JPH03116901A - Zinc oxide varistor - Google Patents
Zinc oxide varistorInfo
- Publication number
- JPH03116901A JPH03116901A JP1254696A JP25469689A JPH03116901A JP H03116901 A JPH03116901 A JP H03116901A JP 1254696 A JP1254696 A JP 1254696A JP 25469689 A JP25469689 A JP 25469689A JP H03116901 A JPH03116901 A JP H03116901A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- sintered
- added
- zinc oxide
- pbo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 21
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 4
- 229910011255 B2O3 Inorganic materials 0.000 abstract 1
- 229910002637 Pr6O11 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 11
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000465 moulding Methods 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〕
本発明は、酸化亜鉛を主成分とし、副成分として少なく
ともプラセオジムの酸化物を含む酸化亜鉛電圧非直線抵
抗体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a zinc oxide voltage nonlinear resistor containing zinc oxide as a main component and at least praseodymium oxide as a subcomponent.
酸化亜鉛（ＺｎＯ）を主成分とし、これに種々の添加物
を加えて混合した後、焼結して成るセラミックスは、電
圧非直線性を示すことが知られており、印加電圧増加に
伴い抵抗が急激に減少し、電流増加が著しいため、電気
回路における異常電圧（サージ）を抑制するバリスタと
して広く実用されている。Ceramics made of zinc oxide (ZnO) as a main component, mixed with various additives, and then sintered are known to exhibit voltage nonlinearity, and their resistance increases as the applied voltage increases. Because the current decreases rapidly and the current increases significantly, it is widely used as a varistor to suppress abnormal voltage (surge) in electric circuits.
バリスタの電圧・電流特性は、次の近位式で示される。The voltage/current characteristics of a varistor are expressed by the following proximal equation:
に
こで■はバリスタに流れる電流、■は印加電圧、Ｃは定
数、αは電圧非直線指数である。すなわち、バリスタ特
性はＣおよびαの二つの定数で表すことができる０通常
、Ｃの代わりにバリスタに１−＾の電流を流したときの
電圧ＶｌｓＡが用いられる。また、電圧非直線性を示す
指数であるαは値が大きいことが重要とされている。
ＺｎＯバリスタは、優れた電圧・電流特性を示し、さら
に素子厚さを制御することにより特性を任意に調節でき
る特徴を備えている。In the figure, ■ is the current flowing through the varistor, ■ is the applied voltage, C is a constant, and α is the voltage nonlinear index. That is, the varistor characteristics can be expressed by two constants, C and α.Normally, instead of C, the voltage VlsA when a current of 1−^ is passed through the varistor is used. Further, it is considered important that α, which is an index indicating voltage nonlinearity, has a large value.
ZnO varistors exhibit excellent voltage and current characteristics, and further have the characteristic that the characteristics can be adjusted arbitrarily by controlling the element thickness.
一方、これらのＺｎＯバリスタを各種電子機器の電源入
力側の線間およびアース間対応として使用する場合、従
来の酸化亜鉛電圧非直線抵抗体は常時電圧印加時におけ
る低電流領域の特性変化が大きく、さらに大電流の長波
尾サージが印加された場合のバリスタ電圧の変化率が大
きいために、素子の小型、高性能化を行うことが難しい
という問題があった。On the other hand, when these ZnO varistors are used between lines and ground on the power input side of various electronic devices, the characteristics of conventional zinc oxide voltage nonlinear resistors change significantly in the low current region when voltage is constantly applied. Furthermore, since the rate of change in the varistor voltage is large when a long wave tail surge of a large current is applied, there is a problem in that it is difficult to miniaturize the device and improve its performance.
従来、酸化亜鉛電圧非直線抵抗体の欠点を除くためには
、−膜面にはＺｎＯに種々の金属酸化物を添加配合した
基本組成に対し、さらに数種類の微量の添加物を加える
方法がとられている。しかしながら、酸化物添加によっ
て、大電流領域の電圧非直線性が改善されても、常時電
圧印加または大電流サージ印加による低電流領域の特性
変化が大きく、寿命性能面で問題があった。Conventionally, in order to eliminate the drawbacks of zinc oxide voltage nonlinear resistors, there was a method of adding trace amounts of several types of additives to the basic composition of ZnO and various metal oxides on the film surface. It is being However, even if the voltage nonlinearity in the large current region is improved by adding oxides, the characteristics in the low current region change significantly due to constant voltage application or large current surge application, which poses a problem in terms of life performance.
本発明は、常時電圧を印加した場合、また大電流サージ
を印加した場合の低電流領域での特性変化が少なく、電
圧非直線性の優れた酸化亜鉛電圧非直線抵抗体を提供す
ることにある。An object of the present invention is to provide a zinc oxide voltage nonlinear resistor with excellent voltage nonlinearity and less change in characteristics in the low current region when a constant voltage is applied or when a large current surge is applied. .
上記の目的を達成するために、本発明の酸化亜鉛電圧非
直線抵抗体は、酸化亜鉛を主成分とし、副成分として少
なくともプラセオジムの酸化物のほかに３〜１００モル
ｐｐｍの一酸化鉛が添加、混合された原料を焼結してな
るものとする。In order to achieve the above object, the zinc oxide voltage nonlinear resistor of the present invention has zinc oxide as a main component, and 3 to 100 mol ppm of lead monoxide is added as a subcomponent in addition to at least praseodymium oxide. , the mixed raw materials are sintered.
酸化亜鉛に、Ｐｒ、Ｃｏ、Ｃｒ、Ｍｇなどの金属の酸化
物を添加した原料にｐｂｏを添加、混合し、焼結した場
合、電子顕微鏡によりバリスタ特性に直接関係する粒界
域にＰｒとｐｂが多く偏析していることが確認された。When pbo is added to a raw material made of zinc oxide and oxides of metals such as Pr, Co, Cr, and Mg and mixed and sintered, an electron microscope shows that Pr and pb are present in the grain boundary region, which is directly related to varistor characteristics. It was confirmed that many were segregated.
このＰ「とｐｂが安定した化合物を生成するため、Ｐｂ
Ｏを添加しない場合にくらべ低電流領域の抵抗値が大き
くなり、電圧・電流特性が向上し、また電圧印加の際の
安定性も改善される。Since this P' and pb form a stable compound, Pb
Compared to the case where O is not added, the resistance value in the low current region is increased, the voltage/current characteristics are improved, and the stability during voltage application is also improved.
ＺｎＯにＰｒａＯ＋＋＋Ｃｏ５０ｅ＋ＫｘＯ，ＣｒｚＯ
ｓ、ＭｇＯ，ＣａＯ，ｋｌ、Ｏ，。ZnO, PraO+++Co50e+KxO, CrzO
s, MgO, CaO, kl, O,.
Ｂ２Ｏ，をそれぞれ０．５．２．０，０．１，０．１，
０．１，０．１，０．０１゜０．０１モル％を添加した
ものを基本組成とし、さらにｐｂｏを０．３〜２００モ
ルｐｐｍの範囲で添加し、ボールミルで十分に混合、粉
砕してスラリー化し、バインダ（粘結剤）を配合し、造
粒した後、直径１７鶴、厚さ約２１ｍの円板状に成形し
た。このとき、密度が３．１ｇ／−になるよう成形圧力
が調整される。B2O, respectively 0.5, 2.0, 0.1, 0.1,
The basic composition is one in which 0.1, 0.1, 0.01゜0.01 mol% is added, and PBO is added in a range of 0.3 to 200 mol ppm, thoroughly mixed and pulverized with a ball mill. The slurry was made into a slurry, a binder (caking agent) was mixed therein, granulated, and then molded into a disc shape with a diameter of 17 mm and a thickness of approximately 21 m. At this time, the molding pressure is adjusted so that the density becomes 3.1 g/-.
次に、１２５０ ’Ｃで１時間空気中で焼成し、焼結体
の両面にＡｇ導電性ペーストをスクリーン印刷し、６０
０℃で５分間焼成し、電極を形成して素子を作り、電気
的特性を測定した。Next, it was fired in air at 1250'C for 1 hour, and Ag conductive paste was screen printed on both sides of the sintered body.
It was baked at 0° C. for 5 minutes, electrodes were formed, a device was manufactured, and its electrical characteristics were measured.
第１図は、低電流領域の特性として素子にｌＯｕ＾の電
流を流したときの電圧 （■１゜ｊＡ）と素子に１＋ｌ
ｌＡの電流を流したときの電圧 （Ｖｌ−Ａ）の比（Ｖ
、。ｍＡ ／ Ｖ ｌ−ａ ）で表わした低電流領域の
特性、第２図は素子に４ＯＡの電流を流したときの電圧
（Ｖ４゜、）と素子に１ｍＡの電流を流したときの電圧
（ｖｌｌ）の比（Ｖ ４ｅａ ／ Ｖ ＋−ａ ）で表
わした大電流サージおける非直線性とｐｂｏ添加量の関
係をそれぞれ示す、第１図および第２図から、低電流領
域での特性および大電流領域での非直線性が１モルｐｐ
−以上のＰｂｏの添加により改善され、１０〜３０モル
ｐｐｍを趨えるとやや低下することがわかる。第３図は
、２ ｍ５ｅｃ、１００Ａのく形波電流を２０回印加し
て前後のＶｌ、Ａの変化率、ΔＶｌ、Ａで表わした長波
尾サージ耐量とｐｂｏ添加量との関係を示し、ＰｂＯの
添加により長波尾サージ耐量が改善されることがわかる
。第１ないし第３図に示すように、ＰｂＯ３〜１００モ
ルｐｐｍの添加により、低電流領域での特性および大電
流領域での非直線性が著しく改善されるとともに、ｈ波
尾サージが印加された場合のバリスタ電圧の変化率が小
さくなるので、本発明に基づく電圧非直線抵抗体は、各
種電子機器の電源入力側の線間およびアース間対応とし
て十分満足すべきものである。なお、常時電圧を印加し
た場合の低電流領域での特性変化も第３図と同様の傾向
を示す。Figure 1 shows the voltage (■1゜jA) when a current of lOu^ flows through the element and the voltage of 1+l
Ratio of voltage (Vl-A) (V
,. Figure 2 shows the characteristics in the low current region expressed in mA/V l-a), and the voltage when a current of 4OA is passed through the element (V4゜) and the voltage when a current of 1mA is passed through the element (vll). ) Figures 1 and 2 show the relationship between the nonlinearity in large current surges expressed as the ratio (V 4ea / V + -a) and the amount of pbo added, respectively, and the characteristics in the low current region and the large current The nonlinearity in the region is 1 mol pp
It can be seen that the addition of Pbo in an amount of - or more improves the Pbo content, and decreases slightly when the amount exceeds 10 to 30 mol ppm. Figure 3 shows the relationship between the change rate of Vl and A before and after applying a square wave current of 2 m5ec and 100A 20 times, the long wave tail surge resistance expressed in ΔVl and A, and the amount of pbo added. It can be seen that the long wave tail surge resistance is improved by adding . As shown in Figures 1 to 3, by adding PbO3 to 100 mol ppm, the characteristics in the low current region and the nonlinearity in the high current region were significantly improved, and an h-wave tail surge was applied. Since the rate of change of the varistor voltage is small in this case, the voltage nonlinear resistor according to the present invention is fully satisfactory as a line-to-line and ground-to-ground resistor on the power input side of various electronic devices. Note that the change in characteristics in the low current region when a constant voltage is applied also shows the same tendency as shown in FIG. 3.
本発明によれば、ＺｎＯを主成分とし、副成分としてＰ
ｒその他の金属の酸化物を含む原料にｐｂｏを３〜１０
０モルｐｐｍの範囲で添加、混合し、焼結することによ
り、電圧印加による低電流領域での特性変化が少なく、
電圧非直線性の優れた酸化亜鉛電圧非直線抵抗体を得る
ことができた。According to the present invention, ZnO is the main component, and P is the subcomponent.
r Add 3 to 10 pbo to raw materials containing oxides of other metals.
By adding, mixing, and sintering in the range of 0 mol ppm, there is little change in characteristics in the low current region due to voltage application.
A zinc oxide voltage nonlinear resistor with excellent voltage nonlinearity could be obtained.
第１図は酸化亜鉛電圧非直線抵抗体の低電流領域特性と
ｐｂｏ添加量との関係線図、第２図は大電流領域での非
直線性とｐｂ。
添加量との関係線図、
第３図は長波尾サージ耐量とＰｂＯ
添加量との関係Figure 1 shows the relationship between the low current region characteristics of a zinc oxide voltage nonlinear resistor and the amount of pbo added, and Figure 2 shows the relationship between the nonlinearity and pb in the high current region. Figure 3 shows the relationship between the long wave tail surge resistance and the amount of PbO added.
Claims (1)
ラセオジムの酸化物のほかに３〜１００モルｐｐｍの一
酸化鉛が添加、混合された原料を焼結してなることを特
徴とする酸化亜鉛電圧非直線抵抗体。1) A zinc oxide voltage characterized by being made by sintering a raw material containing zinc oxide as a main component and mixed with at least praseodymium oxide and 3 to 100 mol ppm of lead monoxide as a subcomponent. Non-linear resistor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1254696A JPH03116901A (en) | 1989-09-29 | 1989-09-29 | Zinc oxide varistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1254696A JPH03116901A (en) | 1989-09-29 | 1989-09-29 | Zinc oxide varistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03116901A true JPH03116901A (en) | 1991-05-17 |
Family
ID=17268588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1254696A Pending JPH03116901A (en) | 1989-09-29 | 1989-09-29 | Zinc oxide varistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03116901A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100441863B1 (en) * | 2002-03-28 | 2004-07-27 | 주식회사 에이피케이 | Fabrication of praseodymium-based zinc oxide varistors |
| WO2010089276A1 (en) * | 2009-02-03 | 2010-08-12 | Epcos Ag | Varistor ceramic, multilayer component comprising the varistor ceramic, production method for the varistor ceramic |
-
1989
- 1989-09-29 JP JP1254696A patent/JPH03116901A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100441863B1 (en) * | 2002-03-28 | 2004-07-27 | 주식회사 에이피케이 | Fabrication of praseodymium-based zinc oxide varistors |
| WO2010089276A1 (en) * | 2009-02-03 | 2010-08-12 | Epcos Ag | Varistor ceramic, multilayer component comprising the varistor ceramic, production method for the varistor ceramic |
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