US3634337A

US3634337A - Barium-modified zinc oxide voltage variable resistor

Info

Publication number: US3634337A
Application number: US869470A
Authority: US
Inventors: Michio Matsuoka; Takeshi Masuyama; Yoshio Iida
Original assignee: Matsushita Electric Industrial Co Ltd
Current assignee: Panasonic Holdings Corp
Priority date: 1968-11-08
Filing date: 1969-10-27
Publication date: 1972-01-11
Anticipated expiration: 1989-01-11
Also published as: GB1285380A; DE1954056C3; DE1954056A1; DE1954056B2; NL6916779A; NL150256B; JPS495557B1; FR2022907A1

Abstract

A VOLTAGE VARIABLE RESISTOR CERAMIC COMPOSITION CONSISTING ESSENTIALLY OF ZINC OXIDE AND, AS AN ADDITIVE, BARIUM OXIDE. THE BARIUM-MODIFIED ZINC OXIDE VOLTAGE VARIABLE RESISTOR HAS IMPROVED VOLTAGE NONLINEAR PROPER-

TIES DUE TO THE FURTHER ADDITION OF STRONTIUM OXIDE, LEAD OXIDE, CALCIUM OXIDE, COBALT OXIDE AND BISMUTH OXIDE.

Description

Jan. 11, 1972 MICHIQ MATSUOKA ET AL BARIUM-MODIFIED ZINC OXIDE VOLTAGE VARIABLE RESISTOR Filed Oct. 27, 1969 EVE INVENTORS M|CH|O MATSUOKA TAKESHI MASUYAMA YOSHIO IIDA ATTORNEYS United States Patent 3,634,337 BARIUM-MODIFIED ZINC OXIDE VOLTAGE VARIABLE RESISTOR Michio Matsuoka, Takeshi Masuyama, and Yoshio Iida,

Osaka-Eu, Japan, assignors to Matsushita Electric Industrial Co., Ltd., Kadoma, Osaka, Japan Filed Oct. 27, 1969, Ser. No. 869,470 Claims priority, application Japan, Nov. 8, 1968, 43/82,].28 Int. Cl. Htllb 1/06 US. Cl. 252-521 8 Claims ABSTRACT on THE DISCLOSURE A voltage variable resistor ceramic composition consisting essentially of zinc oxide and, as an additive, barium oxide. The barium-modified zinc oxide voltage variable resistor has improved voltage nonlinear properties due to the further addition of strontium oxide, lead oxide, calcium oxide, cobalt oxide and bismuth oxide.

This invention relates to compositions of voltage variable resistor ceramics having non-ohmic resistance, and more particularly to compositions of varistors comprising zinc oxide having non-ohmic resistance due to the bulk thereof.

Various voltage variable resistors such as silicon carbide varistors, selenium rectifiers and germanium or silicon p-n junction diodes have been widely used for stabilization of voltage or current of electrical circuits. The electrical characteristics of such a voltage variable resistor are expressed by the relation:

where V is the voltage across the resistor, I is the current flowing through the resistor, C is a constant corresponding to the voltage at a given current and exponent n is a numerical value greater than 1. The value of n is calculated by the following equation:

n: lfl 2/ 1) 810 a/ 1) where V and V are the voltages at given currents I and I respectively. The desired value of C depends upon the kind of application to which the resistor is to be put. It is ordinarily desirable that the value of n be as large as possible since this exponent determines the extent to which the resistors depart from ohmic characteristics.

In conventional varistors comprising germanium or silicon p-n junction diodes, it is diificult to control the 0 value over a wide range because the voltage variable property of these varistors is not attributed to the bulk but to the p-n junction. On the other hand, silicon carbide varistors have voltage variable properties due to the con: tacts among the individual grains of silicon carbide bonded together by a ceramic binding material, and the C-value is controlled by changing a dimension in a direction in which the current flows through the varistors. Silicon carbide varistors, however, have a relatively low n-value and are prepared by firing in non-oxidizing atmosphere, especially for the purpose of obtaining a lower C-value.

An object of the present invention is to provide a composition of a voltage variable resistor having nonohmic properties due to the bulk thereof and having a controllable C-value.

Another object of the present invention is to provide a composition of a voltage variable resistor characterized by a high n-value.

These and other objects of the invention will become apparent upon consideration of the following description 3,634,337 Patented Jan. 11, 1972 taken together with the accompanying drawing in which the single figure is a partly cross-sectional view of a voltage variable resistor according to the invention.

Before proceeding with a detailed description of the voltage variable resistors contemplated by the invention, their construction will be described with reference to the aforesaid figure of drawing wherein reference character 10 designates, as a whole, a voltage variable resistor comprising, as its active element, a sintered body having a pair of

electrodes

2 and 3 applied to opposite surfaces thereof. Said sintered body 1 is prepared in a manner hereinafter set forth and is in any form such as circular, square or rectangular plate form. Wire leads 5 and 6 are attached conductively to the

electrodes

2 and 3, respectively, by a connection means 4 such as solder or the like.

A voltage variable resistor according to the invention comprises a sintered body of a composition consisting essentially of 90.0 to 99.95 mole percent of zinc oxide and 0.05 to 10.0 mole percent of barium oxide. Such a voltage variable resistor has non-ohmic resistances due to the bulk itself. Therefore, its C-value can be changed without impairing the n-value by changing the distance between said opposite surfaces. The shorter distance results in the lower C-value.

The higher n-value can be obtained when said sintered body consisting essentially of 97.0 to 99.9 mole percent of zinc oxide and 0.1 to 3.0 mole percent of barium oxide in accordance with the invention.

According to the present invention, the stability for ambient temperature and the electric load life test can be improved when said sintered body consists essentially of 82.0 to 99.9 mole percent of zinc oxide, 0.05 to 10.0 mole percent of barium oxide and 0.05 to 8.0 mole percent of calcium oxide.

Further, the stability for ambient temperature and the electric load life test is extremely improved when said sintered body consists essentially of 94.0 to 99.8 mole percent of zinc oxide, 0.1 to 3.0 mole percent of barium oxide and 0.1 to 3.0 mole percent of calcium oxide.

According to the present invention, the n-value is elevated when said sintered body consists essentially of 82.0 to 99.9 mole percent of zinc oxide, 0.05 to 10.0 mole per cent of barium oxide and 0.05 to 8.0 mole percent of one oxide selected from the group consisting of strontium oxide, lead oxide and cobalt oxide.

The n-value is further elevated when said sintered body is of a composition consisting essentially of 94.0 to 99.8 mole percent of zinc oxide, 0.1 to 3.0 mole percent of barium oxide and 0.1 to 3.0 mole percent of one oxide selected from the group consisting of strontium oxide, lead oxide and cobalt oxide.

According to the present invention, a combination of a high n-value and a low C-value can be obtained when said sintered body is of a composition consisting essentially of 74.0 to 99.85 mole percent zinc oxide, 0.05 to 10.0 mole percent of barium oxide, 0.05 to 8.0 mole percent of bismuth oxide and 0.05 to 8.0 mole percent of one oxide selected from the group consisting of strontium oxide and lead oxide.

Further, the C-value is lowered and the n-value is extremely elevated when said sintered body is of a composition consisting essentially of 91.0 to 99.7 mole percent of zinc oxide and 0.1 to 3.0 mole percent of barium oxide, 0.1 to 3.0 mole percent of bismuth oxide, and 0.1 to 3.0 mole percent of one oxide selected from the group consisting of strontium oxide and lead oxide.

According to the present invention, the high n-value also can be obtained when said sintered body is of a composition consisting essentially of 74.0 to 99.85 mole percent of zinc oxide, 0.05 to 10.0 mole percent of barium oxide and 0.05 to 8.0 mole percent of lead oxide and 0.05 to 8.0 mole percent of one oxide selected from the group consisting of strontium oxide and cobalt oxide.

Further, the extremely high n-value can be obtained when said sintered body is of a composition consisting essentially of 91.0 to 99.7 mole percent of zinc oxide and 0.1 to 3.0 mole percent of barium oxide, 0.1 to 3.0 mole percent of lead oxide, and 0.1 to 3.0' mole percent of one oxide selected from the group consisting of strontium oxide and cobalt oxide.

The sintered body 1 can be prepared by a per se well known ceramic technique. The starting materials of the compositions described in the foregoing description are mixed in a wet mill so as to produce homogeneous mixtures. The mixtures are dried and pressed in a mold into desired shapes at a pressure from 100 kg./cm. to 1000 kg./cm. The pressed bodies are sintered in air at a given temperature for 1 to 3 hours, and then furnacecooled to room temperature (about to about C.).

The available sintering temperature is determined in view of electrical resistivity, non-linearity and stability and ranges from 1000 to 1450 C.

The pressed bodies are preferably sintered in nonoxidizing atmosphere such as nitrogen and argon when it is desired to reduce the electrical resistivity.

The mixtures can be preliminarily calcined at 700 to 1000 C. and pulverized for easy fabrication in the subsequent pressing step. The mixture to be pressed can be admixed with a suitable binder such as water, polyvinyl alcohol, etc.

It is advantageous that the sintered body be lapped at the opposite surfaces by abrasive powder such as silicon carbide in a particle size of 300 meshes to 1500 meshes.

The sintered bodies are provided, at the opposite surfaces thereof, with electrodes in any available and suitable method such as electroplating method, vacuum evaporat tion method, metallizing method by spraying or silver painting method.

The voltage variable properties are not practically affected by the kinds of electrodes used, but are affected by the thickness of the sintered bodies. Particularly, the C- value varies in proportion to the thickness of the sintered bodies, while the n-value is almost independent of the thickness. This surely means that the voltage variable property is due to the bulk of the body, but not to the electrode.

Lead wires can be attached to the electrodes in a per se conventional manner by using conventional solder having a low melting point. It is convenient to employ a conductive adhesive comprising silver powder and resin in an or anic solvent in order to connect the lead wires to the V electrodes.

Voltage variable resistors according to this invention have a high stability to temperature and in the load life test, which is carried out at C. at a rating power for 500 hours. The n.-value and C-value do not change remarkably after heating cycles and load life test. It is advantageous for achievement of a high stability to humidity that the resultant voltage variable resistors are embedded in a humidity proof resin such as epoxy resin and phenol resin in a per se well known manner.

Presently preferred illustrative embodiments of the invention are as follows.

EXAMPLE 1 A mixture of zinc oxide and barium oxide in a composition of Table 1 are mixed in a wet mill for 3 hours. The mixture is dried and then calcined at 700 C. for 1 hour. The calcined mixture is pulverized by the motordriven ceramic mortar for 30 minutes and then pressed in a mold into a shape of 17.5 mm. in diameter and 2.5 mm. in thickness at a pressure of 500 kg./cm.

The pressed body is sintered in air at 1350 C. for 1 hour, and then furnace-cooled to room temperature (about 15 to about 30 C.). The sintered disc is lapped at the opposite surfaces thereof by silicon carbide in a particle size of 600 meshes. Resulting sintered disc has a size of 14 mm. in diameter and 1.5 mm. in thickness. The silver point electrodes commercially available are attached to the opposite surfaces of sintered disc by painting. Then lead wires are attached to the silver electrodes by soldering. The electric characteristics of the resultant resistors are shown in Table 1. It will be readily understood that the zinc oxide sintered body incorporated with barium oxide in an amount of 0.05 to 10.0 mole percent is available for the voltage variable resistor, and particularly the addition of barium oxide in an amount of 0 .1 to 3.0 mole percent makes the voltage nonlinear property more excellent.

Starting materials composed of 99.5 mole percent of zinc oxide and 0.5 mole percent of barium oxide are mixed, dried, calcined and pulverized in the same manner as those of Example 1. The pulverized mixture is pressed in a mold into a disc of 17.5 mm. in diameter and 5 mm. in thickness at a pressure of 500 kg./cm.

The pressed body is sintered in air at 1350 C. for 1 hour, and then furnace-cooled to room temperature. The sintered disc is ground at the opposite surfaces thereof into the thickness shown in Table 2 by silicon carbide in a particle size of 600 meshes. The ground disc is provided with the electrodes and lead wires at the opposite surface in a manner similar to that of Example 1. The electric characteristics of the resultant resistors are shown in Table 2; the C-value varies approximately in proportion to the thickness of the sintered disc while the n-value is essentially independent of the thickness. It will be readily realized that the voltage nonlinear properties of the resistors are attributed to the sintered body itself.

EXAMPLE 3 Zinc oxide incorporated with barium oxide and calcium oxide in the composition of Table 3 is fabricated into the voltage variable resistors by the same process as that of Example 1. The resulting resistors are tested according to the methods used in the electronic components parts. The load life test is carried out at 70 C. ambient temperature at 0.5 watt rating power for 500 hours. The heating cycle test is carried out by repeating 5 times the cycle in which said resistors are kept at C. ambient temperature for 30 minutes, cooled rapidly to 20 C. and then kept at such temperature for 30 minutes. Table 3 shows a difference in C-values and n-values after the load life test. It can be readily realized that the combination of barium oxide and calcium oxide as additive is effective for the electrical and environmental stability.

TABLE 3 TABLE 5 Load life test Heating cycle test BaO SrO C PbO 139.0 02.0 (mol. (mol. (mol. (mol. (r1101. (mol. AC An AC A'n percent) percent) percent) percent) 0 (at 1 ma.) n percent) percent) (percent) (percent) (percent) (percent) r o 0. 05 0. 05 0. 05 600 8. 0 0. 05 0. 05 8. 5 9. 2 -9. 0 8. 6 0. 05 0. 05 8 840 7. 9 0. 05 0. 5 -7. 2 --6. 2 -7. 1 5. 2 0. 05 8 0. 05 570 6.1 0. 05 8 7. 0 --6. 0 -5. 0 5. 9 o. 05 8 s 550 s. 0 0. 5 0. 05 -e. 2 -8. 7 -7. 9 8. 7 1o 0. 05 0. 05 530 7. 9 0.5 8 -7.0 -s.5 -s.0 -8.8 0.05 s 515 8.3 10 0. 05 6. 9 -7. 1 -6. 2 -7. 1 10 8 0. 05 500 8.0 10 0.5 6.7 6.5 -5.9 5.3 10 10 8 8 490 8.4 10 8 -9. c -9. 3 -s. 7 9. 0 0.1 0.1 0.1 275 13 0.1 0.1 -4.2 --4.3 4.8 -4.2 0.1 0,1 a 290 14 0.1 0.5 3.8 -2.9 3.2 2.2 0.1 a 0.1 300 14 0.1 a 4.1 -3.7 -a.3 -4.0 0.1 3 a 300 14 0. 5 0.1 2. 5 -4. 5 -4. 5 3. 0 3 0.1 0.1 125 15 0.5 3 -2.7 -4.4 4.7 2.5 a 0.1 a 110 17 3 0.1 3. 0 -3. 6 -3. 4 -2. 8 3 a 0.1 135 14 3 0.5 -3.7 -2.9 3.6 3.0 15 a 3 a 150 14 3 a 4.9 -4.s -4.0 -3.0 0.5 0.5 0.5 39 25 0.5 0.5 1.2 -1.1 0.8 1.3 0.05 0.05 490 8.3 0. 05 0.05 8 480 8.4 0. 05 8 0. 05 500 8.3 0. 05 8 8 520 7.8 10 0. 05 0. 05 480 7. 0 10 0.05 8 450 8.1 it 2 :28 a EXAMPLE 4 0.1 0.1 0.1 270 12 0.1 0.1 285 12 Zinc oxide contalnmg additions of Table 4 and Table 0,1 3 ,1 28 12 5 1s fabncated 1nto the voltage variable reslstors by the M 3 3 14 3 0.1 0.1 100 13 same process as that of Example 1. The n-values of the 3 105 15 resulting resistors are shown in Tables 4 and 5. it will be 3 g readily seen that the combmation of barium oxide wlth 0.5 0.5 0.5 as 24 one oxide selected from the group of strontmm oxlde. cobalt oxide and lead oxide as additives results 1n an excellent voltage-nonlinear property and a remarkably 3 EXAMPLE 5 excellent n-value can be obtained by an additive combination of barium oxide and lead oxide with strontium oxide or cobalt oxide.

TABLE 4 C00 PbO (mol. mol. percent) percent) SrO (moi. percent) BaO (mol. percent) C (at 1 ma.)

Zinc oxide containing additions of Table 6 is fabricated into the voltage variable resistors by the same process as that of Example 1. The electrical properties of the resulting resistors are shown in Table 6. It will be easily realized that the combination of barium oxide and bismuth oxide with lead oxide or strontium oxide as additives results in a remarkably excellent n-value and at the same time in a lower C-value.

TABLE 6 138.0 B1203 PbO SrO (mo mo (moi. (mol. percent) percent) percent) percent) 0 (at 1 ma.) *0

What is claimed is:

1. A voltage variable resistor ceramic composition consisting essentially of zinc oxide and 0.05 to 10.0 mole percent of barium oxide.

2. A voltage variable resistor ceramic composition as claimed in claim 1, wherein said composition consists essentially of zinc oxide and 0.1 to 3.0 mole percent of barium oxide.

3. A voltage variable resistor ceramic composition as claimed in claim 1, wherein said composition further includes 0.05 to 8.0 mole percent of oxide selected from the group consisting of strontium oxide, lead oxide, calcium oxide and cobalt oxide.

4. A voltage variable resistor ceramic composition as claimed in claim 2, wherein said composition further includes 0.1 to 3.0 mole percent of one oxide selected from the group consisting of strontium oxide, lead oxide, cobalt oxide and calcium oxide.

5. A voltage variable resistor ceramic composition as claimed in claim 1, wherein said composition further includes 0.05 to 8.0 mole percent of bismuth oxide and 0.05 to 8.0 mole percent of one oxide selected from the group consisting of strontium oxide and lead oxide.

6. A voltage variable resistor ceramic composition as claimed in claim 2, wherein said composition further includes 0.1 to 3.0 mole percent of bismuth oxide and 0.1 to 3.0 mole percent of one oxide selected from the group consisting of strontium oxide and lead oxide.

7. A voltage variable resistor ceramic composition as claimed in claim 1, wherein said composition further includes 0.05 to 8.0 mole percent of lead oxide and 0.05 to 8.0 mole percent of one oxide selected from the group consisting of strontium oxide and cobalt oxide.

8. A voltage variable resistor ceramic composition as claimed in claim 2, wherein said composition further includes 0.1 to 3.0 mole percent of lead oxide and 0.1 to 3.0 mole percent of one oxide selected from the group consisting of strontium oxide and cobalt oxide.

References Cited UNITED STATES PATENTS 2,892,988 6/1959 Schusterius 252-520 DOUGLAS J. DRUMMOND, Primary Examiner US. Cl. X.R. 2525 1 8