US3928245A - Metal oxide voltage-variable resistor composition - Google Patents

Metal oxide voltage-variable resistor composition Download PDF

Info

Publication number
US3928245A
US3928245A US377218A US37721873A US3928245A US 3928245 A US3928245 A US 3928245A US 377218 A US377218 A US 377218A US 37721873 A US37721873 A US 37721873A US 3928245 A US3928245 A US 3928245A
Authority
US
United States
Prior art keywords
oxide
molar percent
composition
trioxide
percent
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 - Lifetime
Application number
US377218A
Other languages
English (en)
Inventor
Herbert Fishman
James S Kresge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Priority to US377218A priority Critical patent/US3928245A/en
Priority to JP49075910A priority patent/JPS5740642B2/ja
Priority to DE2432613A priority patent/DE2432613C2/de
Application granted granted Critical
Publication of US3928245A publication Critical patent/US3928245A/en
Priority to US05/822,623 priority patent/USRE29731E/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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

  • the invention relates generally to metal oxide nonlinear voltage-variable resistors, and is particularly applicable to, but not limited to, zinc oxide resistors for overvoltage surge protection devices.
  • overvoltage surge protective devices include as an essential element a non-linear voltage-variable resistor.
  • the resistor may be made of silicon carbide, which is commonly used for such a purpose, orit may also'be made of a metal oxide composition, such as zinc oxide.
  • Overvoltage surge protection devices and their function are discussed in, for example, the following:
  • Metal oxide compositions for non-linear resistors are described in some detail in, for example, the following:
  • zinc oxide resistors consist substantially of zinc oxide
  • certain impurities added to the zinc oxide in minute quantities are necessary to give the resistor the characteristics which are desired for a given application. These characteristics are termed the strength, the exponent, and the stability.
  • the strength of surge arrester valve element is a measure of its ability to resist current channeling in the bulk material under severe loading conditions. The phenomenon by which such channeling occurs is not presently fully understood, and the strength of a given valve element material is thus determined on a relative basis by empirical methods.
  • the exponent of a valve element material is, in effect, the degree of non-linearity of the resistance relative to the applied voltage.
  • a high exponent material is more likely to be suitable as surge arrester valve than is a low exponent material, as it will provide a more distinct switching operation.
  • Stability refers to the ability of the valve element to retain its initial current-voltage characteristics after a period of operation under typical operating conditions.
  • a metal oxide non-linear voltage-variable resistor of the type comprising silicon dioxide as an impurity comprises in addition thereto, the impurities barium oxide and boron oxide.
  • the addition of the impurities barium oxide and boron oxide results in improved stability of the resistor.
  • FIG. 1 shows a sectioned perspective of an arrester valve element of sintered material having a composition in accordance with a preferred embodiment of the invention.
  • FIG. 2 shows the relative stabilities of prior art valve elements as compared to the valve element of FIG. I.
  • a preferred embodiment of the envention is the surge arrester valve element disc 10 shown in FIG. 1.
  • the disc 10 is a sintered body of zinc oxide compound provided on both faces with a contact layer 12 of silver, and also provided about the perimeter with an insulating coating 14 to prevent flashover.
  • the disc 10 is pressed from a powder having the following composition, in mole percent:
  • the disc 10 is pressed into shape, it is sintered in generally the same way as are the more commonly used silicon carbide discs.
  • the silver layers 12 and the antiflashover collar 14 are applied in later steps. After sintering, the disc 10 is about 0.9 inch thick and about 3 2% inches in diameter.
  • One or more of such discs may then be incorporated in a surge arrester assembly, such as for instance in a surge arrester of the type rated at 258 kilovolts.
  • the impurities are belleved to form various reaction products.
  • the precise nature and molar concentration of such products in the sintered disc is not presently fully understood. It does 10 seem likely, for instance, that the barium carbonate reacts at the sintering temperature to form barium oxide. If this does in fact occur, then it seems also likely that the molar precentage of the barium oxide is nearly the same as that of the barium carbonate, from which it was formed. For this reason, the composition of the final sintered disc is given here in terms of the composition of the powder from which it was pressed, though it is recognized that conceivably the actual composition may vary slightly therefrom in molar percentages due to this formation of the reaction products. Also, some elements with a relatively low boiling temperature, such as bismuth, may well be partly lost by evaporation in the heating process so that the final composition after sintering can have as much as bismuth in it.
  • FIG. 2 A rough indication of the degree of improved stability that can be obtained by the addition of the impurities barium oxide and boron oxide to silicon oxide containing compositions as compared to their addition to compositions that do not contain silicon dioxide is given in the FIG. 2.
  • the graph of FIG. 2 represents the percentage change in current of four different disc samples in a time interval during which they were subjected to conditions designed to approximate those under which they would operate in a surge arrester. The curves indicate only rough approximations of the actual valves of current during the time intervals.
  • the curve 16 shows generpercent less ally the stability of a first sample disc pressed from a powder containing no silicon dioxide and having the following composition:
  • the curve 18 in FIG. 2 shows generally the stability of a second disc sample made from a powder having the same composition as the sample for the curve 16, but in 60 which a corresponding portion of the zinc oxide has been replaced by 0.1 molar percent of each of the impurities barium carbonate and boron oxide. It contains about 0.1 molar percent of each of the impurities barium oxide and boron oxide after sintering.
  • This 65 second sample was tested with an initial current of 0. 12 milliampere per square centimeter under generally the same conditions as the first sample of curve 16. It can be seen from the curve 18 that the stability of the second sample was somewhat improved over the first sample, in that the current rose to a lower level during the first hours, despite the higher initial current.
  • the curve 20 of FIG. 2 shows generally the stability of a third sample disc pressed from a powder having a composition which is the same as that for the first sample, except that 0.25 molar percent of the zinc oxide has been replaced by silicon dioxide. While this composition with silicon dioxide has a higher exponent than does the composition of the first sample, the stability of the third sample composition is not nearly as good. In fact, the stability of the third sample is so poor that in order to yield meaningful data, the initial current for it could only be brought to 0.03 millampere per square contimeters. It can be seen from the curve 20 that even at this low current, the stability of the third sample was very poor, the current rapidly increasing to over percent during just the first 25 hours.
  • the curve 22 of FIG. 2 shows generally the stability of a fourth sample disc pressed from a powder having the same composition as the third sample, except that a corresponding portion of the zinc oxide has been replaced by 0.1 molar percent barium carbonate and 0.1 molar percent boron oxide.
  • the sample was tested at the same initial current of 0.12 milliampere per square centimeters, as was the second sample. It is seen from the curve 22 that the improvement in the stability for the fourth sample, as compared to the third sample, is much greater than would be expected from the improvement that resulted in the second sample when the same impurities were added to the first sample composition.
  • the reasons for the dramatic nature of the improved stability when barium carbonate and boron oxide are added to a silicon dioxide-containing zinc oxide powder for a sintered disc are not at this time fully understood.
  • the disc of the preferred embodiment has a given specific composition, it is to be understood that the individual impurity contents of the disc may be varied to degrees known to those skilled in the art without departing from the spirit of the invention.
  • the silicon dioxide may, for example, be only half of the concentration as given in the preferred embodiment.
  • composition defined in claim 1 wherein the boron oxide is present to a concentration of on the order of about 0.1 molar percent.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)
US377218A 1973-07-09 1973-07-09 Metal oxide voltage-variable resistor composition Expired - Lifetime US3928245A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US377218A US3928245A (en) 1973-07-09 1973-07-09 Metal oxide voltage-variable resistor composition
JP49075910A JPS5740642B2 (enrdf_load_stackoverflow) 1973-07-09 1974-07-04
DE2432613A DE2432613C2 (de) 1973-07-09 1974-07-06 Spannungsabhängiger Widerstand
US05/822,623 USRE29731E (en) 1973-07-09 1977-08-08 Metal oxide voltage-variable resistor composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US377218A US3928245A (en) 1973-07-09 1973-07-09 Metal oxide voltage-variable resistor composition

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US05/822,623 Reissue USRE29731E (en) 1973-07-09 1977-08-08 Metal oxide voltage-variable resistor composition

Publications (1)

Publication Number Publication Date
US3928245A true US3928245A (en) 1975-12-23

Family

ID=23488228

Family Applications (2)

Application Number Title Priority Date Filing Date
US377218A Expired - Lifetime US3928245A (en) 1973-07-09 1973-07-09 Metal oxide voltage-variable resistor composition
US05/822,623 Expired - Lifetime USRE29731E (en) 1973-07-09 1977-08-08 Metal oxide voltage-variable resistor composition

Family Applications After (1)

Application Number Title Priority Date Filing Date
US05/822,623 Expired - Lifetime USRE29731E (en) 1973-07-09 1977-08-08 Metal oxide voltage-variable resistor composition

Country Status (3)

Country Link
US (2) US3928245A (enrdf_load_stackoverflow)
JP (1) JPS5740642B2 (enrdf_load_stackoverflow)
DE (1) DE2432613C2 (enrdf_load_stackoverflow)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127511A (en) * 1976-07-01 1978-11-28 Bbc Brown, Boveri & Company, Limited Ceramic electrical resistor with nonlinear voltage characteristic
US4148135A (en) * 1978-03-10 1979-04-10 General Electric Company Method of treating metal oxide varistors to reduce power loss
US4186367A (en) * 1977-08-05 1980-01-29 Siemens Aktiengesellschaft Thick film varistor and method of producing same
US4246621A (en) * 1977-07-15 1981-01-20 Yuken Kogyo Company Limited Energizing circuit for solenoid valve
US4272411A (en) * 1979-03-08 1981-06-09 Electric Power Research Institute Metal oxide varistor and method
FR2484997A1 (fr) * 1980-06-18 1981-12-24 Gen Electric Composition a l'oxyde de zinc pour varistance
US4340921A (en) * 1978-05-17 1982-07-20 General Electric Company HVDC Power transmission system with metallic return conductor
US4371860A (en) * 1979-06-18 1983-02-01 General Electric Company Solderable varistor
US4374049A (en) * 1980-06-06 1983-02-15 General Electric Company Zinc oxide varistor composition not containing silica
US4424547A (en) 1980-11-04 1984-01-03 General Electric Company Surge suppressor construction
US4490014A (en) * 1979-05-10 1984-12-25 General Electric Company Liquid crystal display with low capacitance zinc oxide varistor
US4579702A (en) * 1982-10-07 1986-04-01 Fuji Electric Company Ltd. Zinc oxide voltage nonlinear resistors
US5616881A (en) * 1995-05-30 1997-04-01 Morton International, Inc. Inflator socket pin collar for integrated circuit initaitor with integral metal oxide varistor for electro-static discharge protections
US5932832A (en) * 1996-04-15 1999-08-03 Autoliv Asp, Inc. High pressure resistant initiator with integral metal oxide varistor for electro-static discharge protection
US6094128A (en) * 1998-08-11 2000-07-25 Maida Development Company Overload protected solid state varistors
EP2857374A1 (en) 2013-10-02 2015-04-08 Razvojni Center eNem Novi Materiali d.o.o. Method for manufacturing varistor ceramics and varistors having low leakage current
CN109053187A (zh) * 2018-10-15 2018-12-21 安徽银点电子科技有限公司 一种高电位梯度的氧化锌压敏电阻材料及其制备方法
CN112048209A (zh) * 2020-09-21 2020-12-08 广东电网有限责任公司电力科学研究院 一种填料、接地网防腐涂料及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397775A (en) 1981-06-01 1983-08-09 General Electric Company Varistors with controllable voltage versus time response
JP6756484B2 (ja) * 2016-01-20 2020-09-16 株式会社日立製作所 電圧非直線抵抗体

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1874785A (en) * 1930-06-23 1932-08-30 Grigsby Grunow Co Oxide coatings and method of preparing the same
US2933458A (en) * 1955-12-19 1960-04-19 Diamond Alkali Co Electrically conductive glass composition containing suboxides of titanium and method of making the same
US3052573A (en) * 1960-03-02 1962-09-04 Du Pont Resistor and resistor composition
US3433749A (en) * 1965-06-30 1969-03-18 Matsushita Electric Ind Co Ltd Glass electrode compositions
US3778743A (en) * 1973-02-23 1973-12-11 Matsushita Electric Ind Co Ltd Voltage-nonlinear resistors
US3805114A (en) * 1972-03-01 1974-04-16 Matsushita Electric Ind Co Ltd Voltage-nonlinear resistors

Family Cites Families (5)

* 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
JPS495557B1 (enrdf_load_stackoverflow) * 1968-11-08 1974-02-07
JPS5143192B2 (enrdf_load_stackoverflow) * 1971-08-19 1976-11-19
US3764566A (en) * 1972-03-24 1973-10-09 Matsushita Electric Ind Co Ltd Voltage nonlinear resistors
JPS5016763Y2 (enrdf_load_stackoverflow) * 1972-12-08 1975-05-24

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1874785A (en) * 1930-06-23 1932-08-30 Grigsby Grunow Co Oxide coatings and method of preparing the same
US2933458A (en) * 1955-12-19 1960-04-19 Diamond Alkali Co Electrically conductive glass composition containing suboxides of titanium and method of making the same
US3052573A (en) * 1960-03-02 1962-09-04 Du Pont Resistor and resistor composition
US3433749A (en) * 1965-06-30 1969-03-18 Matsushita Electric Ind Co Ltd Glass electrode compositions
US3805114A (en) * 1972-03-01 1974-04-16 Matsushita Electric Ind Co Ltd Voltage-nonlinear resistors
US3778743A (en) * 1973-02-23 1973-12-11 Matsushita Electric Ind Co Ltd Voltage-nonlinear resistors

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127511A (en) * 1976-07-01 1978-11-28 Bbc Brown, Boveri & Company, Limited Ceramic electrical resistor with nonlinear voltage characteristic
US4246621A (en) * 1977-07-15 1981-01-20 Yuken Kogyo Company Limited Energizing circuit for solenoid valve
US4186367A (en) * 1977-08-05 1980-01-29 Siemens Aktiengesellschaft Thick film varistor and method of producing same
US4148135A (en) * 1978-03-10 1979-04-10 General Electric Company Method of treating metal oxide varistors to reduce power loss
FR2419572A1 (fr) * 1978-03-10 1979-10-05 Gen Electric Procede pour reduire la perte de puissance de varistors en oxyde metallique
US4340921A (en) * 1978-05-17 1982-07-20 General Electric Company HVDC Power transmission system with metallic return conductor
US4272411A (en) * 1979-03-08 1981-06-09 Electric Power Research Institute Metal oxide varistor and method
US4490014A (en) * 1979-05-10 1984-12-25 General Electric Company Liquid crystal display with low capacitance zinc oxide varistor
US4371860A (en) * 1979-06-18 1983-02-01 General Electric Company Solderable varistor
US4374049A (en) * 1980-06-06 1983-02-15 General Electric Company Zinc oxide varistor composition not containing silica
FR2484997A1 (fr) * 1980-06-18 1981-12-24 Gen Electric Composition a l'oxyde de zinc pour varistance
US4424547A (en) 1980-11-04 1984-01-03 General Electric Company Surge suppressor construction
US4579702A (en) * 1982-10-07 1986-04-01 Fuji Electric Company Ltd. Zinc oxide voltage nonlinear resistors
US5616881A (en) * 1995-05-30 1997-04-01 Morton International, Inc. Inflator socket pin collar for integrated circuit initaitor with integral metal oxide varistor for electro-static discharge protections
US5932832A (en) * 1996-04-15 1999-08-03 Autoliv Asp, Inc. High pressure resistant initiator with integral metal oxide varistor for electro-static discharge protection
US6094128A (en) * 1998-08-11 2000-07-25 Maida Development Company Overload protected solid state varistors
EP2857374A1 (en) 2013-10-02 2015-04-08 Razvojni Center eNem Novi Materiali d.o.o. Method for manufacturing varistor ceramics and varistors having low leakage current
CN109053187A (zh) * 2018-10-15 2018-12-21 安徽银点电子科技有限公司 一种高电位梯度的氧化锌压敏电阻材料及其制备方法
CN112048209A (zh) * 2020-09-21 2020-12-08 广东电网有限责任公司电力科学研究院 一种填料、接地网防腐涂料及其制备方法

Also Published As

Publication number Publication date
JPS5740642B2 (enrdf_load_stackoverflow) 1982-08-28
DE2432613C2 (de) 1985-01-24
DE2432613A1 (de) 1975-01-30
JPS5033493A (enrdf_load_stackoverflow) 1975-03-31
USRE29731E (en) 1978-08-15

Similar Documents

Publication Publication Date Title
US3928245A (en) Metal oxide voltage-variable resistor composition
EP1150306B1 (en) Current/voltage non-linear resistor and sintered body therefor
US3959543A (en) Non-linear resistance surge arrester disc collar and glass composition thereof
CA1279113C (en) Voltage non-linear resistor and its manufacture
EP0029749B1 (en) Voltage dependent resistor and method of making same
US4450426A (en) Nonlinear resistor and process for producing the same
US4272411A (en) Metal oxide varistor and method
EP0581969A1 (en) Zinc oxide varistor and production thereof
EP0316015A2 (en) Material for resistor body and non-linear resistor made thereof
US4460497A (en) Voltage stable nonlinear resistor containing minor amounts of aluminum and selected alkali metal additives
EP0497566B1 (en) Voltage non-linear resistor
US5614138A (en) Method of fabricating non-linear resistor
CA1100749A (en) Pre-glassing method of producing homogeneous sintered zno non-linear resistors
EP0473419B1 (en) Voltage non-linear resistor and method of producing the same
CA1276731C (en) Voltage non-linear resistor
US4452729A (en) Voltage stable nonlinear resistor containing minor amounts of aluminum and boron
US5039971A (en) Voltage non-linear type resistors
EP0320196B1 (en) Voltage non-linear type resistors
CA1061472A (en) Voltage-dependent resistor
US4420737A (en) Potentially non-linear resistor and process for producing the same
US4452728A (en) Voltage stable nonlinear resistor containing minor amounts of aluminum, boron and selected alkali metal additives
US3925261A (en) Exponential resistance material and method of manufacturing same
JPS606522B2 (ja) 半導体組成物
JPS644651B2 (enrdf_load_stackoverflow)
US5142264A (en) High energy absorbing varistor