US3899449A - Low temperature coefficient of resistivity cermet resistors - Google Patents

Low temperature coefficient of resistivity cermet resistors Download PDF

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Publication number
US3899449A
US3899449A US359244A US35924473A US3899449A US 3899449 A US3899449 A US 3899449A US 359244 A US359244 A US 359244A US 35924473 A US35924473 A US 35924473A US 3899449 A US3899449 A US 3899449A
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United States
Prior art keywords
weight percent
range
present
composition
oxide
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Expired - Lifetime
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US359244A
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English (en)
Inventor
Clifford Joseph Pukaite
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Globe Union Inc
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Globe Union Inc
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Publication date
Application filed by Globe Union Inc filed Critical Globe Union Inc
Priority to US359244A priority Critical patent/US3899449A/en
Priority to CA197,202A priority patent/CA1037705A/en
Priority to AU67890/74A priority patent/AU479484B2/en
Priority to IN890/CAL/74A priority patent/IN142722B/en
Priority to GB1706474A priority patent/GB1459327A/en
Priority to DE2421861A priority patent/DE2421861C2/de
Priority to BR3843/74A priority patent/BR7403843D0/pt
Priority to FR7416228A priority patent/FR2229122B1/fr
Priority to CH644674A priority patent/CH620544A5/de
Priority to IT22551/74A priority patent/IT1012245B/it
Priority to AR253700A priority patent/AR202024A1/es
Priority to JP49052127A priority patent/JPS6037601B2/ja
Priority to ES426228A priority patent/ES426228A1/es
Priority to US05/565,870 priority patent/US4006278A/en
Application granted granted Critical
Publication of US3899449A publication Critical patent/US3899449A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • 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
    • H01C7/06—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 including means to minimise changes in resistance with changes in temperature

Definitions

  • vanadium oxide is used in conjunction with noble metal metallizing compositions in relatively small amounts to prevent agglomeration of the metal particles and to improve the solderability, conductivity and/or adhesion properties of the metallizing materials.
  • the same indication of improvement in solderability for these compositions by adding vanadium pentoxide is also indicated in US. Pat. No. 3,440,182.
  • vanadium pentoxide is uti lized to control TCR in a resistor composition of the bismuth ruthenate type which utilizes a glass frit binder consisting of 80% lead oxide, 10 si1icon oxide and 10% boron oxide.
  • 'Aglass was prepared from the teachings of this particular patentand combined with a conductive phase used to fabricate the-resistors of this invention composedfi'of.
  • ruthenium dioxide; vanadium pentoxide, and aluminum trioxide as set forth in Example l 1. It had a sheet resistiyity of .5.49K ohm/sq./mil.
  • This glass material was combined with a conductive material composed of ruthenium dioxide in an amount of 5.34 w eight percent preparedfrom ruthenium resinate containing 5.26 weight pereentruthenium dioxide, iridium dioxide in an amount of 7v.2 weight percent pre pared from iridium resinate containing 6.99 weight percent iridium dioxide, 2.95 weightpercent bismuth trioxide, 4.18 weight percentvanadiurn pentoxide and the previously described glass in the; ,amount .of 80.41 weight percent.
  • the resistivelmaterial prepared had a sheet resistivityof 24,000 ohms/sqjmil.
  • the cermet resistor composition of this invention can be prepared either by utilizing the ruthenium and iridfium dioxides in a resinate form for ultimate conversion to the dioxidefor can be prepared by utilizing the ruthenium and/or iridium dioxides themselves as starting materials.
  • a description of'the cermet resistor composition' as prepared from the resinates of ruthenium and iridium will first be" given.
  • the particular resinates of ruthenium and iridium employed in the Examples of Table III andin" Examples 20, 21 and 22 are designated A-l 124 arid A-l 123, respectively, by the supplier, Engelhard Industries, Inc., 'I-lanovia Liquid Gold Division of East Newark; N. J. They are resinate solutions containing4l0% ruthenium or'5.26% ruthenium dioxide and 6.0% iridium or 6.99% iridium dioxide, respectively.
  • the range of starting materials for the resinateprepared compositions and for the glass are described in the following Tables I and II.
  • the vehicle may consist of any number of high boiling point organic liquids such as l-ethyl-2-hexanol which, in combination with the resistive powder, have a viscosity suitable for screen printing, dipping, or painting onto a substrate.
  • Example 20 illustrates the utilization of vanadium pentoxide predissolved in the glass desig- 5 nated FB-l99N to the extent of 6.48% b wei ht. 2.
  • MIX constituents together 1n a ball mill with acey g tone to form a slurry and ball mill with a grinding me- Example 20 dium alumina for 0.1 to 8.0 hours.
  • Type A* Type P" 1:0 wt. '7 v. ,o wt. /1 2.83 2.77 3.15 1.90 1.90 1.50 1.73 1.73 A1 O wt. 0.75 1.41 6.90 7.00 a.
  • Glass FB-199N *** wt. /1 90.73 90.26 85.22 94.1 86.50 i94.75 92.49 92.49 Average Sheer v Resistivity**** 6180 8600 27,900 53,200 1 12,900 449,100 400,000 30,000
  • This material is processed in the same method as indicated for the oxide starting materials under the head- 60 ing Oxide Method.”
  • vanadium oxide can be introduced through a vanadiuni'resirrate precursor material. Examples 21 and 22 following illustrate these.
  • Example 21 Ingredients 7( By Weight Oxide Ruthenium Resinate 10.48 (5.26% RuO Iridium Resinate 13.93 (6.99% lrO. V 0 4.84 Bi Q, 3.02 Glass FB- 199N (As indicated in Tables Ill and V) 67.72
  • Example 22 indicates utilization of vanadium oxide introduced as vanadium resinate.
  • Example 22 Results: Sheet Resistivity: 280 ohmslsqjmil. TCR ppm/"C:
  • the important conditions for achieving the low temperature coefficient of resistivity are the utilization of vanadium oxide with ruthenium dioxide, which preferably can also include iridium dioxide, in the designated amount with a particular glass composition.
  • the vanadium oxide as well as the ruthenium and iridium dioxides can be utilized as oxides or derived from resinate precursors. While vanadium pentoxide is the preferred oxide of vanadium, other oxides such as vanadium trioxide or those oxides resulting from the pyrolysis of vanadium resinate can likewise be employed to advantage.
  • cermet resistor composition having a low temperature coefficient of resistivity which can be effected at the extremes and generally less than 20 ppm/C, maintained over a broad temperature range.
  • the vanadium oxide can be utilized in various stages of oxidation and in the form of theresinate as can the ruthenium and the iridium dioxides.
  • the materials are easily processed into resistive paints. No additional capital investment need be incurred to substitute the cermet resistor compositions of this invention for more conventional compositions, and they can be easily fabricated into thick film resistors without additional skills being required by the fabricator.
  • a substrate composed ofhigh temperature, electrically nonconductive material comprising: a conductive phase composed of vanadium oxide in the range from about 1.00 to about 10.00 weight'percent and ruthenium dioxide in the range of from about 1 .00 to about 30.00 weight percent, and an interdispersed glass phase in the range of about 50100 to about 98.00 weight percent, said glass phase composed of lead oxide in the range of about 35.00 to about 45.00 weight percent, boron trioxide in the range of about 15.00 to about 25.00 weight percent and silicon dioxide present in the range of about 30.00 to about 40.00 weight percent.
  • the cermet resistor composition as defined in claim 1 further including iridium dioxide present in the range of about 1.00 to about 15.00 weight percent.
  • cermet resistor composition as defined in claim 3 wherein said glass phase is composed of lead oxide present in the range of about 38.00 to about 45.00 weight percent, said boron trioxide is present in the range of about 17.00 to about 21.00 and said silicon dioxide is present in the range of about 33.00 to about 37.00 weight percent.
  • composition as defined in claim 2 wherein said composition further includes bismuth trioxide present in an amount not greater than about 10.00 weight percent.
  • composition as defined in claim 2 wherein said composition includes aluminum trioxide present in an amount not greater than about 10.00 weight percent.
  • glass frit present in the range of about 5.00 to 40.00 weight percent, said glass frit comprising lead oxide present in the range of about 35.00
  • composition as defined in claim 11 further 5

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Non-Adjustable Resistors (AREA)
  • Conductive Materials (AREA)
  • Glass Compositions (AREA)
  • Details Of Resistors (AREA)
US359244A 1973-05-11 1973-05-11 Low temperature coefficient of resistivity cermet resistors Expired - Lifetime US3899449A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US359244A US3899449A (en) 1973-05-11 1973-05-11 Low temperature coefficient of resistivity cermet resistors
CA197,202A CA1037705A (en) 1973-05-11 1974-04-09 Low temperature coefficient of resistivity cermet resistors
AU67890/74A AU479484B2 (en) 1973-05-11 1974-04-16 Low temperature coefficient of resistivity cermet resistors
IN890/CAL/74A IN142722B (de) 1973-05-11 1974-04-18
GB1706474A GB1459327A (en) 1973-05-11 1974-04-18 Resistor composition
DE2421861A DE2421861C2 (de) 1973-05-11 1974-05-06 Elektrischer Vanadium-Ruthenium-Widerstand
BR3843/74A BR7403843D0 (pt) 1973-05-11 1974-05-10 Composicao para resistor tipo "cermet" de baixo coeficiente de resistividade em funcao da temperatura e resistor tipo "cermet"
FR7416228A FR2229122B1 (de) 1973-05-11 1974-05-10
CH644674A CH620544A5 (de) 1973-05-11 1974-05-10
IT22551/74A IT1012245B (it) 1973-05-11 1974-05-10 Resistori metalloceramici a basso coefficiente di temperatura di resistivita
AR253700A AR202024A1 (es) 1973-05-11 1974-05-10 Composicion de resistor de cermet
JP49052127A JPS6037601B2 (ja) 1973-05-11 1974-05-10 サ−メツト抵抗体組成
ES426228A ES426228A1 (es) 1973-05-11 1974-05-11 Procedimiento de obtencion de composiciones para resistorescerametalicos.
US05/565,870 US4006278A (en) 1973-05-11 1975-04-07 Low temperature coefficient of resistivity cermet resistors

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US359244A US3899449A (en) 1973-05-11 1973-05-11 Low temperature coefficient of resistivity cermet resistors

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US05/565,870 Division US4006278A (en) 1973-05-11 1975-04-07 Low temperature coefficient of resistivity cermet resistors

Publications (1)

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US3899449A true US3899449A (en) 1975-08-12

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US359244A Expired - Lifetime US3899449A (en) 1973-05-11 1973-05-11 Low temperature coefficient of resistivity cermet resistors

Country Status (12)

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US (1) US3899449A (de)
JP (1) JPS6037601B2 (de)
AR (1) AR202024A1 (de)
BR (1) BR7403843D0 (de)
CA (1) CA1037705A (de)
CH (1) CH620544A5 (de)
DE (1) DE2421861C2 (de)
ES (1) ES426228A1 (de)
FR (1) FR2229122B1 (de)
GB (1) GB1459327A (de)
IN (1) IN142722B (de)
IT (1) IT1012245B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292619A (en) * 1978-01-12 1981-09-29 U.S. Philips Corporation Resistance material
US4362656A (en) * 1981-07-24 1982-12-07 E. I. Du Pont De Nemours And Company Thick film resistor compositions
US5250958A (en) * 1987-12-10 1993-10-05 Matsushita Electric Industrial Co., Ltd. Thermal head and manufacturing method thereof
US20040005472A1 (en) * 2000-05-23 2004-01-08 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112309606A (zh) * 2019-07-31 2021-02-02 湖北中烟工业有限责任公司 一种复合型金属浆料组合物及其制备方法和用途

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3304199A (en) * 1963-11-12 1967-02-14 Cts Corp Electrical resistance element
US3440182A (en) * 1965-07-29 1969-04-22 Du Pont Copper/vanadium oxide compositions,noble metal metalizing compositions containing vanadium oxide additives,and electrical conductor elements made therewith
US3679607A (en) * 1966-10-24 1972-07-25 Int Nickel Co Oxide resistor materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA944938A (en) * 1970-01-16 1974-04-09 Rajnikant B. Amin Critical temperature resistors comprising a selected glass and vanadium dioxide or metal-doped vanadium dioxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3304199A (en) * 1963-11-12 1967-02-14 Cts Corp Electrical resistance element
US3440182A (en) * 1965-07-29 1969-04-22 Du Pont Copper/vanadium oxide compositions,noble metal metalizing compositions containing vanadium oxide additives,and electrical conductor elements made therewith
US3679607A (en) * 1966-10-24 1972-07-25 Int Nickel Co Oxide resistor materials

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292619A (en) * 1978-01-12 1981-09-29 U.S. Philips Corporation Resistance material
US4362656A (en) * 1981-07-24 1982-12-07 E. I. Du Pont De Nemours And Company Thick film resistor compositions
US5250958A (en) * 1987-12-10 1993-10-05 Matsushita Electric Industrial Co., Ltd. Thermal head and manufacturing method thereof
US20040005472A1 (en) * 2000-05-23 2004-01-08 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties
US6872453B2 (en) 2000-05-23 2005-03-29 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties
US20050147825A1 (en) * 2000-05-23 2005-07-07 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties
US7311976B2 (en) 2000-05-23 2007-12-25 Saint-Gobain Glass France Glazing coated with at least one layer having thermochromic properties

Also Published As

Publication number Publication date
BR7403843D0 (pt) 1974-12-03
CA1037705A (en) 1978-09-05
DE2421861A1 (de) 1974-12-05
JPS5016097A (de) 1975-02-20
FR2229122B1 (de) 1982-06-11
AR202024A1 (es) 1975-05-09
ES426228A1 (es) 1976-07-01
IN142722B (de) 1977-08-20
JPS6037601B2 (ja) 1985-08-27
DE2421861C2 (de) 1984-03-29
IT1012245B (it) 1977-03-10
FR2229122A1 (de) 1974-12-06
CH620544A5 (de) 1980-11-28
AU6789074A (en) 1975-10-16
GB1459327A (en) 1976-12-22

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