US3916037A - Resistance composition and method of making electrical resistance elements - Google Patents

Resistance composition and method of making electrical resistance elements Download PDF

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Publication number
US3916037A
US3916037A US337140A US33714073A US3916037A US 3916037 A US3916037 A US 3916037A US 337140 A US337140 A US 337140A US 33714073 A US33714073 A US 33714073A US 3916037 A US3916037 A US 3916037A
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United States
Prior art keywords
iridium
resistance
composition
weight
range
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Expired - Lifetime
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US337140A
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English (en)
Inventor
Lynn J Brady
Marion E Ellis
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CTS Corp
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CTS Corp
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Priority to US337140A priority Critical patent/US3916037A/en
Priority to CA192,965A priority patent/CA1027749A/en
Priority to AU66035/74A priority patent/AU474753B2/en
Priority to JP49022901A priority patent/JPS5757803B2/ja
Priority to FR7406850A priority patent/FR2220087B1/fr
Priority to GB915274A priority patent/GB1462526A/en
Priority to BR1423/74A priority patent/BR7401423D0/pt
Priority to DE2409505A priority patent/DE2409505B2/de
Priority to IT67560/74A priority patent/IT1009193B/it
Application granted granted Critical
Publication of US3916037A publication Critical patent/US3916037A/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

Definitions

  • ABSTRACT [52] US. Cl. 427/101; 427/102; 427/103;
  • the present invention relates to a resistance composition and to a method of making a resistance composition and an electrical resistance element therefrom and, in particular, to an improved resistance composition of the cermet type containing in any form at least one of the noble metals, e.g., an oxide or compound thereof, in a fine particle size preferably 325 mesh or smaller and glass particles or suitable ceramic materials,
  • TCR low temperature coefficient of resistance
  • dR/Rdt rate of change in resistance with respect to a change in temperature
  • STOL short time overload
  • the TCR and STOL tests of a cermet resistance element are extremely important considerations in present day electronics especially for cermet resistors used in high voltage circuits, e.g., bleeder circuits in television sets If the TCR and STOL resistance values are too high, inevitable changes in the ambient temperature and applied voltages in modern applications could lead to serious consequences. It is particularly important to control these properties over a wide range of resistance values. Cermet resistors having a wide range of resistance values have been known for many years. For example, Daily et al. (US. Pat. No.
  • cermet resistance element having a TCR of approximately 100 parts per million per degree Centigrade (PPM/C) for ohmic values throughout a resistance range of less than 100 ohms per square to 180,000 ohms per square. Faber et al. discovered that cermet resistance elements could be produced reliably and predictably by using a specified percentage of an oxide of ruthenium and/or an oxide of iridium in making a cermet resistance composition. l-lolmes (US. Pat. No.
  • 3,324,049) also assigned to the same assignee as the present invention discloses means for controlling the TCR of a cermet resistance element though the TCR was controlled only at a specific temperature. It therefore would be desirable to produce resistors within the i 50 PPM/"C TCR range over the resistance range of 50 ohms per square to K ohms per square not only at a specified temperature but within the entire temperature range of 55C to +l25C.
  • voltage stability preferably is defined as the maximum voltage or wattage that can be applied to the end terminals of a resistor without having an overall resistance change of more than 0.25%.
  • the short time overload test is conducted by applying to each resistor a voltage potential equal to 2.5 times the rated continuous working voltage of the resistor.
  • the working voltage or voltage rating is the maximum sustained voltage that can be safely applied to a resistor without risk of breakdown or failure during its life expectancy.
  • the voltage potential is applied for a five second duration and the resistance is measured approximately 30 minutes after application of the voltage potential to determine the percent change of resistance.
  • the potential is applied up to a maximum of 3,000 volts per inch of linear resistor. In subjecting resistors having a low sheet resistivity or ohms per square to a voltage stability test, a specified overload voltage cannot be applied to the terminals of the resistor without exceeding the overload wattage rating of a resistor.
  • Resistors having a high sheet resistivity and a high voltage withstanding capability can be made by following the teachings of Brady US. Pat. No. 3,655,440.
  • a low TCR, for example, of i 50 parts per million cannot be achieved throughout the entire temperature range of 55C to +l25C. It would, therefore, be desirable to make cermet resistors having not only a low STOL resistance but also having a low TCR of i 50 parts per million throughout the entire temperature range of 55C and +C.
  • Another object of the present invention is to provide an improved cermet resistance composition and resistance elements made therefrom.
  • Another object of the present invention is to provide a method for preparing a resistance composition for making resistors having a TCR within i 100 parts per million per degree Centigrade throughout the temperature range of 55C to +125C and over the resistance range of 50 ohms per square to 250K ohms per square and which exhibit improved voltage overload characteristics.
  • a further object of the present invention is to produce cermet resistors having a i 50 PPM/C throughout the temperature range of 55C to +125C and over the resistance range of 50 ohms per square to 100K ohms per square.
  • the present invention comprises mixing together a screening agent, a glass frit and a conductive fraction consisting of ruthenium dioxide or compounds thereof and an organoiridium compound in solution to form a resistance composition.
  • the composition is then applied to a ceramic substrate by conventional methods and fired to produce a cermet resistance element.
  • FIG. 1 is a plot of resistance versus temperature of a resistance element made in accord with the present invention and a prior art resistance element;
  • FIG. 2 is a plot of TCR versus temperature of the resistance elements referred to in FIG. 1;
  • FIG. 3 is an operational diagram of a preferred form of the present invention for producing resistance compositions and elements.
  • this formula is not an accurate reflection of the TCR of a given resistor at a specific temperature over a temperature range since it only provides an average TCR value between the test point and the room temperature reference point. For example, it is customary to measure the TCR of a given resistor at 55C and +125C using room temperature as the reference temperature. The resulting TCR values indicate only the average TCR value between the test temperatures and the reference temperature but give no indication of the actual TCR at any specific temperature.
  • the correct formula for determining the TCR of a resistor at a specific temperature T is:
  • FIG. 1 shows values of resistance versus temperature of a resistor made from a resistance composition prepared in accord with the teachings of the present invention and a prior art resistor.
  • Prior art resistors also show other types of curves such as linear curves and various convex and concave curves such as U-shaped and S- shaped.
  • the significant distinction of the present invention is that the rate of change of resistance over the range of 55C to +125C is significantly less with a resistor made with the resistance composition prepared in accord with the present invention than with a prior art resistor.
  • the spread of resistance for a prior art resistor was about 360 ohms and the spread for a resistor made in accord with the present invention was about ohms or more than 400 percent better.
  • TCR curves of FIG. 2 are approximations based upon the slopes of the curves of FIG. 1, the results are fairly typical of actual calculated values of TCR for prior art resistors and resistors made in accord with the present in vention.
  • the spread of TCR values of the present invention from 5 5C to +125C is relatively small compared to the spread of TCR values of a prior art resistor.
  • the spread of TCR valves of resistors from 50 ohm to K ohms of the present invention is within i 50 PPM/C.
  • the spread of TCR for a prior art resistor was from 1O PPM/C to +132 PPM/C and the spread for the resistor made in accord with the present invention was from +15 PPM/C to +40 PPM/C.
  • the narrow spread of the TCR values of the present invention exists not only over the temperature range of 55C to +C but also exists over a resistance range of constituents ohms per square to 100K ohms per square.
  • resistance compositions of the present invention are produced by mixing together finely divided glass particles or glass frit, a vehicle and a conductive fraction consisting of ruthenium dioxide and iridium, said iridium being present as an organometallic compound in solution.
  • the ingredients are blended together and applied to the surface of a high temperature resistant electrically nonconductive substrate and then fired.
  • any conventional vehicle or screening agent capable of being completely volatilized or decomposed by heat can be used.
  • the vehicle should contain a viscosifying agent to keep the glass frit in suspension after the mixture has been screened on the substrate.
  • Ethylcellulose dissolved in a pine oil solution is an example of a screening agent also serving as a viscosifying material.
  • the organometallic compound in solution can be, e.g., a metal resinate, glycinate, etherate, esterate or napthanate.
  • the following formulations are exemplary of the basic resistance compositions that can be produced in accordance with the present invention using iridium resinate and ruthenium dioxide as the principle conductive fraction. Some of the improved properties of fired resistance elements formed from such compositions are also stated for each example.
  • Each of the resistance elements was produced by screening the resistance composition onto a high temperature substrate, it being understood that the vehicle and other Organic materials are decomposed and volatilized upon firing.
  • the five primary formulations set forth above comprise a resistive system covering the range from 50 ohms per square to 250K ohms per square.
  • Intermediate resistance values are obtained by blending adjacent primary formulations. That is, to obtain resistance values between 50 ohms and 400 ohms, Example A and Example B are blended. To obtain resistance values between 400 ohms and 3,000 ohms, Example B and Example C are blended.
  • TCRs of i 100 PPM/"C can be obtained for the blends without additional TCR adjustment and often TCRs of i 50 PPM/"C are achieved without any additional adjustment.
  • Example F below shows a blend of 50% Example C with 50% Example D to obtain a sheet resistance of 11.5K ohms per square and a TCR within 2 50 PPM/C.
  • Examples A through F are produced in the following manner.
  • a conventional screening agent or vehicle, ruthenium dioxide particles, glass frit, and iridium resinate are weighed into a suitable container and mixed well with a spatula by hand stirring to produce a resistance composition.
  • the conductive fraction employed in the examples is a ruthenium dioxide powder obtainable either by dehydating ruthenium oxide hydrate or by heating ruthenium to ruthenium dioxide and ball milling the ruthenium dioxide to obtain the desired particle size. If the glass frit has not been ground to suitable particle size, the mixed ingredients of the composition are ground on a roll mill. The composition is then screened on a ceramic substrate and fired in a kiln at about 850C.
  • the iridium resinate used contained approximately 6% iridium metal. If an iridium resinate is used that contains more or less than 6% iridium metal, then adjustments should be made to the amount of iridium resinate added to the mixture to obtain the desired properties.
  • the desired properties are generally obtainable with between 2% to of iridium metal and ruthenium metal by weight in the mixture before firing, the iridium metal present as an organometallic compound in solution and the ruthenium present as RuO the RuO to iridium ratio usually being greater than 2:1.
  • a method of forming an electrical resistance element having a TCR in the range of i 1.00 PPM/"C over the temperature range of 55C to +lC comprising the steps of:
  • organometallic compound in solution is iridium resinate and contains less than 3% iridium metal by weight of said resistance composition.
  • step of firing the resistance element includes the step of heating the electrically nonconductive base and layer of resistance composition applied thereon to a temperature sufficient to melt the powder-like particles of glass, reduce the iridium resinate, and volatilize the organic screening agent and burn off the carbonaceous residue, but below the temperature necessary to soften the base, to produce film of glass on the base containing ruthenium dioxide and iridium in some form dispersed therein.
  • a resistance composition for making cermet resistance elements having a TCR in the range of i 100 PPM/"C over the temperature range of -55C to +125C comprising at least 30% by weight of a finely divided nonconductive vitreous binder and l to by weight of a conductive fraction comprising particles of ruthenium dioxide and iridium, said iridium being present in an organometallic compound in solution.
  • composition of claim 6 wherein said organometallic compound in solution is iridium resinate and wherein the ratio of the ruthenium dioxide to the iridium in the resistance composition is greater than 2:1.
  • the resistance composition of claim 11 wherein the resistance element has a TCR in the range of i 100 PPM/C over the resistance range of 50 ohms to 250K ohms.
  • the resistance composition of claim 11 wherein the resistance element has a TCR in the range of i 50 PPM/"C over the temperature range of 55C to +l25C.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Conductive Materials (AREA)
  • Non-Adjustable Resistors (AREA)
  • Glass Compositions (AREA)
US337140A 1973-03-01 1973-03-01 Resistance composition and method of making electrical resistance elements Expired - Lifetime US3916037A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US337140A US3916037A (en) 1973-03-01 1973-03-01 Resistance composition and method of making electrical resistance elements
CA192,965A CA1027749A (en) 1973-03-01 1974-02-19 Resistance composition and method of making electrical resistance elements
AU66035/74A AU474753B2 (en) 1973-03-01 1974-02-26 Resistance composition and method of making electrical resistance elements
FR7406850A FR2220087B1 (enrdf_load_stackoverflow) 1973-03-01 1974-02-28
JP49022901A JPS5757803B2 (enrdf_load_stackoverflow) 1973-03-01 1974-02-28
GB915274A GB1462526A (en) 1973-03-01 1974-02-28 Resistance composition and method of making electrical resistance elements
BR1423/74A BR7401423D0 (pt) 1973-03-01 1974-02-28 Processo de producao de um elemento de resistencia eletrica e composicao de resistencia para producao de elementos de resistencia
DE2409505A DE2409505B2 (de) 1973-03-01 1974-02-28 Widerstandsmasse zur Herstellung einer metallkeramischen Widerstandsschicht
IT67560/74A IT1009193B (it) 1973-03-01 1974-03-06 Procedimento e composizione per la fabbricazione di elementi resistivi elettrici

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Application Number Priority Date Filing Date Title
US337140A US3916037A (en) 1973-03-01 1973-03-01 Resistance composition and method of making electrical resistance elements

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US3916037A true US3916037A (en) 1975-10-28

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US337140A Expired - Lifetime US3916037A (en) 1973-03-01 1973-03-01 Resistance composition and method of making electrical resistance elements

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US (1) US3916037A (enrdf_load_stackoverflow)
JP (1) JPS5757803B2 (enrdf_load_stackoverflow)
AU (1) AU474753B2 (enrdf_load_stackoverflow)
BR (1) BR7401423D0 (enrdf_load_stackoverflow)
CA (1) CA1027749A (enrdf_load_stackoverflow)
DE (1) DE2409505B2 (enrdf_load_stackoverflow)
FR (1) FR2220087B1 (enrdf_load_stackoverflow)
GB (1) GB1462526A (enrdf_load_stackoverflow)
IT (1) IT1009193B (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006278A (en) * 1973-05-11 1977-02-01 Globe-Union Inc. Low temperature coefficient of resistivity cermet resistors
US4104421A (en) * 1974-11-29 1978-08-01 Sprague Electric Company Method of making a glass containing resistor having a sub-micron metal film termination
US4139832A (en) * 1976-03-19 1979-02-13 Hitachi, Ltd. Glass-coated thick film resistor
FR2414780A1 (fr) * 1978-01-12 1979-08-10 Philips Nv Materiau de resistance
US4436829A (en) 1982-02-04 1984-03-13 Corning Glass Works Glass frits containing WO3 or MoO3 in RuO2 -based resistors
US4464416A (en) * 1981-03-11 1984-08-07 The United States Of America As Represented By The Depart Of Energy Method of forming metallic coatings on polymeric substrates
US4464421A (en) * 1982-02-04 1984-08-07 Corning Glass Works Glass frits containing WO3 or MoO3 in RuO2 -based resistors
US5463367A (en) * 1993-10-14 1995-10-31 Delco Electronics Corp. Method for forming thick film resistors and compositions therefor

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4830780A (enrdf_load_stackoverflow) * 1971-08-23 1973-04-23
US4311980A (en) * 1978-10-12 1982-01-19 Fabrica Italiana Magneti Marelli, S.P.A. Device for pressure measurement using a resistor strain gauge
JPS59152855A (ja) * 1983-02-22 1984-08-31 旭化成株式会社 強靭な多層アクリルシ−ト状成形品

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3252831A (en) * 1964-05-06 1966-05-24 Electra Mfg Company Electrical resistor and method of producing the same
US3304199A (en) * 1963-11-12 1967-02-14 Cts Corp Electrical resistance element
US3539392A (en) * 1966-06-14 1970-11-10 Plessey Co Ltd Resistors
US3607789A (en) * 1968-05-02 1971-09-21 Precision Electronic Component Electroconductive glaze and method for preparation
US3620840A (en) * 1968-12-13 1971-11-16 Methode Dev Co Resistance material and resistance elements made therefrom
US3655440A (en) * 1969-03-03 1972-04-11 Cts Corp Electrical resistance elements, their composition and method of manufacture
US3673117A (en) * 1969-12-19 1972-06-27 Methode Dev Co Electrical resistant material
US3681261A (en) * 1970-07-27 1972-08-01 Owens Illinois Inc Resistors,compositions,pastes,and method of making and using same

Patent Citations (8)

* 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
US3252831A (en) * 1964-05-06 1966-05-24 Electra Mfg Company Electrical resistor and method of producing the same
US3539392A (en) * 1966-06-14 1970-11-10 Plessey Co Ltd Resistors
US3607789A (en) * 1968-05-02 1971-09-21 Precision Electronic Component Electroconductive glaze and method for preparation
US3620840A (en) * 1968-12-13 1971-11-16 Methode Dev Co Resistance material and resistance elements made therefrom
US3655440A (en) * 1969-03-03 1972-04-11 Cts Corp Electrical resistance elements, their composition and method of manufacture
US3673117A (en) * 1969-12-19 1972-06-27 Methode Dev Co Electrical resistant material
US3681261A (en) * 1970-07-27 1972-08-01 Owens Illinois Inc Resistors,compositions,pastes,and method of making and using same

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006278A (en) * 1973-05-11 1977-02-01 Globe-Union Inc. Low temperature coefficient of resistivity cermet resistors
US4104421A (en) * 1974-11-29 1978-08-01 Sprague Electric Company Method of making a glass containing resistor having a sub-micron metal film termination
US4139832A (en) * 1976-03-19 1979-02-13 Hitachi, Ltd. Glass-coated thick film resistor
FR2414780A1 (fr) * 1978-01-12 1979-08-10 Philips Nv Materiau de resistance
US4292619A (en) * 1978-01-12 1981-09-29 U.S. Philips Corporation Resistance material
US4464416A (en) * 1981-03-11 1984-08-07 The United States Of America As Represented By The Depart Of Energy Method of forming metallic coatings on polymeric substrates
US4436829A (en) 1982-02-04 1984-03-13 Corning Glass Works Glass frits containing WO3 or MoO3 in RuO2 -based resistors
US4464421A (en) * 1982-02-04 1984-08-07 Corning Glass Works Glass frits containing WO3 or MoO3 in RuO2 -based resistors
US5463367A (en) * 1993-10-14 1995-10-31 Delco Electronics Corp. Method for forming thick film resistors and compositions therefor

Also Published As

Publication number Publication date
CA1027749A (en) 1978-03-14
DE2409505B2 (de) 1978-08-10
AU474753B2 (en) 1976-07-29
AU6603574A (en) 1975-08-28
JPS507098A (enrdf_load_stackoverflow) 1975-01-24
JPS5757803B2 (enrdf_load_stackoverflow) 1982-12-07
GB1462526A (en) 1977-01-26
FR2220087B1 (enrdf_load_stackoverflow) 1978-01-06
IT1009193B (it) 1976-12-10
DE2409505A1 (de) 1974-09-19
BR7401423D0 (pt) 1974-11-05
FR2220087A1 (enrdf_load_stackoverflow) 1974-09-27

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