US3863193A - Voltage-nonlinear resistors - Google Patents

Voltage-nonlinear resistors Download PDF

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Publication number
US3863193A
US3863193A US388169A US38816973A US3863193A US 3863193 A US3863193 A US 3863193A US 388169 A US388169 A US 388169A US 38816973 A US38816973 A US 38816973A US 3863193 A US3863193 A US 3863193A
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United States
Prior art keywords
oxide
mole percent
voltage
value
sintered body
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Expired - Lifetime
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US388169A
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English (en)
Inventor
Mikio Matsuura
Atsushi Iga
Yasuo Wakahata
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/112—ZnO type

Definitions

  • n a numerical value greater than 1. The value of n is calculated by the following equation:
  • V, and V are the voltages at given currents l, and 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.
  • Nonlinear resistors comprising sintered bodies of zinc oxide with or without additives and non-ohmic electrode applied thereto, have already been disclosed as seen in U.S. Pat. Nos. 3,496,5 l 2, 3,570,002, 3,503.02) and 3,689,863.
  • the nonlinearity of such varistors is attributed to the interface between the sintered body of zinc oxide with or without additives and silver paint electrode, and is controlled mainly by changing the compositions of said sintered body and silver paint electrode. Therefore, it isnot easy to control the C-value over a wide range after the sintered body is prepared.
  • varistors comprising germanium or silicon p-n junction diodes
  • the silicon carbide varistors have nonlinearity due to the contacts among the individual grains of silicon carbide bonded together by a ceramic binding material, i.e. to the bulk, and C-value is controlled by changing a, dimension in the direction in which the current flows through the varistors.
  • the silicon carbide varistors have high surge resistance thus rendering them suitable as surge absorbers.
  • the silicon carbide varistors however, have a relatively low n-value ranging from 3 to 7 which results in poor surge suppression as well as poor D.C. stabilization.
  • Another defect of the silicon carbide varistor as a DC. stabilizer is their change in C-value and n-value during D.C. load application.
  • An object of the present invention is to provide a voltage-nonlinear resistor having high n-value, high power dissipation for surge energy and high stability for DC load even in a range of current less than 0.lmA/cm?
  • This object of the invention will become apparent upon consideration of the following description taken together with the accompanying drawing in which the FIGURE is a cross-sectional view through a voltagenonlinear resistor in accordance with the invention.
  • a voltagenonlinear resistor comprising, as its active element, a sintered body having a pair of electrodes 2 and 3 in an ohmic contact applied to opposite surfaces thereof.
  • Said sintered body 1- is prepared in a manner hereinafter set forth and is 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-nonlinear resistor comprises a sintered body of a composition comprising, as an additive, 0.0l 10.0 mole percent of bismuth oxide (Bi O 0.01 to 10 mole percent of cobalt oxide (C0 0 0.01 to 5.0 mole percent of boron trioxide (B 0 and 0.01 to 5.0 mole percent of at least one member selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), strontium oxide (SrO) and the remainder of zinc oxide (ZnO) as a main constituent, and electrodes applied to opposite surfaces of said sintered body.
  • MgO magnesium oxide
  • CaO calcium oxide
  • BaO barium oxide
  • ZnO zinc oxide
  • Such a voltage-nonlinear resistor has non-ohmic resistance 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.
  • said resistor has high n-
  • the n-value and stability with DC. load and surge power can be further improved and the C-value can be controlled when said additive consists essentially of 0.1 to 3.0 mole percent of bismuth oxide (B50 0.] to 3.0 mole percent of cobalt oxide (C0 0 0.01 to 5.0 mole percent of boron trioxide (B 03) and 0.01 to 5.0 mole percent of at least one member selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO) and strontium oxide (SrO), 0.1 3.0 mole percent of manganese oxide (MnO) and one member selected from the group consisting of 0.05 to 3.0 mole percent of antimony oxide (Sb O and 0.] to 3.0 mole percent of titanium oxide (TiO).
  • the addition of antimony oxide increases the C-value of the resultant voltage-nonlinear resistor and the addtion of titanium oxide lowers the C-value of the resultant voltage nonlinear resistor.
  • the pressed bodies are sintered in air at L000" to.
  • the mixtures can be preliminarily calcined at 700 to 1,000C 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 he lapped at the opposite surfaces by abrasive powder such as silicon carbide in a particle size of 50a in mean diameter to H) p. in mean diameter.
  • the sintered bodies are provided, at the opposite surfaces thereof with electrodes in any available and suitable method such as silver painting, vacuum evaporation or flame spraying of metal such as Al, Zn, Sn etc.
  • the voltage-nonlinear properties are not practically affected by the kind ofelectrodes 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 nonlinear property is due to the bulk itself, but not to the electrodes.
  • Electrode wires can be attached to the electrodes in a per se conventional manner by using conventional solder. It is convenient to employ a conductive adhesive comprising silver powder and resin in an organic solvent in order to connect the lead wires to the electrodes.
  • Voltage-nonlinear resistors according to this invention have a high stability to temperature, for the DC. load test, which is carried out by applying a rating power of 1 watt at C ambient temperature for 500 hours, and for the surge test, which is carried out by applying surge wave form of 8 X 20p.sec, 500A/cm The n-value do not change remarkably after the. heating cycles, the load life test, humidity test, and surge test.
  • EXAMPLE 1 Starting material composed of 97.0 mole percent of zinc oxide, l.0 mole percent of bismuth oxide, 10 mole percent of cobalt oxide, and 0.5 mole percent of boron trioxide and 0.5 mole percent of magnesium oxide is mixed in a wet mill for 24 hours. The mixture is dried and pressed in a mold into discsof 17.5mm in diameter and 7mm in thickness at a pressure of 250 Kg/cm".
  • the pressed bodies are sintered in air at the condition shown in Table l, and then furnace-cooled to room temperature.
  • the sintered body is lapped at the opposite surfaces'thereof into the thickness shown in Table l by silicon carbide abrasive in particle size of 30 p. in mean diameter.
  • the opposite surfaces of the sintered body are provided with a spray metallized film of aluminum in a per se well known technique.
  • the electrical properties of the resultant resistors are shown in Table 3.
  • the change rates ofC and n values after D.C. load and impulse test are also shown in Table 3.
  • the impulse test is carried out by applying two impulses of 8 X 20 usec, 500A, and D.C. load life test is carried out by the same method as that of Example 2. It will be readily realized that the further addition of manganese oxide results in the higher n-value and smaller change rates than those of Example 2.
  • EXAMPLE 6 The resistors of Example 2,3,4 and 5 are tested in accordance with a method widely used in the electronic component parts.
  • the heating cycle test is carried out by repeating five times the cycle in which said resistors are kept at 85C ambient temperature for 30 minutes.
  • Table 6 shows the average change rates of C-value and n-value of resistors after heating cycle test and humidity test. It is easily understood that each sample has a small change rate.
  • MgO magnesium oxide
  • CaO calcium oxide
  • BaO barium oxide
  • said sintered body further includes, as an addi- 10.() mole percent of cobalt oxide (C0 0 0.01 to 5.0 mole percent of boron trioxide (B 0 and 0.01 to 5.0 mole percent of at least one member selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO) and strontium oxide (SrO) and electrodes in contact with said body.
  • MgO magnesium oxide
  • CaO calcium oxide
  • BaO barium oxide
  • strontium oxide SrO
  • Manganese oxide 0.05 to 3.0 mole percent of manganese oxide (MnO).
  • said sinteredbody further includes, as an addi- 2.
  • Voltage-nonlinear resistor according to claim 1 live one member Selected from the group consisting of wherein said additive consists essentially of 0.1 to 3.0 l0 mole P 0f ly Oxide zon) mole percent of bismuth oxid (M 0 0,] t 3 l and 0.1 to 3.0.mole percent of titanium oxide (TiO percent of cobalt oxide (C0 0 0.01 to 5.0 mole per- 5.
  • NiO nickel oxide

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)
US388169A 1972-08-14 1973-08-14 Voltage-nonlinear resistors Expired - Lifetime US3863193A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP47081643A JPS529299B2 (enrdf_load_stackoverflow) 1972-08-14 1972-08-14

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US3863193A true US3863193A (en) 1975-01-28

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US (1) US3863193A (enrdf_load_stackoverflow)
JP (1) JPS529299B2 (enrdf_load_stackoverflow)
CA (1) CA1019560A (enrdf_load_stackoverflow)
FR (1) FR2196513B1 (enrdf_load_stackoverflow)
GB (1) GB1400344A (enrdf_load_stackoverflow)
HK (1) HK19877A (enrdf_load_stackoverflow)
IT (1) IT990249B (enrdf_load_stackoverflow)
MY (1) MY7700149A (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3999159A (en) * 1974-04-05 1976-12-21 Matsushita Electric Industrial Co., Ltd. Voltage-dependent resistor
EP0037577A1 (en) * 1980-04-07 1981-10-14 Hitachi, Ltd. Nonlinear resistor and process for producing the same
US4451815A (en) * 1982-09-27 1984-05-29 General Electric Company Zinc oxide varistor having reduced edge current density
US4516105A (en) * 1981-07-16 1985-05-07 Tokyo Shibaura Denki Kabushiki Kaisha Metal oxide varistor with non-diffusable electrodes
US5115221A (en) * 1990-03-16 1992-05-19 Ecco Limited Varistor structures
US5155464A (en) * 1990-03-16 1992-10-13 Ecco Limited Varistor of generally cylindrical configuration
US5220316A (en) * 1989-07-03 1993-06-15 Benjamin Kazan Nonlinear resistor control circuit and use in liquid crystal displays
US5235310A (en) * 1990-03-16 1993-08-10 Harris Corporation Varistor having interleaved electrodes
US5294374A (en) * 1992-03-20 1994-03-15 Leviton Manufacturing Co., Inc. Electrical overstress materials and method of manufacture
US5837178A (en) * 1990-03-16 1998-11-17 Ecco Limited Method of manufacturing varistor precursors
US5973588A (en) * 1990-06-26 1999-10-26 Ecco Limited Multilayer varistor with pin receiving apertures
US6183685B1 (en) 1990-06-26 2001-02-06 Littlefuse Inc. Varistor manufacturing method
US6620696B2 (en) * 2000-03-15 2003-09-16 Murata Manufacturing Co., Ltd. Voltage nonlinear resistor, method for fabricating the same, and varistor
CN116031033A (zh) * 2023-01-31 2023-04-28 厦门赛尔特电子有限公司 一种直流低残压型压敏电阻及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5196487U (enrdf_load_stackoverflow) * 1975-01-31 1976-08-03

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA831691A (en) * 1967-10-09 1970-01-06 Matsuoka Michio Non-linear resistors of bulk type

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA831691A (en) * 1967-10-09 1970-01-06 Matsuoka Michio Non-linear resistors of bulk type

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3999159A (en) * 1974-04-05 1976-12-21 Matsushita Electric Industrial Co., Ltd. Voltage-dependent resistor
EP0037577A1 (en) * 1980-04-07 1981-10-14 Hitachi, Ltd. Nonlinear resistor and process for producing the same
US4516105A (en) * 1981-07-16 1985-05-07 Tokyo Shibaura Denki Kabushiki Kaisha Metal oxide varistor with non-diffusable electrodes
US4451815A (en) * 1982-09-27 1984-05-29 General Electric Company Zinc oxide varistor having reduced edge current density
US5220316A (en) * 1989-07-03 1993-06-15 Benjamin Kazan Nonlinear resistor control circuit and use in liquid crystal displays
US6334964B1 (en) 1990-03-16 2002-01-01 Littelfuse, Inc. Varistor ink formulations
US5155464A (en) * 1990-03-16 1992-10-13 Ecco Limited Varistor of generally cylindrical configuration
US5235310A (en) * 1990-03-16 1993-08-10 Harris Corporation Varistor having interleaved electrodes
US5837178A (en) * 1990-03-16 1998-11-17 Ecco Limited Method of manufacturing varistor precursors
US5115221A (en) * 1990-03-16 1992-05-19 Ecco Limited Varistor structures
US6743381B2 (en) 1990-03-16 2004-06-01 Littlefuse, Inc. Process for forming varistor ink composition
US5973588A (en) * 1990-06-26 1999-10-26 Ecco Limited Multilayer varistor with pin receiving apertures
US6183685B1 (en) 1990-06-26 2001-02-06 Littlefuse Inc. Varistor manufacturing method
US5294374A (en) * 1992-03-20 1994-03-15 Leviton Manufacturing Co., Inc. Electrical overstress materials and method of manufacture
US6620696B2 (en) * 2000-03-15 2003-09-16 Murata Manufacturing Co., Ltd. Voltage nonlinear resistor, method for fabricating the same, and varistor
CN116031033A (zh) * 2023-01-31 2023-04-28 厦门赛尔特电子有限公司 一种直流低残压型压敏电阻及其制备方法

Also Published As

Publication number Publication date
JPS529299B2 (enrdf_load_stackoverflow) 1977-03-15
GB1400344A (en) 1975-07-16
FR2196513B1 (enrdf_load_stackoverflow) 1977-05-13
HK19877A (en) 1977-05-06
JPS4938191A (enrdf_load_stackoverflow) 1974-04-09
FR2196513A1 (enrdf_load_stackoverflow) 1974-03-15
IT990249B (it) 1975-06-20
CA1019560A (en) 1977-10-25
MY7700149A (en) 1977-12-31

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