US3232886A - Resistor compositions - Google Patents

Resistor compositions Download PDF

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Publication number
US3232886A
US3232886A US224915A US22491562A US3232886A US 3232886 A US3232886 A US 3232886A US 224915 A US224915 A US 224915A US 22491562 A US22491562 A US 22491562A US 3232886 A US3232886 A US 3232886A
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United States
Prior art keywords
noise
resistor
silver
palladium
weight
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
US224915A
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English (en)
Inventor
Hoffman Lewis Charles
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and 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
Priority to NL298178D priority Critical patent/NL298178A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US224915A priority patent/US3232886A/en
Priority to DE19631496620D priority patent/DE1496620B1/de
Priority to FR948067A priority patent/FR1370295A/fr
Priority to GB36943/63A priority patent/GB982789A/en
Application granted granted Critical
Publication of US3232886A publication Critical patent/US3232886A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06526—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H01C17/0654—Oxides of the platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06553—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of a combination of metals and oxides
    • 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

Definitions

  • This invention relates to resistor compositions; and more particularly, it relates to conductive glass frit-precious metal resistor compositions suitable for production of electrical resistors having an improved low current norse.
  • Precious metal resistor compositions containing a glass frit binder which may be applied and fired on a ceramic base to produce an electrical resistor have been known for some years. Such compositions are described in US. Patent Nos. 2,924,540, 3,052,257 and 2,950,995 and have been used commercially to some extent. Such previously known resistor compositions were not entirely satisfactory because resistors produced therefrom had an undesirably high noise character.
  • the objects may be accomplished by mixing 20 to 49 percent by weight of finely divided glass frit with 80 to 51 percent of finely divided low oxide content palladium and silver in which the ration of palladium to silver is between 55:45 to 45:55.
  • FIG. 1 is a ternary diagram of the palladium-silverfrit ternary mixtures showing in area ABCD the essential ternary mixtures to produce the resistor compositions of this invention
  • FIG. 2 is a noise rating conversion diagram showing the straight-line relationship between noise voltage in microvolts per decade and noise index in decibles per decade.
  • Noise is measured by comparing the output from the resistor under D.C. load with the output of a signal gen-.- erator over a decade of frequency.
  • the Bureau of Standards has developed a special circuit which is incorporated in the resistor noise test set model 315 manufactured by Quan-Tech Laboratories, Inc., Boonton, NJ.
  • Noise is expressed by the ratio of the root means square noise voltage in microvolts to the applied DC. voltage in volts expressed in decibels, when the associated pass band is one frequency decade. Noise in microvolts 3,232,886 Patented Feb. 1, 1966 iCe per volt and decibels per decade are easily interconverted, as shown in FIG. 2 of the drawings; but in this memorandum all noise figures will be in decibels per decade.
  • the area ABCD of the diagram discloses the area of lowest noise in the system glass frit-palladium-silver.
  • the resistance, in ohms per square per mil thickness of resistance coating, and the current noise in decibles per dcade are given for 21 points in the ABCD area.
  • Another requirement for low noise resistors is to start with palladium containing less than about 1% combined oxygen.
  • Pd powder when heated will at first oxidize, oxidation beginning at about 350 to 400 C.; and upon further heating to a higher temperature, 650 to 750 C., some of the formed PdO will decompose with oxygen evolution.
  • the Pd in the resistor composition contains too much 0 i.e., more than about 1%, the firing of the composition to fuse the glass frit binder will not remove sutficient 0 from the Pd to produce a resistor composition that will have a sufficiently low noise index.
  • the content of combined 0 in the PdPdO should be less than about 1% by weight.
  • PdO in the Pd is, however, essential. If oxygen-free Pd is used in the composition and the composition is fired in an oxygen-free atmosphere, e.g. argon, the fired resistor will not have reproducible resistance values and will have objectionable high positive temperature coefiicients of resistance.
  • the Pd should therefore contain an essential minimum of combined oxygen of about 0.1%.
  • the Pd should be finely divided to between about 0.5 to 50 microns in diameter and may be obtained from any source of production that will produce a Pd containing not to exceed 1% of combined oxygen.
  • a very desirable source of Pd is that produced by the reaction of hydrizine sulfate with PdCl in the presence of less than 12 cc. of concentrated aqueous ammonia per gram of palladium.
  • the silver powder used in the low noise resistors of this invention may be produced by chemical precipitation or by mechanical means as long as the particle size is of the order of 0.1 to 50 microns in diameter. There is nobeneficialetrect to be gained by after treatment nor deleterious effect as a result of oxidation. Any silver oxide present will decompose at such low temperature that it is substantially absent at the firing temperature of the glazed resistor.
  • the composition of the glass frit is not critical. Borosilicate glasses such as lead borosilicate, cadmium borosilicate and similar glasses are suitable for the production of the low noise resistors of this invention. If, however, it is desirable to produce low drift and low TCR (temperature coefficient of resistance) resistors, then it would be advisable to use the Na O-ZnO-Al O B O -SiO -ZrO frits disclosed and claimed in my copending application Serial No. 225,121, filed of even date herewith.
  • the finely divided dry mixture may be made into a paste or liquid by the addition of a vehicle in a known manner. Fifteen percent to sixty percent by weight of an inert liquid, for example, water, methyl, ethyl, propyl,
  • butyl orhigher alcohols such as acetates, p'ropionates, the terpenes and liquid resins such as pine oil or alpha or beta terpineol and the like may be used to prepare a suitable consistency for application purposes.
  • the vehicles may contain or be composed of volatile liquids to promote fast setting after application, or they may contain waxes, thermoplastic resins, or wax-like materials which are thermofluid by nature whereby the composition may be applied to a ceramic insulator while at elevated temperature to set upon contact with a cold ceramic base.
  • a inch x 1 inch x inch alumina plate was first provided with spaced dried silver terminals.
  • the squeegee resistor composition was stencilled over the terminations so as to provide an area of overlap and an area of film having a thickness of about 1 mil in direct contact with the alumina.
  • the plate was then fired at a temperature of 760 C. for 12 minutes. Wires were soldered to the silver terminal overlap.
  • This resistor when tested in the resistor noise test set model 315 manufactured by Quan-Tech Laboratories, Inc. of Boonton, N.J., had a noise index of 30.6 decibels per decade.
  • a resistor composition consisting essentially of to 49 percent by weight of finely divided glass frit and 51 to 80 percent of finely divided palladium and silver in the weight ratio of palladium to silver of 55:45 to :55, said palladium containing between 0.1% and 1% of combined oxygen and consisting of particles of from 0.5 to microns in diameter, and said silver consisting of particles of from 0.1 to 50 microns in diameter.
  • a resistor composition as defined in claim 1 containing between 15 and by weight of the composition of a liquid inert vehicle.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Non-Adjustable Resistors (AREA)
  • Conductive Materials (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
  • Glass Compositions (AREA)
US224915A 1962-09-20 1962-09-20 Resistor compositions Expired - Lifetime US3232886A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL298178D NL298178A (enrdf_load_html_response) 1962-09-20
US224915A US3232886A (en) 1962-09-20 1962-09-20 Resistor compositions
DE19631496620D DE1496620B1 (de) 1962-09-20 1963-09-17 Metallteilchen enthaltende Glasurmasse,insbesondere zur Verwendung fuer elektrische Widerstaende
FR948067A FR1370295A (fr) 1962-09-20 1963-09-19 Composition de résistance électrique
GB36943/63A GB982789A (en) 1962-09-20 1963-09-19 Improvements in and relating to resistor compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US224915A US3232886A (en) 1962-09-20 1962-09-20 Resistor compositions

Publications (1)

Publication Number Publication Date
US3232886A true US3232886A (en) 1966-02-01

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US224915A Expired - Lifetime US3232886A (en) 1962-09-20 1962-09-20 Resistor compositions

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US (1) US3232886A (enrdf_load_html_response)
DE (1) DE1496620B1 (enrdf_load_html_response)
GB (1) GB982789A (enrdf_load_html_response)
NL (1) NL298178A (enrdf_load_html_response)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312922A (en) * 1964-06-19 1967-04-04 Minnesota Mining & Mfg Solid state switching device
US3413240A (en) * 1965-03-25 1968-11-26 Du Pont Compositions
US3428476A (en) * 1965-06-22 1969-02-18 Engelhard Min & Chem Method for producing hydrogen diffusion cells
US3434877A (en) * 1965-07-16 1969-03-25 Rca Corp Metallic connection and the method of making same
US3872360A (en) * 1973-01-08 1975-03-18 Du Pont Capacitors with nickel containing electrodes
US5221644A (en) * 1991-12-13 1993-06-22 Delco Electronics Corporation Thick film sense resistor composition and method of using the same
US5345212A (en) * 1993-07-07 1994-09-06 National Starch And Chemical Investment Holding Corporation Power surge resistor with palladium and silver composition
US5366813A (en) * 1991-12-13 1994-11-22 Delco Electronics Corp. Temperature coefficient of resistance controlling films
US9142229B2 (en) 2013-03-15 2015-09-22 Seagate Technology Llc Heat assisted magnetic recording head having thermal sensor with high-TCR transparent conducting oxide
US9978412B1 (en) 2015-11-06 2018-05-22 Seagate Technology Llc Transparent thermocouple for heat-assisted magnetic recording device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2924540A (en) * 1958-05-23 1960-02-09 Du Pont Ceramic composition and article
US3052573A (en) * 1960-03-02 1962-09-04 Du Pont Resistor and resistor composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1132220B (de) * 1959-10-28 1962-06-28 Du Pont Metallteilchen enthaltende Glasurmasse zur Herstellung elektrischer Widerstaende undelektrischer Widerstand

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2924540A (en) * 1958-05-23 1960-02-09 Du Pont Ceramic composition and article
US3052573A (en) * 1960-03-02 1962-09-04 Du Pont Resistor and resistor composition

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312922A (en) * 1964-06-19 1967-04-04 Minnesota Mining & Mfg Solid state switching device
US3413240A (en) * 1965-03-25 1968-11-26 Du Pont Compositions
US3428476A (en) * 1965-06-22 1969-02-18 Engelhard Min & Chem Method for producing hydrogen diffusion cells
US3434877A (en) * 1965-07-16 1969-03-25 Rca Corp Metallic connection and the method of making same
US3872360A (en) * 1973-01-08 1975-03-18 Du Pont Capacitors with nickel containing electrodes
US5221644A (en) * 1991-12-13 1993-06-22 Delco Electronics Corporation Thick film sense resistor composition and method of using the same
US5341119A (en) * 1991-12-13 1994-08-23 Delco Electronics Corporation Measurement circuit utilizing a low TCR thick film sense resistor
US5366813A (en) * 1991-12-13 1994-11-22 Delco Electronics Corp. Temperature coefficient of resistance controlling films
US5345212A (en) * 1993-07-07 1994-09-06 National Starch And Chemical Investment Holding Corporation Power surge resistor with palladium and silver composition
US5464564A (en) * 1993-07-07 1995-11-07 National Starch And Chemical Investment Holding Corporation Power surge resistor pastes containing tungsten dopant
US9142229B2 (en) 2013-03-15 2015-09-22 Seagate Technology Llc Heat assisted magnetic recording head having thermal sensor with high-TCR transparent conducting oxide
US9978412B1 (en) 2015-11-06 2018-05-22 Seagate Technology Llc Transparent thermocouple for heat-assisted magnetic recording device

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Publication number Publication date
DE1496620B1 (de) 1970-03-12
NL298178A (enrdf_load_html_response)
GB982789A (en) 1965-02-10

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