形成させる方法がとられている。A method of forming a high-resistance layer consisting of a network-like grain boundary layer mainly composed of subcomponents such as 0II) and a spinel phase existing in the grain boundary region in the vicinity thereof has been adopted.
即ち、ＺｎＯ系の電圧非直線抵抗体はＺｎＯとＢｉ、Ｏ
，あるいはＰｒ１Ｏ＋＋ とによって焼結体の基本構
造を構成し、バリスタ特性を保持するものであって、さ
らに酸化コバルト（Ｃｏｏ）。In other words, a ZnO-based voltage nonlinear resistor is composed of ZnO, Bi, and O.
, or Pr1O++ constitutes the basic structure of the sintered body and maintains varistor characteristics, and further includes cobalt oxide (Coo).
酸化マンガン（ＭｎＯ）酸化アルミニウム（ＡｌｔＯｊ
）等の添加によってバリスタ特性を改善し、酸化アンチ
モン（Ｓｂ、Ｏ，）、酸化クロム（Ｃｒ２０、）、酸化
ホウ素（ＢＺ○、）等の添加で前記バリスタ特性の安定
化を図り、またさらに、酸化ニッケル（Ｎｉｐ）、酸化
タングステン（ＷＯｓ）。Manganese oxide (MnO) Aluminum oxide (AltOj
) etc. to improve the varistor characteristics, and addition of antimony oxide (Sb, O, ), chromium oxide (Cr20, ), boron oxide (BZ○, ), etc. to stabilize the varistor characteristics, and further, Nickel oxide (Nip), tungsten oxide (WOs).
酸化珪素（Ｓｉｎｇ） 等の添加によって粒界層の安
定化を図っている。The grain boundary layer is stabilized by adding silicon oxide (Sing), etc.
このような電圧非直線抵抗体は、ＺｎＯに対して、前記
添加成分を、水酸化物、炭酸塩、硝酸塩、有機塩等加熱
によって分解する塩のうちの何れかの形で所定量添加し
た上で混合後、造粒し、そして円板状のバリスタ本体の
形状に成形してから１１００°〜１４００℃好ましくは
１２００〜１３５０°Ｃで１〜５時間焼成するという方
法でつくることができる。Such a voltage nonlinear resistor is made by adding a predetermined amount of the above-mentioned additive component to ZnO in the form of a salt that decomposes when heated, such as hydroxide, carbonate, nitrate, or organic salt. It can be produced by a method of mixing, granulating, molding into the shape of a disc-shaped varistor body, and then firing at 1100° to 1400°C, preferably 1200 to 1350°C, for 1 to 5 hours.
しかしながら、前記の雰囲気酸素による選択酸化に依存
し、Ｂ ｉｚ Ｏｓ 、Ｐｒｉ ｏｌ１等添加成分によ
ってバリスタ特性の保持改善を行う従来方法で得られる
ＺｎＯ系電圧非直線抵抗体は、優れたバリスタ特性を有
するとしても、なお、常時課電電圧に対する漏洩電流の
増加は比較的に大きく、また衝撃電流負荷による電圧陣
下が大きく、必ずしも十分に満足し得るものではながっ
た。このため、さらに、焼結体の成分組成を変えたり、
焼成温度を加減する等のいろいろな改善策が講じられて
きたが、例えばｔ流漏洩を防止するために添加成分によ
って粒界層を厚くすると、繰返し衝撃電流負荷による衝
％ｌ！電流耐量の隨下が大きくなる、というような問題
もあり、ＺｎＯ系の電圧非直線抵抗体のバリスタ特性は
ある程度制限された妥協的なものにならざるを得ないと
いう状況にあった。However, the ZnO-based voltage nonlinear resistor obtained by the conventional method that relies on the selective oxidation using atmospheric oxygen and improves the retention of varistor characteristics with additive components such as B iz Os and Prior 1 has excellent varistor characteristics. Even so, the increase in leakage current with respect to the constantly applied voltage was relatively large, and the voltage drop due to the impact current load was large, so that it was not necessarily completely satisfactory. For this reason, it is possible to further change the composition of the sintered body,
Various improvement measures have been taken, such as adjusting the firing temperature, but for example, if the grain boundary layer is made thicker with additives to prevent t-flow leakage, the shock %l! There is also the problem that the current withstand capacity decreases significantly, and the varistor characteristics of the ZnO-based voltage nonlinear resistor have to be somewhat limited and compromise-like.
従って、本発明の目的は、従来のＺｎＯ系の電圧非直線
抵抗体、特にＺｎＯＢｉｒｄｓの電圧非直線抵抗体につ
いて、その製造時において、焼結体の主成分ＺｎＯその
ものによるバリスタ特性の強化を図り、衝撃電流負荷に
よる非直線性の劣化を抑制して安定化させ、且つ漏洩電
流が少な（て従来以上に寿命特性に優れた電圧非直線抵
抗体が得られる方法の提供にある。Therefore, an object of the present invention is to strengthen the varistor characteristics of conventional ZnO-based voltage nonlinear resistors, particularly ZnOBirds voltage nonlinear resistors, by the main component ZnO itself of the sintered body during its manufacture. The object of the present invention is to provide a method for obtaining a voltage nonlinear resistor that suppresses and stabilizes deterioration of nonlinearity due to an impact current load, has less leakage current (and has better life characteristics than conventional ones).
前記の目的を達成するため、本発明は、酸化亜鉛（Ｚｎ
Ｏ）に、酸化ビスマス（Ｂ １ ｚ Ｏｘ ）酸化コバ
ルト（Ｃｏｏ）、 酸化マンガン（ＭｎＯ）酸化アン
チモン（Ｓｂｚ Ｏｘ ）、 ｖｉ化ツクロムｃｒｚｏ
ｓ）、酸化ホウ素（Ｂ、ｏｓ ）及び酸化ニッケル（Ｎ
ｉｐ）を塩の形で添加して混合した原料粉を用い、成形
して焼結する酸化亜鉛系電圧非直線抵抗体の製造方法に
おいて、前記原料粉に、酸化剤として過酸化亜鉛（Ｚｎ
Ｏｔ）を外配で ０．５〜１０モル％含有させる電圧非
直線抵抗体の製造方法を提案するものである。In order to achieve the above object, the present invention utilizes zinc oxide (Zn
O), bismuth oxide (B1zOx), cobalt oxide (Coo), manganese oxide (MnO), antimony oxide (SbzOx), trichrome vi oxide crzo
s), boron oxide (B, os ) and nickel oxide (N
In the method for manufacturing a zinc oxide-based voltage nonlinear resistor, the raw material powder is formed and sintered using a raw material powder to which zinc peroxide (Zn
This paper proposes a method for manufacturing a voltage nonlinear resistor containing 0.5 to 10 mol% of Ot) in the outer layer.
前記製造法における焼成により、主体となるＺｎＯ結晶
の周囲に添加酸化物による高抵抗層が形成されると共に
、ＺｎＯ結晶そのものの粒界の選択酸化が行われ、サー
ジに対して安定的な抵抗性を示す絶縁層が形成される。By firing in the above manufacturing method, a high resistance layer is formed by the added oxide around the main ZnO crystal, and the grain boundaries of the ZnO crystal itself are selectively oxidized, resulting in stable resistance to surges. An insulating layer exhibiting the following is formed.
即ち、添加したＺｎＯ□は原料粉による成形体内に、略
均等に混合された状態で強力な酸化剤として作用し、焼
成時に酸素を放出し、焼結体内のＺｎＯの粒界において
未酸化金属亜鉛や還元性物質を酸化し、結晶粒界におい
て十分な酸化絶縁層を形成するので、サージに対して安
定なバリスタ素子を形成できる。That is, the added ZnO□ acts as a strong oxidizing agent when mixed almost uniformly in the molded body made of raw material powder, releases oxygen during firing, and forms unoxidized metal zinc at the grain boundaries of ZnO in the sintered body. Since a sufficient oxidized insulating layer is formed at grain boundaries by oxidizing a reducing substance and a reducing substance, a varistor element that is stable against surges can be formed.
しかし、Ｚｎ０ｔの添加が０．５モル％未満では効果が
薄く、１０モル％を超えた状態では、過剰な酸素が多量
に発生して素子内に欠陥を斉らし、バリスタ特性を損な
う。However, if the addition of Zn0t is less than 0.5 mol %, the effect is weak, and if it exceeds 10 mol %, a large amount of excess oxygen is generated, causing defects in the device and impairing the varistor characteristics.
ＺｎＯに、自記で、ＢｉｚＯｓを０．５モル％。 In ZnO, 0.5 mol% of BizOs was added by hand.
Ｃｏｏを１．０モル％、ＭｎＯを０．５モル％、５ｂｘ
Ｏ１を１．０モル％、Ｃｒ＝ Ｏｘを０．５モル％＋Ｂ
ｆｆｉ０３を０．１モル％、ＮｉＯを１．０モル％をそ
れぞれ塩の形で加えた原料粉に、ＺｎＯ□を外配で０．
５〜１０．０モル％の間で変化させて加えたものを、そ
れぞれ湿式メディアミルで混合し、バインダを加えた後
、スプレードライヤーで造粒した。この素材粉を粉末成
形用プレスで直径２４１．及び厚さ３１．の円板に成形
し、１３００°Ｃで１時間焼成して直径２０．、及び厚
さ２．５ 、、のバリスタ素子を得た。Coo 1.0 mol%, MnO 0.5 mol%, 5bx
1.0 mol% O1, 0.5 mol% Cr=Ox+B
0.1 mol % of ffi03 and 1.0 mol % of NiO were added in the form of salt to the raw material powder, and 0.0 mol % of ZnO□ was added outside.
The amounts added varying between 5 and 10.0 mol % were mixed using a wet media mill, and after adding a binder, they were granulated using a spray dryer. This raw material powder was processed into a powder molding press with a diameter of 241 mm. and thickness 31. It was molded into a disc with a diameter of 20mm and baked at 1300°C for 1 hour. A varistor element with a thickness of 2.5 and a thickness of 2.5 was obtained.
また、比較試料として、同様の方法でＺｎ０ｚを加えな
いバリスタ素子及び０．１．０．３．１２及び１５モル
％含む本発明範囲外のバリスタ素子をつくった。何れも
その両面に銀電極を塗布して７００°Ｃで焼き付けた後
、リード線を付けてバリスタとした。In addition, as comparative samples, varistor elements without Zn0z and varistor elements containing 0.1.0.3.12 and 15 mol% of Zn0z outside the scope of the present invention were produced in the same manner. After applying silver electrodes to both sides and baking them at 700°C, lead wires were attached to make varistors.
これらのバリスタについて、直流電流１ｍＡを流したと
きの電圧即ちバリスタ電圧Ｖ、ｍＡを測定した後、電流
波形８×２０マイクロ秒で１０．０００Ａの衝撃電流を
かけた。その後再びバリスタ電圧■１■Ａを測定した。After measuring the voltage when a direct current of 1 mA was applied to these varistors, that is, the varistor voltage V, mA, an impact current of 10.000 A was applied with a current waveform of 8 x 20 microseconds. Thereafter, the varistor voltage (1) A was measured again.
以上のバリスタ素子試料について、衝撃電流負荷前後即
ちサージ前後におけるバリスタ電圧及びその変化率を第
１表に示した。Table 1 shows the varistor voltage and its rate of change before and after the shock current load, that is, before and after the surge, for the above varistor element samples.
第１表
以上のように、本発明の実施試料としてＺｎＯ□を本発
明の範囲内で加えた素材粉を用いてつくったバリスタ素
子は、１０，０ＯＯＡという大きい衝撃電流を加えても
、バリスタ電圧の変化率が １．７％以下と小さく安定
しており、長期使用においても漏洩電流が少なく、信転
できることを示している。As shown in Table 1, the varistor element made using the raw material powder containing ZnO□ within the scope of the present invention as a practical sample of the present invention has a varistor voltage of The rate of change is small and stable at 1.7% or less, indicating that leakage current is small and reliable even during long-term use.
一方、本発明の範囲外の方法でつくった比較試料につい
ては１０，０ＯＯＡの衝撃電流を加えることにより、素
子内に斉らされる欠陥が比較的大きくなり、サージ電圧
の変化率が約２％以上に大きく、不安定になることを示
している。On the other hand, for a comparative sample made by a method outside the scope of the present invention, by applying an impact current of 10,000 A, the defects uniformed within the device became relatively large, and the rate of change in surge voltage decreased by about 2%. It is larger than the above, indicating that it will become unstable.
〔発明の効果］
以上の説明から明らかなように、本発明によれば、バリ
スタ素子主成分のＺｎＯの結晶粒界における選択酸化を
均−且つ十分に行うことができるので、安定した電圧非
直線性を示し、常時課ｔｔ圧に対して漏洩電流が少なく
、寿命特性に優れた電圧非直線抵抗体の製造方法が提供
できる。[Effects of the Invention] As is clear from the above description, according to the present invention, selective oxidation can be uniformly and sufficiently performed at the grain boundaries of ZnO, which is the main component of a varistor element, so that stable voltage non-linearity can be achieved. It is possible to provide a method for manufacturing a voltage nonlinear resistor that exhibits high performance, has low leakage current with respect to constantly applied tt pressure, and has excellent life characteristics.
Claims (1)
ガン、酸化アンチモン、酸化クロム、酸化ホウ素及び酸
化ニッケルを塩の形で添加して混合した原料粉を用い、
成形して焼結する酸化亜鉛系電圧非直線抵抗体の製造方
法において、前記原料粉に、酸化剤として過酸化亜鉛を
外配で０．５〜１０モル％含有させることを特徴とする
電圧非直線抵抗体の製造方法。Using raw material powder mixed with zinc oxide, bismuth oxide, cobalt oxide, manganese oxide, antimony oxide, chromium oxide, boron oxide, and nickel oxide in salt form,
A method for manufacturing a zinc oxide voltage nonlinear resistor by molding and sintering, characterized in that the raw material powder contains 0.5 to 10 mol% of zinc peroxide as an oxidizing agent. Method of manufacturing a linear resistor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2157268A JPH0448703A (en) | 1990-06-15 | 1990-06-15 | Manufacture of voltage nonlinear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2157268A JPH0448703A (en) | 1990-06-15 | 1990-06-15 | Manufacture of voltage nonlinear resistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0448703A true JPH0448703A (en) | 1992-02-18 |
Family
ID=15645945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2157268A Pending JPH0448703A (en) | 1990-06-15 | 1990-06-15 | Manufacture of voltage nonlinear resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0448703A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2900768A1 (en) * | 2006-05-05 | 2007-11-09 | Areva T & D Sa | USE OF B2O3 IN A SEMICONDUCTOR CERAMIC TO REDUCE LEAKAGE CURRENT AND POSSIBLY TO STABILIZE ELECTRICAL PROPERTIES |
-
1990
- 1990-06-15 JP JP2157268A patent/JPH0448703A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2900768A1 (en) * | 2006-05-05 | 2007-11-09 | Areva T & D Sa | USE OF B2O3 IN A SEMICONDUCTOR CERAMIC TO REDUCE LEAKAGE CURRENT AND POSSIBLY TO STABILIZE ELECTRICAL PROPERTIES |
| WO2007128785A1 (en) * | 2006-05-05 | 2007-11-15 | Areva T&D Sa | Use of b203 in a tin oxide-based semi conductive ceramic for reducing the leakage current thereof and for possibly stabilizing the electrical properties thereof |
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