JPS6325684B2 - - Google Patents
Info
- Publication number
- JPS6325684B2 JPS6325684B2 JP55100526A JP10052680A JPS6325684B2 JP S6325684 B2 JPS6325684 B2 JP S6325684B2 JP 55100526 A JP55100526 A JP 55100526A JP 10052680 A JP10052680 A JP 10052680A JP S6325684 B2 JPS6325684 B2 JP S6325684B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- voltage
- borate glass
- zno
- zinc borate
- 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.)
- Expired
Links
- 239000005385 borate glass Substances 0.000 claims description 17
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- YISOXLVRWFDIKD-UHFFFAOYSA-N bismuth;borate Chemical compound [Bi+3].[O-]B([O-])[O-] YISOXLVRWFDIKD-UHFFFAOYSA-N 0.000 claims description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 239000000615 nonconductor Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Description
本発明はZnOを主成分とする酸化物電圧非直線
抵抗素子の改良に関する。従来電圧非直線抵抗素
子（以下バリスタと称す）はサージ吸収素子、電
圧安定化素子、避雷器等に広く用いられ、ZnOを
主成分とするバリスタが開発されているが、半永
久的に使用される避雷器用バリスタにおいては未
だ充分な特性が得られていない。
即ち、避雷器が設置される電気回路においてバ
リスタは一般に常時一定電圧が印加された状態で
使用され、落雷の際には雷による大電流パルスの
サージ吸収素子として使用される必要がある。一
般にバリスタの特性は次式で示されるαおよび
Viの値で評価されている。
Ｉ／ｉ＝（Ｖ／Vi）〓
Ｉは素子内を流れる電流、Ｖは印加電圧、Vi
は電流値がｉのときの電圧で通常１ｍＡの値をと
り、立ち上がり電圧と称されている。αが大なる
程電圧制御能が優れているので、実用上30以上が
望ましい。Viは使用される電圧がいくらである
かによつて定められるものであり、それぞれ指定
された値に調整されることが望ましい。又α，
Viだけでなく洩れ電流IRの値も重要である。バリ
スタを過電圧保護用として使用する場合、回路の
使用を電圧の1.6倍の立ち上がり電圧のバリスタ
を使用するのが通常である。このような使用法の
場合、通常バリスタにはできるかぎり電流が流れ
ないのが望ましいため、IRに値は少ないことが要
求される。
このような一定電圧印加ないしは、サージ印加
による特性変化と改善する試みの一つにZnOを主
成分とするバリスタに種々のガラスを含有させる
試みがなされているが、その効果は殆んど耐サー
ジ特性にのみ有効であつたり、逆に一定電圧印加
による特性変化のみに有効であつたりして、両者
に有効に作用するガラスは提案されていなかつ
た。
本発明はZnOを主成分とし、副成分として
Bi2O3，Co2O3，Sb2O3，MnOをそれぞれ0.1〜3.0
モル％，0.05〜2.0モル％，0.05〜3.0モル％，0.05
〜2.0モル％配合し、必要に応じNiO，Cr2O3，
SiO2，Al2O3をそれぞれ0.05〜2.0モル％，0.05〜
2.0モル％，0.1〜3.0モル％，0.001〜1.0モル％配
合した原料に対してSiO2を含まない硼酸亜鉛ガ
ラスもしくは硼酸ビスマスガラスを重量比で0.05
〜1.0％添加配合した酸化物電圧非直線抵抗素子
に係るもので避雷器に好適なバリスタ素子に要請
される長期間一定電圧印加に対する立ち上がり電
圧およびもれ電流の変化率が小さく課電寿命特性
が優れ、かつ大電流パルス印加に対する立ち上が
り電圧の変化率が小さいすなわち耐サージ特性が
優れたバリスタを得ることができる。
以下本発明を実施例により説明すれば原料とし
て99％以上の純度を有するZnO，Bi2O3，Co2O3，
Sb2O3，MnCO3，NiO，Cr2O3，SiO2，Al
（NO3）3・9H2Oおよび硼酸亜鉛ガラスを用いた。
前記硼酸亜鉛ガラスはB2O3，ZnOを含むが、
SiO2は含まない。
これらを所定量だけ秤量し、純水を用いてボー
ルミルにより24時間混合した。その後乾燥し700
℃〜900℃で仮焼結し、小量のバインダ（PVA5
％水溶液）を加え、直径55mmの円板状に加圧成型
し、1100〜1300℃で２時間焼成して得られた焼結
体を厚さ20mmに研磨した後直径40mmのアルミニウ
ム溶射電極を設けた。α，Vi，もれ電流等の特
性は、定電流電源を使用するか、ないしはカーブ
トレーサーのパルスにより電流電圧特性を測定し
て算定した。なおViは電流１ｍＡ（電流密度0.08
ｍＡ／cm2）のときの厚さ１mmあたりの電圧とし、
以下之をV1ｍＡと称する。またαはV1ｍＡと
V0.1ｍＡの値から算定した。またもれ電流はV1ｍ
Ａの1/2の周波数50Hzの電圧を印加し、抵抗分に
相当する値を算出した。
課電寿命特性は80℃に保たれた恒温槽中で
0.1W／cm2の電力を24時間印加した後室温にもど
してV0.01ｍＡおよびIRの値を測定して変化率を算
出し、これで特性評価を行なつた。
耐サージ特性は10KA（電流波形８×20μsec）
のパルスを30秒の間隔で10回印加した後V0.01ｍ
Ａを測定して変化率を算出し、これで特性評価を
行なつた。
又、上記した硼酸亜鉛ガラスの替りに硼酸ビス
マスガラスを用いた他は、上記の実施例と同様に
して焼結体を得、これにアルミニウム溶射電極を
取付けた後、諸特性の測定を行なつた。ここで硼
酸ビスマスガラスとは、SiO2を含まず、少なく
ともB2O3及びBi2O3を含むガラス組成物をいう。
第１表は本発明の実施例の硼酸亜鉛ガラスの組
成を示す。
The present invention relates to improvements in oxide voltage nonlinear resistance elements containing ZnO as a main component. Conventional voltage nonlinear resistance elements (hereinafter referred to as varistors) are widely used in surge absorption elements, voltage stabilization elements, lightning arresters, etc. Varistors whose main component is ZnO have been developed, but lightning arresters that are used semi-permanently Sufficient characteristics have not yet been obtained for varistors for use in the automotive industry. That is, in an electrical circuit in which a lightning arrester is installed, a varistor is generally used with a constant voltage applied to it at all times, and in the event of a lightning strike, it needs to be used as a surge absorbing element for large current pulses caused by lightning. Generally, the characteristics of a varistor are α and
It is evaluated by the value of Vi. I/i=(V/Vi)〓 I is the current flowing in the element, V is the applied voltage, Vi
is the voltage when the current value is i, usually takes a value of 1 mA, and is called the rising voltage. The larger α is, the better the voltage control ability is, so 30 or more is desirable in practice. Vi is determined by the voltage used, and is preferably adjusted to a specified value. Also α,
In addition to Vi, the value of leakage current I R is also important. When using a varistor for overvoltage protection, the circuit typically uses a varistor with a rise voltage that is 1.6 times the voltage. In this type of usage, it is generally desirable that as little current as possible flows through the varistor, so a small value for I R is required. One attempt to improve this change in characteristics due to constant voltage application or surge application has been to incorporate various types of glass into ZnO-based varistors, but these efforts have little effect on surge resistance. Glasses that are effective only in changing the characteristics, or conversely only in changing the characteristics due to the application of a constant voltage, have not been proposed. The present invention uses ZnO as the main component and as a subcomponent.
Bi 2 O 3 , Co 2 O 3 , Sb 2 O 3 , MnO each from 0.1 to 3.0
Mol%, 0.05~2.0mol%, 0.05~3.0mol%, 0.05
~2.0 mol%, NiO, Cr 2 O 3 , as necessary.
0.05 to 2.0 mol% and 0.05 to 2.0 mol% of SiO 2 and Al 2 O 3 , respectively
2.0 mol%, 0.1-3.0 mol%, 0.001-1.0 mol% of raw materials mixed with zinc borate glass or bismuth borate glass that does not contain SiO 2 at a weight ratio of 0.05
It is related to an oxide voltage non-linear resistance element containing ~1.0% additive, and has a small rate of change in rise voltage and leakage current when a constant voltage is applied over a long period of time, which is required for a varistor element suitable for lightning arresters, and has excellent energized life characteristics. It is possible to obtain a varistor which has a small rate of change in rising voltage with respect to the application of a large current pulse, that is, has excellent anti-surge characteristics. The present invention will be explained below with reference to examples. ZnO, Bi 2 O 3 , Co 2 O 3 , having a purity of 99% or more are used as raw materials.
Sb 2 O 3 , MnCO 3 , NiO, Cr 2 O 3 , SiO 2 , Al
(NO 3 ) 3 ·9H 2 O and zinc borate glass were used.
The zinc borate glass contains B 2 O 3 and ZnO,
Contains no SiO2 . A predetermined amount of these was weighed and mixed with pure water in a ball mill for 24 hours. Then dry 700
Temporarily sintered at ~900℃ and a small amount of binder (PVA5
% aqueous solution), pressure molded into a disc shape with a diameter of 55 mm, and fired at 1100 to 1300 °C for 2 hours. The resulting sintered body was polished to a thickness of 20 mm, and then an aluminum sprayed electrode with a diameter of 40 mm was installed. Ta. Characteristics such as α, Vi, and leakage current were calculated by using a constant current power supply or by measuring current-voltage characteristics using pulses from a curve tracer. Note that Vi is a current of 1 mA (current density 0.08
mA/cm 2 ), the voltage per 1 mm of thickness,
The following is referred to as V 1 mA. Also, α is V 1 mA
Calculated from the value of V 0.1 mA. Also, the leakage current is V 1 m
A voltage with a frequency of 50 Hz, which is 1/2 of A, was applied, and a value corresponding to the resistance was calculated. The energized life characteristics are measured in a constant temperature oven maintained at 80℃.
After applying a power of 0.1 W/cm 2 for 24 hours, the temperature was returned to room temperature, the values of V 0.01 mA and IR were measured, the rate of change was calculated, and the characteristics were evaluated. Surge resistance is 10KA (current waveform 8 x 20μsec)
After applying 10 pulses at 30 seconds intervals, V 0.01 m
A was measured, the rate of change was calculated, and the characteristics were evaluated. In addition, a sintered body was obtained in the same manner as in the above example except that bismuth borate glass was used instead of the above-mentioned zinc borate glass, and after attaching an aluminum sprayed electrode to this, various properties were measured. Ta. Here, bismuth borate glass refers to a glass composition that does not contain SiO 2 but contains at least B 2 O 3 and Bi 2 O 3 . Table 1 shows the composition of zinc borate glasses of Examples of the present invention.
【表】
上記の硼酸亜鉛ガラスＡ，Ｂ，Ｃ，Ｄ及びＥに
ついて実施した結果を第２表に示す。表中〇印は
本発明に係る実施例である。[Table] Table 2 shows the results of the tests conducted on the above zinc borate glasses A, B, C, D and E. The circles in the table are examples according to the present invention.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
第３表に、本発明の他の実施例において用いた
硼酸ビスマスガラスの組成を示す。[Table] Table 3 shows the composition of bismuth borate glass used in other examples of the present invention.
【表】
上記の硼酸ビスマスガラスA′，B′及びC′につ
いて実施した結果を第４表に示す。表中〇印は本
発明に係る実施例である。[Table] Table 4 shows the results obtained for the above bismuth borate glasses A', B' and C'. The circles in the table are examples according to the present invention.
【表】【table】
【表】【table】
【表】【table】
【表】
又従来の硼酸亜鉛ガラスの組成の一例を第５表
に示す。これらのガラスを添加して本発明と同様
な組成によつて焼結された電圧非直線抵抗素子の
特性を第６表に示す。[Table] An example of the composition of conventional zinc borate glass is shown in Table 5. Table 6 shows the characteristics of voltage nonlinear resistance elements sintered with the same composition as the present invention with the addition of these glasses.
【表】【table】
【表】
第２表及び第４表から明らかなごとく本発明の
実施例は優れた電圧非直線性を示し、大電流パル
ス印加に対する変化率が小さく、しかも一定電圧
印加に対する変化率が小さいバリスタが得られ
る。
実施例の添加量が本発明の添加量の範囲外にな
ると、αが60未満、V1ｍＡが220V以上または
180V未満となり、IRが50μA以上、電圧印加によ
るV0.01ｍＡの変化が４％より大となり、電力印
加によるIRの変化が３％より大となる。又大電流
パルスによるV0.01ｍＡの変化が10％より大とな
るので、避雷器用バリスタとしては不適当な特性
となる。
又第５表及び第６表にも明らかなごとくSiO2
を含む従来の硼酸亜鉛ガラスの場合は何れも本発
明の実施例の特性に比較して劣り、実用性に乏し
いことが判る。[Table] As is clear from Tables 2 and 4, the examples of the present invention exhibit excellent voltage nonlinearity, and the varistor exhibits a small rate of change when a large current pulse is applied, and a small rate of change when a constant voltage is applied. can get. If the amount added in the example is outside the range of the amount added in the present invention, α is less than 60, V 1 mA is 220 V or more, or
It becomes less than 180V, I R is 50 μA or more, the change in V 0.01 mA due to voltage application is greater than 4%, and the change in I R due to power application is greater than 3%. Further, since the change in V 0.01 mA due to a large current pulse is greater than 10%, the characteristics are inappropriate for a varistor for a lightning arrester. Also, as is clear from Tables 5 and 6, SiO 2
It can be seen that all of the conventional zinc borate glasses containing the above have inferior properties compared to those of the examples of the present invention, and are of little practical use.
Claims (1)
Co2O3，Sb2O3，MnOをそれぞれ0.1〜3.0モル％，
0.05〜2.0モル％，0.05〜3.0モル％，0.05〜2.0モ
ル％配合した原料に対してSiO2を含まない硼酸
亜鉛ガラスもしくは硼酸ビスマスガラスを重量比
で0.05〜1.0％添加配合した酸化物電圧非直線抵
抗素子。 ２ ZnOを主成分とし、副成分としてBi2O3，
Co2O3，Sb2O3，MnOをそれぞれ0.1〜3.0モル％，
0.05〜2.0モル％，0.05〜3.0モル％，0.05〜2.0モ
ル％配合し、さらに、NiO，Cr2O3，SiO2，
Al2O3の少なくとも一種をそれぞれ0.05〜2.0モル
％，0.05〜2.0モル％，0.1〜3.0モル％，0.001〜
1.0モル％配合した原料に対してSiO2を含まない
硼酸亜鉛ガラスもしくは硼酸ビスマスガラスを重
量比で0.05〜1.0％添加配合した酸化物電圧非直
線抵抗素子。[Claims] 1 ZnO as the main component, with Bi 2 O 3 as subcomponents,
0.1 to 3.0 mol% each of Co 2 O 3 , Sb 2 O 3 , and MnO,
Oxide voltage non-conductors are made by adding 0.05 to 1.0% by weight of zinc borate glass or bismuth borate glass, which does not contain SiO 2 , to the raw materials containing 0.05 to 2.0 mol%, 0.05 to 3.0 mol%, and 0.05 to 2.0 mol%. Linear resistance element. 2 ZnO as main component, Bi 2 O 3 as subcomponent,
0.1 to 3.0 mol% each of Co 2 O 3 , Sb 2 O 3 , and MnO,
0.05-2.0 mol%, 0.05-3.0 mol%, 0.05-2.0 mol%, and further contains NiO, Cr2O3 , SiO2 ,
At least one type of Al 2 O 3 is 0.05-2.0 mol%, 0.05-2.0 mol%, 0.1-3.0 mol%, 0.001-
An oxide voltage nonlinear resistance element in which 0.05 to 1.0% by weight of zinc borate glass or bismuth borate glass that does not contain SiO 2 is added to a raw material containing 1.0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10052680A JPS5726403A (en) | 1980-07-24 | 1980-07-24 | Oxide voltage nonlinear resistance element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10052680A JPS5726403A (en) | 1980-07-24 | 1980-07-24 | Oxide voltage nonlinear resistance element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5726403A JPS5726403A (en) | 1982-02-12 |
| JPS6325684B2 true JPS6325684B2 (en) | 1988-05-26 |
Family
ID=14276398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10052680A Granted JPS5726403A (en) | 1980-07-24 | 1980-07-24 | Oxide voltage nonlinear resistance element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5726403A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102016104990A1 (en) | 2016-03-17 | 2017-09-21 | Epcos Ag | Ceramic material, varistor and method for producing the ceramic material and the varistor |
-
1980
- 1980-07-24 JP JP10052680A patent/JPS5726403A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5726403A (en) | 1982-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1045369A (en) | Zinc oxide voltage-nonlinear resistor | |
| US4374049A (en) | Zinc oxide varistor composition not containing silica | |
| JPS6325684B2 (en) | ||
| US4060661A (en) | Voltage-dependent resistor | |
| JPH0136684B2 (en) | ||
| JPS5811084B2 (en) | Voltage nonlinear resistor | |
| JPS6329802B2 (en) | ||
| JPH0425681B2 (en) | ||
| JPS6221242B2 (en) | ||
| JPS6329804B2 (en) | ||
| JP2715718B2 (en) | Voltage non-linear resistor | |
| JPS634681B2 (en) | ||
| JPH05234716A (en) | Zinc oxide varistor | |
| JPS6329805B2 (en) | ||
| JPS5853487B2 (en) | Voltage nonlinear resistor | |
| JPS6329801B2 (en) | ||
| JPS6236615B2 (en) | ||
| JPS5853488B2 (en) | Voltage nonlinear resistor | |
| JPS6329803B2 (en) | ||
| JPS6113603A (en) | Voltage nonlinear resistor | |
| JPS622501A (en) | Voltage/current non-linear resistor | |
| JPH0354441B2 (en) | ||
| JPH0580802B2 (en) | ||
| JPH0223008B2 (en) | ||
| JPS6059724B2 (en) | Voltage nonlinear resistance element and its manufacturing method |