JPH03261101A - Manufacture of voltage nonlinear resistor of zinc oxide - Google Patents
Manufacture of voltage nonlinear resistor of zinc oxideInfo
- Publication number
- JPH03261101A JPH03261101A JP2059263A JP5926390A JPH03261101A JP H03261101 A JPH03261101 A JP H03261101A JP 2059263 A JP2059263 A JP 2059263A JP 5926390 A JP5926390 A JP 5926390A JP H03261101 A JPH03261101 A JP H03261101A
- Authority
- JP
- Japan
- Prior art keywords
- zinc oxide
- voltage
- raw material
- oxide
- sintering
- 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 46
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006104 solid solution Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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 voltage nonlinear resistor containing zinc oxide as a main component and at least praseodymium oxide as a subcomponent.
酸化亜鉛を主成分とし、これに種々の添加物を加えて混
合した後、焼結してなるセラミックスは、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 as a main component, mixed with various additives, and then sintered are known to exhibit voltage nonlinearity, and their resistance increases rapidly as the applied voltage increases. Because the current increases significantly, it is widely used as a varistor to suppress abnormal voltage (surge) in electrical circuits.
バリスタの電圧−電流特性は次の近似式で示される。The voltage-current characteristics of the varistor are expressed by the following approximate equation.
１−（−） α
に
こで１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の二つの定数で表わすことができる。連
室、Ｃの代わりにバリスタに１謬＾の電流を流したとき
の電圧Ｖ工、が用いられる。1-(-) α where 1 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. In place of C, the voltage V when a current of 1 yen flows through the varistor is used.
特に、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０ｗｌ化亜鉛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 particular, it is important that α, which is an index indicating voltage nonlinearity, has a large value. Zinc varistors with 0wt exhibit excellent voltage-current characteristics, and the characteristics can be adjusted arbitrarily by controlling the element thickness. It has adjustable features.
従来の酸化亜鉛電圧非直線抵抗体は対称型の電圧−電流
特性についてみると、大電流の長波尾サージおよび常時
電圧印加時におけるｖｌ、の正方向の変化率と負方向の
変化率との差が大きく、特に負方向の変化率が大きいた
め信頼性が劣るという欠点があった。Regarding the symmetrical voltage-current characteristics of conventional zinc oxide voltage nonlinear resistors, the difference between the rate of change in the positive direction and the rate of change in the negative direction of vl during large current long wave tail surges and constant voltage application. is large, and the rate of change in the negative direction is particularly large, resulting in poor reliability.
本発明の目的は、従来の酸化亜鉛電圧非直線抵抗体にお
ける上記欠点を除き、信頼性が高く、大電流サージ印加
時や常時電圧を印加した場合の電圧安定性が良好で、電
圧非直線性の優れた酸化亜鉛電圧非直線抵抗体の製造方
法を提供することにある。The purpose of the present invention is to eliminate the above-mentioned drawbacks of conventional zinc oxide voltage nonlinear resistors, to provide high reliability, good voltage stability when applying large current surges or constant voltage, and to eliminate voltage nonlinearity. An object of the present invention is to provide an excellent method for manufacturing a zinc oxide voltage nonlinear resistor.
上記の目的を達成するために、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を含む金
属の酸化物を混合した原料を焼結してなる酸化亜鉛電圧
非直線抵抗体の製造方法において、原料に一酸化ニッケ
ル（Ｎｉｐ）を０．００５〜０．１モル％の範囲で添加
するものとする。In order to achieve the above object, the present invention provides a method for producing a zinc oxide voltage nonlinear resistor by sintering a raw material containing zinc oxide as a main component and a metal oxide containing at least praseodymium as a subcomponent. In the above, nickel monoxide (Nip) is added to the raw material in a range of 0.005 to 0.1 mol%.
〔作用〕
酸化亜鉛にＰｒその他の金属の酸化物のほかにＮｉＯを
添加、混合して焼結した場合、特性Ｘ線倣から酸化亜鉛
相は多くのＮｉを固溶していることがわかった。 ０．
００５〜０．１モル％の範囲で酸化物の形で添加された
Ｎｉは焼結、冷却過程で酸化亜鉛相に微妙に出入し、粒
界近傍に固溶体を形成する。[Effect] When NiO is added to zinc oxide in addition to oxides of Pr and other metals and the mixture is sintered, characteristic X-ray scanning reveals that the zinc oxide phase contains a large amount of Ni in solid solution. . 0.
Ni added in the form of an oxide in the range of 0.005 to 0.1 mol % subtly enters and exits the zinc oxide phase during the sintering and cooling process, forming a solid solution near the grain boundaries.
Ｎｉが粒界に析出しないでこのような固溶体とし存在す
ることにより、信頼性の高い電圧・を流特性を発揮し、
また電圧印加の際の安定性も改善される。By existing as a solid solution without precipitating at the grain boundaries, Ni exhibits highly reliable voltage and current characteristics.
Stability during voltage application is also improved.
酸化亜鉛にＰｒ１Ｏ＋＋を０．５モル％、 Ｃ０５Ｏａ
を２．０モル％、 Ｋ、Ｏ，Ｃｒ、Ｏ，、ＭｇＯおよび
ＣａＯをそれぞれ０．１ モル％、 ＡＪ、Ｏ，および
Ｂｔｕｓをそれぞれ０．０１モル％添加したものを基本
組成とし、さらにＮｉＯをｏ、ｏｏｓ〜０．１モル％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、造粒したのち
、直径１７箇厚さ約２鶴の円板状に底形した。このとき
、密度が３．１ｇ／ｃＩｍ’になるように成形圧力が調
整される。0.5 mol% of Pr1O++ in zinc oxide, C05Oa
The basic composition was 2.0 mol% of K, O, Cr, O, , MgO, and CaO, 0.01 mol% of each of AJ, O, and Btus, and further NiO was added in the range of o, oos to 0.1 mol%, thoroughly mixed in a ball mill, pulverized to form a slurry, blended with a binder (binding agent), and granulated. The bottom was shaped like a crane's disk. At this time, the molding pressure is adjusted so that the density is 3.1 g/cIm'.
次に、１２５０℃で１時間空気中で焼威し、焼結体の両
面にＡｇ導電性ペーストをスクリーン印刷し、６００℃
で５分間焼成して電極を形成し、得られた素子の電気的
特性を測定した。Next, the sintered body was baked in air for 1 hour at 1250°C, and Ag conductive paste was screen printed on both sides of the sintered body.
The electrodes were formed by firing for 5 minutes, and the electrical characteristics of the obtained device were measured.
第１図は、ＮｉＯ添加量と素子に１ｍＡの電流を流した
ときの電圧■＋ａＡとの関係を実線で、非直線指数αと
の関係を点線で示す、第１図より、０．００５モル％以
上のＮｉＯの添加により電圧非直線性が改善され、０．
１モル％を超えるとαが著しく低下することがわかる。Figure 1 shows the relationship between the amount of NiO added and the voltage ■+aA when a current of 1 mA is passed through the device as a solid line, and the relationship with the nonlinear index α as a dotted line. From Figure 1, 0.005 mol % or more of NiO improves voltage nonlinearity.
It can be seen that when the content exceeds 1 mol %, α is significantly reduced.
第２図は、長波尾サージ耐量とし２ ｍ５ｅｃ、 １２
０Ａのく形波電流を２０日間印加した場合のＶ、Ｂ値の
正方向の変化率を実線で、負方向の変化率を点線で示す
、また第３図は、高温負荷特性として、８５℃中で２Ｗ
の直流電荷を１０００時間連続印加したのちの■１ｏの
変化率を、同様に正方向を実線で、負方向を点線で示す
、第２図、第３図かられかるように、ＮｉＯの添加量が
０．００５モル％と０．１モル％の範囲にある電圧非直
線抵抗体は極性特性が小さい、このことは、対称型の電
圧・電流特性を維持する上で重要であり、寿命特性およ
び安定性はバリスタ素子としての信頼性を保証するもの
である。Figure 2 shows the long wave tail surge resistance of 2 m5ec, 12
The solid line shows the rate of change in the positive direction of the V and B values and the dotted line shows the rate of change in the negative direction when a 0A square wave current is applied for 20 days. Figure 3 also shows the high temperature load characteristics at 85°C. 2W inside
After continuously applying a DC charge of 1000 hours, the rate of change of 1o is similarly shown by the solid line in the positive direction and the dotted line in the negative direction, as shown in Figures 2 and 3, the amount of NiO added Voltage nonlinear resistors in which the Stability guarantees reliability as a varistor element.
本発明によれば、酸化亜鉛を主成分とする原料にプラセ
オジムなどの酸化物に加えてＮｉＯを０．００５〜０．
１モル％の範囲で添加し、焼結することにより、電圧非
直線性にすぐれ、正方向と負方向の特性の差が小さく、
電圧安定性の良好な酸化亜鉛電圧非直線抵抗体を製造す
ることができた。According to the present invention, in addition to an oxide such as praseodymium, 0.005 to 0.0% of NiO is added to a raw material containing zinc oxide as a main component.
By adding in a range of 1 mol% and sintering, it has excellent voltage nonlinearity, and the difference in characteristics in the positive and negative directions is small.
A zinc oxide voltage nonlinear resistor with good voltage stability could be manufactured.
第１図は本発明に基づりＮｉＯ添加量と素子に１ｍＡを
流したときの電圧ＶＩＩＩＡおよび非直線指数αとの関
係線図、第２図はＮｉＯ添加量と長波尾サージ耐量との
関係線図、第３図はＮｉＯ添加量と高温負荷特性との関
係線図である。
仁４人午理士山ロ 巖Figure 1 is a relationship diagram between the amount of NiO added and voltage VIIIA and nonlinear index α when 1 mA is applied to the device based on the present invention, and Figure 2 is a relationship line between the amount of NiO added and long wave tail surge resistance. 3 are relationship diagrams between the amount of NiO added and high temperature load characteristics. Jin 4 person Urashiyamaro Iwao
Claims (1)
ラセオジムを含む金属の酸化物を混合した原料を焼結し
てなる酸化亜鉛電圧非直線抵抗体の製造方法において、
原料に一酸化ニッケルを０．００５〜０．１モル％の範
囲で添加することを特徴とする酸化亜鉛電圧非直線抵抗
体の製造方法。(1) In a method for manufacturing a zinc oxide voltage nonlinear resistor, which is obtained by sintering a raw material containing zinc oxide as a main component and a metal oxide containing at least praseodymium as a subcomponent,
A method for manufacturing a zinc oxide voltage nonlinear resistor, which comprises adding nickel monoxide to a raw material in a range of 0.005 to 0.1 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2059263A JPH03261101A (en) | 1990-03-09 | 1990-03-09 | Manufacture of voltage nonlinear resistor of zinc oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2059263A JPH03261101A (en) | 1990-03-09 | 1990-03-09 | Manufacture of voltage nonlinear resistor of zinc oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03261101A true JPH03261101A (en) | 1991-11-21 |
Family
ID=13108312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2059263A Pending JPH03261101A (en) | 1990-03-09 | 1990-03-09 | Manufacture of voltage nonlinear resistor of zinc oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03261101A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007302508A (en) * | 2006-05-11 | 2007-11-22 | Sumitomo Metal Mining Co Ltd | Oxide sintered compact, target and transparent conductive film using the same |
-
1990
- 1990-03-09 JP JP2059263A patent/JPH03261101A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007302508A (en) * | 2006-05-11 | 2007-11-22 | Sumitomo Metal Mining Co Ltd | Oxide sintered compact, target and transparent conductive film using the same |
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