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Publication numberUS3916366 A
Publication typeGrant
Publication dateOct 28, 1975
Filing dateOct 25, 1974
Priority dateOct 25, 1974
Publication numberUS 3916366 A, US 3916366A, US-A-3916366, US3916366 A, US3916366A
InventorsJefferson Clinton F
Original AssigneeDale Electronics
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Thick film varistor and method of making the same
US 3916366 A
Abstract
A thick film varistor comprising a substrate material having a varistor film or material printed thereon. Terminal conductors are electrically connected to the varistor film to terminate the varistor. The varistor material is comprised of a reacted material consisting of nickel oxide and lithium carbonate. The varistor material may also comprise glass frit material, solvent material and binder materials mixed with the reacted material. If desired, electrically conductive metal powders may be incorporated in the varistor material to vary the resistivity of the varistor material. The method of making varistor is also disclosed.
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Description  (OCR text may contain errors)

United States Patent Jefferson 5] Oct. 28, 1975 THICK FILM VARISTOR AND METHOD OF 3,689,863 9/1972 Matsuoka a a1. 338/20 MAKING THE SAME 3,760,318 9/1973 Masuyama et a1 338/20 Inventor: Clinton F. Jefferson, Norfolk, Nebr.

Dale Electronics, Inc., Columbus, Nebr.

Filed: Oct. 25, 1974 Appl. No.: 517,880

Assignee:

US. Cl. 338/21; 29/610; 252/516; 252/519; 338/306; 338/307;

Int. Cl. H01C 7/12 Field of Search 338/20, 21, 306-309, 338/325, 328; 252/516, 519; 29/610 References Cited UNITED STATES PATENTS 4/1965 Murphy et a1. 252/516 X 2/1969 Garfinkel et aL... 8/1972 Matsuoka et a1. 252/518 Primary Examiner-C. L. Albritton Attorney, Agent, or Firm-Zarley, McKee, Thomte & Voorhees [57] ABSTRACT A thick film varistor comprising a substrate material having a varistor film or material printed thereon. Terminal conductors are electrically connected to the varistor film to terminate the varistor. The varistor material is comprised of a reacted material consisting of nickel oxide and lithium carbonate. The varistor material may also comprise glass frit material, solvent material and binder materials mixed with the reacted material. If desired, electrically conductive metal powders may be incorporated in the varistor material to vary the resistivity of the varistor material. The method of making varistor is also disclosed.

10 Claims, 4 Drawing Figures U.S. Patent Oct. 28, 1975 THICK FILM VARISTOR AND METHOD OF MAKING THE SAME BACKGROUNDOF THE INVENTION This invention relates to a thick film varistor and more particularly to a thick film varistor having the varistor film or material printed on a substrate material wherein the film is comprised of a reacted material consisting of nickel oxide and lithium carbonate.

The 'art of making thick film resistors is well known and is described in the prior art. This invention relates to an improved process and the formulations thereof for the preparation of thick film symmetrical nonohmic resistors, known to'the industry as symmetrical varistors.

Therefore, is a principal object of the invention to provide an improved thick film varistor.

A further object of the invention is to provide a method of producing a thick film varistor having improved operating characteristics.

. A further object of the invention is to provide an economical method of producing a thick film varistor.

. A further object of the invention is to provide a thick film varistor wherein the varistor characteristics may be modified by the incorporation of a metal powder so as to modify the resistivity thereof.

These and other objects will be apparent to those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS This invention consists in the construction, arrangements and combination of the various parts of the device, whereby the objects contemplated are attained as hereinafter more fully set forth, specifically pointed out in the claims, and illustrated in the accompanying drawings, in which:

FIG. 1 is a perspective view of a varistor produced by the method of this invention:

FIG. 2 is a perspective view of a modified form of the varistor:

FIG. 3 is a perspective view of a still further modified form of the varistor; and

FIG. 4 is a sectional view as seen along lines 4 4 of FIG. 2.

DESCRIPTION OF THE PREFERRED EMBODIMENT In FIG. 1, the numeral refers to one form of the varistor while the numerals 12 and 14 refer to other forms of the varistors in FIGS. 2 and 3 respectively. Varistor 10 comprises a pair of terminal conductors and 22 having the varistor material 18 sandwiched therebetween. Conductors 20 and 22 and material 18 are positioned on a ceramic substrate body or material 16.

Varistor 12 comprises electrical conductors 26 and 28 having the varistor material 19 electrically connected thereto and extending therebetween. Conductors 26,28 and material 19 are positioned on the ceramic substrate body or material 24.

With respect to FIG. 3, the numerals 30 refer to terminal conductors which are electrically connected by the varistor material. Conductors 30 and varistor material 32 are positioned on substrate body or material 34.

The varistor is prepared by the following process. Conductive nickel oxide powder is prepared by ball milling nickel oxide powder with lithium carbonate powder in an acetone solution to obtain a homogeneous mixture which is then dried. The dried powders are then reacted at elevated temperatures between 1050-l 200C to obtain a conductive nickel oxide. The amount of lithium carbonate in the mixture influences the conductivity of the resultant oxide powders, and percentages of l to 6 percent of lithium carbonate by weight have been found to be preferred. The reacted material nickel oxide and lithium carbonate is then ball milled in acetone until a desired particle size is obtained. The powders are then dried and screened through a 325 mesh sieve.

The nickel oxide-lithium carbonate mixture is then formulated into a thick film paste using procedures well known to those skilled in the art of formulating thick film resistor materials. Glass frit in the lead borosilicate system may be used if desired, as can other glass systems, with the choice of the glass system depending on the subsequent firing temperatures at which the thick film varistor is to 'be fired- Solvents and thixotropic binders may be used, such as butyl carbitol acetate, and ethyl cellulose, but the solvents and binders may be se lected from other materials.

The resistivity of the material may be modified by the addition of conductive metal powder such as silver powder or nickel powder. The conductive metal powders control the value of k in the formula I kV" where I I= Current in amperes, k constant, V Voltage and N an exponent. The metal powders may be used in various amounts depending upon the value of k required. Silver powders are found to be the most effective in controlling the low-current valueof the resistivity and weight ratios of Ni -xLi ozAg of :0.0' to 50:50 have been found to produce excellent thick film varistor pastes.

The thick film varistor paste prepared according to the method described above is then printed on the substrate bodies 16, 24 or 34 (and conductors) in FIGS. 1, 2 and 3 respectively (such as Al O in a manner familiar to the thick film industry. It should be understood that other suitable substrate materials known to the industry may also be used. The terminal conductors illustrated in FIGS. 1, 2 and 3 are used to terminate the varistor and may be comprised of such materials as Pt- Au, Pd-Au, Pd-Ag or Pt-Ag. It has been found that silver bearing conductors result in the best terminations and are the preferred embodiment. The thick film varistors are then dried and fired at temperatures of 600 to 950C peak temperatures. The total furnace profile may vary from 20 minutes to 1 hour depending on the peak furnace temperature and the composition of the glass frit selected in the formulation.

The pattern used to print the thick film varistor may be varied and any conventional pattern currently used to print thick film varistors may be used. The selection of the pattern is based on the desired varistor characteristics. It has been found that for high current, low voltage applications, the pattern or embodiment shown in FIG. 1 is preferred while the design illustrated in FIG. 2 is preferred for low current applications. The parallel combination of varistors shown in FIG. 3 may be used when the current voltage characteristics of the parallel varistors are closely matched.

Depending on the configuration used for the varistor pattern, different varistor formulations are found to be desirable. The varistor configuration of FIG. 1 requires less conductive varistor paste than do the configurations of FIGS. 2 and 3. varistor formulations which have been found to be useful for the different varistor designs are shown in Table 1 below.

Table l Compositions, For design For, design of Ingredients FIG. I FIGS. 2 and 3 Ni, ,Li 0,powder 34.12 17.06 Ag or Ni powders v 17.06 Glass Frit 22.75 22.75 Ethyl-Cellulose 7.84 7.84 Butyl Carbitol 35.29 35.29 Acetate Thus it can be seen that a method has been provided for making'athick film varistor having improved operqsating characteristics. Thus it can be seen that the varistor and method ofvmaking the same accomplishes all of 'its stated objectives.

.-.- I said varistor material being comprised of a reacted material Consisting of nickel oxide and lithium carbonate. I 2. The-varistor of claim 1 wherein said lithium carbonate comprises 1 to 6 percent by weight of the said material. 1

reacted material and .wherein said nickel oxide comprises 94 to 99 percent by weight of the reacted material.

3. The varistor of claim 1 wherein said varistor material also comprisesa glass frit material mixed with said reacted material.

4. The varistor of claim 3 wherein said varister material also comprises solvent and binder materials mixed with said glass frit material and said reacted material.

5. The varistor of claim 3 wherein said varistor material also comprises electrically conductive metal powders mixed with said glass frit material and said reacted 6. The varistor of claim is silver powder. I

7. The varistor ofv claim 5 wherein said metal powder is nickel powder. i

8. The varistor of claim 4 wherein said solvent material is butyl carbitol acetate and wherein said binder material is ethyl cellulose.

9. The varistor of claim 1 wherein said varistor mate- 5 wherein said metal powder rial approximately comprises 17.06 percent by weight. I

nickel oxide-lithium carbonate; 17.06 percent by weight nickel powder; 22.75 percent by weight glass frit; 7.84 percent'by weight ethyl cellulose; and 35.29 percent by weight butyl carbitol acetate.

10. The varistor of claim 1 wherein said varistor material approximately comprises 34.12 percent by weight nickel oxide-lithium carbonate; 22.75 percent by weight glass frit; 7.84 percent by weight ethyl cellulose; and 35.29 percent by weight butyl carbitol acetate.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3180841 *Aug 28, 1962Apr 27, 1965Int Resistance CoResistance material and resistor made therefrom
US3429831 *Jan 18, 1965Feb 25, 1969Gen ElectricLithiated nickel oxide crystals
US3682841 *Dec 1, 1970Aug 8, 1972Matsushita Electric Ind Co LtdVoltage dependent resistors in a bulk type
US3689863 *Nov 24, 1970Sep 5, 1972Matsushita Electric Ind Co LtdVoltage dependent resistors in a surface barrier type
US3760318 *Aug 24, 1972Sep 18, 1973Matsushita Electric Ind Co LtdProcess for making a voltage dependent resistor
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4097834 *Apr 12, 1976Jun 27, 1978Motorola, Inc.Non-linear resistors
US4460624 *Aug 31, 1982Jul 17, 1984Thomson-CsfProcess for the manufacture of thick layer varistors on a hybrid circuit substrate
US4559579 *May 10, 1983Dec 17, 1985Thomson CsfDevice for the protection of an electronic component and/or circuit against the disturbances (voltages) generated by an external electromagnetic field
US4584553 *Jun 5, 1984Apr 22, 1986Nippon Soken, Inc.Coated layer type resistor device
US4657699 *Dec 17, 1984Apr 14, 1987E. I. Du Pont De Nemours And CompanyThick films of semiconductive materials and glass in an organic medium
US4660017 *Feb 12, 1986Apr 21, 1987Marcon Electronics Co., Ltd.Chip-type varistor
US4888465 *Jun 16, 1988Dec 19, 1989Robert Krups Stiftung & Co. Kg.Hot beverage machine with thick film electric heater
US4959090 *Jul 25, 1989Sep 25, 1990Ciba-Geigy CorporationGlass enamel coating compositions
US5334412 *Dec 23, 1991Aug 2, 1994Ferro CorporationEnamel for use on glass and a method of using the same
US5837178 *Jun 18, 1993Nov 17, 1998Ecco LimitedMultilayer, screen printing
US5973588 *Feb 6, 1995Oct 26, 1999Ecco LimitedMultilayer varistor with pin receiving apertures
US6008719 *Oct 3, 1997Dec 28, 1999Thomson-CsfElectrical control device with crosstalk correction, and application thereof to magnetic write/read heads
US6183685Jun 6, 1995Feb 6, 2001Littlefuse Inc.Varistor manufacturing method
US6334964Jul 14, 1999Jan 1, 2002Littelfuse, Inc.Varistor ink formulations
US6549114 *Aug 19, 1999Apr 15, 2003Littelfuse, Inc.Protection of electrical devices with voltage variable materials
US6743381Sep 4, 2001Jun 1, 2004Littlefuse, Inc.Thixotropic ink for use in manufacturing a multilayer varistor using a screen printing
US6856233 *Mar 11, 2002Feb 15, 2005Rohm Co., Ltd.Chip resistor
US7034652Jul 10, 2002Apr 25, 2006Littlefuse, Inc.Electrostatic discharge multifunction resistor
US7035072Jul 10, 2002Apr 25, 2006Littlefuse, Inc.Electrostatic discharge apparatus for network devices
US7189297 *Dec 6, 2004Mar 13, 2007Matsushita Electric Industrial Co., Ltd.Electro Static Discharge (ESD); making a slurry of varistor particles and a resin binder, and forming a varistor green sheet from this slurry; high-performance and uniformity
US7570149Aug 31, 2005Aug 4, 2009Fujitsu LimitedElectronic circuit device including electric element and varistor on substrate and its manufacture method
EP0115638A2 *Dec 28, 1983Aug 15, 1984Hitachi, Ltd.Thick film circuit board
EP2337070A1 *Dec 17, 2009Jun 22, 2011ABB Technology AGElectronic device with non-linear resistive field grading and method for its manufacturing
WO1983001153A1 *Aug 13, 1982Mar 31, 1983Interfaces 15Integrated protection device against overvoltages in an electronic circuit and electronic circuit protected by such device
WO1983004157A1 *May 10, 1983Nov 24, 1983Inf Milit Spatiale AeronautDevice for the protection of an electronic device against voltages generated by an electromagnetic field
WO1989003862A1 *Oct 18, 1988May 5, 1989Ray AndrewsGlass enamel
WO2011080093A1 *Dec 16, 2010Jul 7, 2011Abb Technology AgPower electronic module with non-linear resistive field grading and method for its manufacturing
Classifications
U.S. Classification338/21, 338/325, 252/519.32, 338/328, 252/516, 338/307, 252/521.2, 338/306, 29/610.1
International ClassificationH01C17/06, H01C7/105, H01C17/065, H01C7/108
Cooperative ClassificationH01C7/108, H01C17/06533
European ClassificationH01C17/065B2F, H01C7/108
Legal Events
DateCodeEventDescription
Feb 7, 1992ASAssignment
Owner name: MANUFACTURERS BANK, N.A.
Free format text: SECURITY INTEREST;ASSIGNOR:DALE ELECTRONICS, INC.;REEL/FRAME:006080/0038
Effective date: 19920110
Feb 7, 1992AS06Security interest
Owner name: DALE ELECTRONICS, INC.
Owner name: MANUFACTURERS BANK, N.A. F/K/A MANUFACTURERS NATIO
Effective date: 19920110
Feb 13, 1986ASAssignment
Owner name: MANUFACTURERS BANK OF DETROIT, A NATIONAL BANKING
Free format text: SECURITY INTEREST;ASSIGNOR:DALE ELECTRONICS, INC., A CORP. OF DE.;REEL/FRAME:004510/0078
Effective date: 19851031
Owner name: NATIONAL ASSOCIATION, BANK HAPOALIM, B.M. AND BAN