EP0163004A1 - Electrical-resistance composition and method of making electrical-resistance elements - Google Patents

Electrical-resistance composition and method of making electrical-resistance elements Download PDF

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Publication number
EP0163004A1
EP0163004A1 EP85101524A EP85101524A EP0163004A1 EP 0163004 A1 EP0163004 A1 EP 0163004A1 EP 85101524 A EP85101524 A EP 85101524A EP 85101524 A EP85101524 A EP 85101524A EP 0163004 A1 EP0163004 A1 EP 0163004A1
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Prior art keywords
elements
srru
binder component
paste
group
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EP85101524A
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German (de)
French (fr)
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EP0163004B1 (en
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Dana L. Dr. Hankey
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WC Heraus GmbH and Co KG
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WC Heraus GmbH and Co KG
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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
    • H01C17/06573—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder
    • H01C17/0658—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder composed of inorganic material
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49082—Resistor making
    • Y10T29/49099—Coating resistive material on a base

Definitions

  • the present invention relates to compositions for producing electrical resistance elements and methods for producing the resistance elements.
  • Electrical resistance elements made from certain compositions are particularly useful for creating micro-miniature circuits for the electronics industry, where the electronic elements (or pastes) are screen printed onto substrates.
  • US Pat. No. 3,304,199 describes an electrical resistance element which is composed of a mixture of Ru0 2 or Ir0 2 and lead borosilicate glass.
  • the mixture is combined with a carrier, e.g. B. an organic screen printing agent, such as ethyl cellulose dissolved in acetone-toluene.
  • a carrier e.g. B. an organic screen printing agent, such as ethyl cellulose dissolved in acetone-toluene.
  • the resulting mixture which contains the carrier, is applied to an electrically non-conductive substrate and then baked in air.
  • US Pat. No. 3,324,049 describes a cermet resistance material which contains 40 to 99% by weight of a lead borosilicate glass, 0.5 to 20% by weight of a noble metal, such as Ag, Au, Pd, Pt, Rh, Ir, Os or Ru and 0.5 to 40 wt .-% MnO 2 or Cu0 contains. The resulting resistance material is then burned in air.
  • a noble metal such as Ag, Au, Pd, Pt, Rh, Ir, Os or Ru
  • U.S. Patent 3,655,440 relates to a resistance composition containing RuO 2 , IrO 2 or PdO, a glassy lead borosilicate binder and an electrically non-conductive crystal growth control agent, e.g. B. A10 3 , which contains submicron small inert particles.
  • a resistance composition containing RuO 2 , IrO 2 or PdO, a glassy lead borosilicate binder and an electrically non-conductive crystal growth control agent, e.g. B. A10 3 , which contains submicron small inert particles.
  • Such a resistance composition is baked in air at 975 to 1025 ° C for 45 minutes to 1 hour.
  • the US Patent 3,682,840 relates to electrical resistance compositions containing lead ruthenate and mixtures thereof with Ru0 2 in conjunction with lead borosilicate binder.
  • U.S. Patent 4,065,743 relates to a glassy enamel resistor containing a glass frit and electrically conductive particles.
  • Such electrically conductive particles contain tin oxide and tantalum oxide.
  • U.S. Patent 4,101,708 is directed to a printable composition of finely divided powder in an inert liquid vehicle for making film resistors that adhere to a dielectric substrate; such compositions contain RuO 2 , a glass containing PbO, Nb 2 0 5 , CaF 2 and an inert carrier.
  • German patent specification 21 15 814 relates to a resistance paste for baking on ceramics in air.
  • This resistance paste contains BaRuO 3 , SrRu0 3 and CaRu0 3 in a lead borosilicate glass.
  • Resistance compositions were also made using Ag-Pd and / or PdO, RuO 2 , Ir0 2 and the so-called "du Pont" pyrochlore compounds.
  • the pyrochlore structures are complex oxides of the general formula A 2 B 2 O 6-7 , with the large cation A in eightfold coordination and the small cation B in octahedral coordination. Their success is mainly due to their stability in changeable atmospheres (reducing) and their ability to change their electrical properties through multiple substitution of elements.
  • Examples of pyrochlore compounds that are specifically used in these compositions and discussed in U.S. Patents 3,553,109, 3,560,410 and 3,583,931 include Bi 2 Ru 2 O 7 and Pb 2 Ru 2 O 7-x , where 0 ⁇ x ⁇ 1.
  • the perovskite crystal structure was described by UM Goldsmith, Skrifter Norske Videnskaps - Akad., Oslo, I: Mat. Naturv.Kl. 2: 8 (1926).
  • the A cation is in twelve coordination with oxygen and the smaller B cation is in octahedral coordination.
  • the perovskite structure has high lattice energy and is generally a very stable structure.
  • Resistance compositions have been applied by screen printing, which require a baking in an oxidizing atmosphere (air), which necessitates the use of expensive precious metals such as Au, Ag, Pt and Pd.
  • the less expensive copper could not be used because copper oxidizes easily. Accordingly, there is a need for a stable copper-compatible resistor composition that can be used in a non-oxidizing atmosphere, such as. B. SLicktoff, could be burned.
  • Typical resistance compositions used previously use lead borosilicate glass binders. After baking in air, it decomposes in the resistance compositions, e.g. B. strontium ruthenate in a lead borosilicate binder, the strontium ruthenate to strontium oxide, which dissolves in the binder, and ruthenium oxide.
  • the strontium ruthenate is stoved in a strontium borosilicate binder under nitrogen, there is no decomposition of the electrically conductive component, i. H. the strontium ruthenate remains unchanged.
  • Another object of the present invention is to provide a thick film resistor system which has property reproducibility and reduced processing sensitivity.
  • the present invention relates to a composition for producing an electrical resistance element, which is composed of an electrically conductive component and a binder.
  • the present invention also relates to a method for producing an electrical resistance element by producing the above-described composition, pasting this composition with an organic carrier, applying the paste by screen printing to a substrate and baking.
  • the binder component can also contain 0.1 to 2.5% by weight of Al 2 O 3 .
  • the binder component may further contain 0.1 to 1.5% by weight of one or more of the following oxides: Bi203, CuO, MgO, Nb 2 O 5 .
  • the binder component can also still contain 0.1 to 1.5% by weight of TiO 2 or NaF. If necessary, the Binder component also contain 5 to 15 wt .-% Ca0.
  • composition for manufacturing electrical resistance elements contains an electrically conductive metal oxide perovskite component and a glass binder component.
  • Preferred electrically conductive components include SrRu 0.8 . Ti 0.2 O 3 , S r R u 0 3 and SrRu 0.9 Ti 0.1 O 3 . Combinations of these components can also be used, such as. B. SrRuO 3 + SrRu 0.8 Ti 0.2 O 3 or S r Ru0 3 + SrRu 0.9 Ti 0.1 O 3 .
  • the conductive components include SrRu 0.95 C d 0.05 O 3 , Sr 0.90 Na 0.10 RuO 3 , Sr 0.90 y 0.10 RuO 3 , Sr 0.80 Na 0.10 La 0.10 RuO 3 and SrRu 0.8 RuTi 0.2 O 3 / SrRu0 3 , SrRu 0.8 Zr 0.2 O 3 , SrRu 0.9 Zr 0.1 O 3 , SrRu 0.75 V 0.25 O 3 and SrRu 0.8 Co 0.2 O 3 .
  • substitutions based on ionic radii and valency of A and B are as follows:
  • the main components of the binder component of the present invention are C ', ie SrO or BaO or Sr0 + BaO, and B 2 O 3 , SiO 2 and Zn0 in the following amounts:
  • binder component can also comprise one or more of the following constituents:
  • Nonlimiting examples of preferred compositions of the binder component include the following:
  • compositions of the binder component include the following:
  • the weight% ratio of binder component / electrically conductive component can vary from 25 to 75% by weight of binder component / 75 to 25% by weight of electrically conductive component, i. H. the binder component can e.g. B. 30, 35, 40, 50, 60, 65 or 70 wt .-%.
  • the binder component and the electrically conductive component are mixed with a suitable "organic carrier" mixed.
  • An organic vehicle is a medium that volatilizes at a relatively low temperature (approximately 400 to 500 ° C) without causing a reduction in other paste components.
  • An organic carrier serves as a transfer medium for screen printing.
  • An organic vehicle for use in the present invention is preferably a resin, e.g. B. an acrylic ester resin, preferably an isobutyl methacrylate, and a solvent, e.g. B. an alcohol, preferably tridecyl alcohol (“TDA").
  • the resin can be any polymer that depolymerizes in nitrogen at or below 400 ° C.
  • solvents that can be used are Terpineol or "TEXANOL" from Eastman Kodak.
  • the solvent for use in the present invention may be any solvent which dissolves the resin in question and which has an appropriate vapor pressure consistent with the subsequent milling and screen printing.
  • the organic carrier consists of 10 to 30% by weight of isobutyl methacrylate and 90 to 70% by weight of TDA.
  • the binder component, the electrically conductive component and the organic carrier are mixed and screen printed onto the copper connection on a suitable substrate, eg. B. from 96% Al 2 0 31 by screen printing and then in a nitrogen atmosphere at a temperature of z. B. 900 ° C a suitable time, e.g. B. 7 minutes, baked.
  • a suitable substrate eg. B. from 96% Al 2 0 31 by screen printing and then in a nitrogen atmosphere at a temperature of z. B. 900 ° C a suitable time, e.g. B. 7 minutes, baked.
  • the electrically conductive component, the binder component and the organic carrier are brought together to form a paste.
  • the paste is then ground to the fineness required for the screen printing technique.
  • the binder component (glass matrix) of the present invention prevents decomposition of the electrically conductive component during baking, i.e. H. the crystal structure (physical) and the chemical composition of the electrically conductive component remain stable and unchanged during baking.
  • the binder is synthesized using analytical grade materials, each in the oxide form except for the strontium, barium and copper compounds which are present as carbonates.
  • the individual components are weighed and homogenized for 1 hour in a V-mixer (which is a dry mixing process). After mixing is complete, the homogenized powders are placed in a cyanite crucible, where they are then melted.
  • the binders are preheated at 600 ° C for 1 hour and then transferred to another oven where they are then melted in a temperature range of 1100 to 1300 ° C for a period of 1 to 1.5 hours.
  • the molten material is removed from the furnace at the melting temperature and poured into a stainless steel tub filled with deionized water.
  • compositions I, II and III As soon as the melt comes into contact with the water, it solidifies and disintegrates into glass fragments (the size or the thermal stress being specified).
  • the deionized water is decanted and the glass is then placed in a ceramic ball mill with grinding cylinders made of aluminum oxide with the addition of isobutyl alcohol. The jars are ground for 24 hours and then wet sieved through a 200 mesh screen. After drying In an explosion-proof convection oven at room temperature, the powders are ready for characterization and for incorporation in the resistance paste. The particle size of the powder is 1 to 2 ⁇ m.
  • the binder components thus produced are then those as stated above as compositions I, II and III. The softening points for compositions I, II and III were determined to be 625 ° C, 635 ° C and 660 ° C.
  • Other binder component compositions made according to Example 1 are as follows:
  • the electrically conductive components are prepared by attaching the appropriate connection (e.g. SrRu03), calculating the equimolar amount of e.g. B. SrCO 3 and RuO 2 , which must be weighed to ensure the stoichlometry and ultimately weighing the individual components. Correction factors for the Ru metal content, water content and other volatile components that are lost when annealing at 600 ° C are also included in the calculation. A similar one Correction factor for the loss on ignition was also included in the calculation for the weights of the other components, if necessary.
  • the RuO 2 has a surface area of more than 70 m 2 / g, while the other components have a surface area of less than 5 m 2 / g.
  • the weighed starting materials are ground in a ceramic ball mill with aluminum oxide grinding devices for 2 hours together with deionized water, that is to say subjected to a wet grinding process. After 2 hours, the homogenized slurry is poured into stainless steel troughs and dried at 80 ° C for 24 hours. The dried mixture is sieved through an 80 mesh screen before calcination.
  • the sieved powders are calcined in crucibles made of high-purity aluminum oxide (purity 99.8%), this step being carried out precisely with microprocessor control.
  • the heating and Abkühlun s Anlagenen g are not critical per se, they are generally from 500 ° C / hr.
  • the holding times at the relevant temperatures (from 800 to 1200 ° C, depending on the connection) vary between 1 and 2 hours.
  • the powders are ground in a Sweeco vibratory mill for 2 hours. This is a high energy milling process using alumina milling media and isopropyl alcohol.
  • the perovskites are sieved wet (200 mesh) at the end of the grinding stage, dried at room temperature in a convection oven (explosion-proof) and prepared for characterization and incorporation in the resistance paste.
  • the electrically conductive components which were produced according to the above-described method, contain the following:
  • Example 3 Combination of binder components of electrically conductive components
  • the binder components made in accordance with Example 1 are combined with electrically conductive components made in Example 2 together with an organic carrier.
  • "ACRYLOID” B67 a resin (an isobutyl methacrylate) from Rohm & Haas, Philadelphia, Pennsylvania, and tridecyl alcohol (“TDA”) in a weight ratio of 30:70 is used as the organic carrier.
  • the relevant binder components, the electrically conductive components and the organic carrier are weighed to produce the desired paste mixture.
  • the solids content (binder + electrically conductive phase) is kept at 70% by weight, based on the total paste weight.
  • the paste is ground in a three-roller mill to a fineness of 10 ⁇ m. Resistance test samples are screen printed with the following printing thicknesses: wet 29 to 32 ⁇ m; fired 10 to 13 ⁇ m.
  • the pastes are then either mil emulsion or through a 325 mesh screen with 0, 6 printed through a 280 mesh screen with a 0.5 mil emulsion.
  • the damp prints are dried for 5 to 10 minutes at 150 ° C before baking.
  • the stoving profile was dependent on the composition of the binder component, e.g.
  • pastes containing Composition I were baked at 850 ° C, while pastes containing Composition II or III were baked at 900 ° C.
  • the 850 ° C profile length was 58 minutes from 100 ° C to 100 ° C, i.e. H. from the furnace entrance to the furnace exit.
  • the heating rate was 45 ° C per minute, the cooling rate 60 ° C per minute, and the residence time at the maximum temperature was 10 minutes.
  • the 900 ° C profile had a duration of 55 minutes from 100 ° C to 100 ° C, a heating rate of 50 ° C per minute and a cooling rate of 60 ° C per minute, the residence time at the maximum temperature varied between 5 and 14 minutes .

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  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Non-Adjustable Resistors (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
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Abstract

Die Erfindung beinhaltet eine Zusammensetzung zur Herstellung elektrischer Widerstandselemente. Diese Zusammensetzung enthält eine elektrisch leitfähige Komponente und eine Bindmittelkomponente. Die elektrisch leitfähige Komponente enthält ein Edelmetalloxid der allgemeinen Formel A'l-xA"xB'l-yB"yO3. Darin sind: A' = Sr oder Ba. Wenn A' = Sr, dann ist A" eins oder mehrere Elemente aus der Gruppe Ba, La, Y, Ca und Na; wenn A' = Ba, dann ist A" eins oder mehrere Elemente aus der Gruppe Sr, La, Y, Ca und Na. B' = Ru. B" ist eins oder meherere der Elemente aus der Gruppe Ti, Cd, Zr, V und Co. Ferner gilt: O < × < 0,2 und O < y < 0,2. Die Bindemittelkomponente enthält:(i) 40 bis 75 Gewichts-% C', wobei C' = SrO, wenn A' = Sr, C' = BaO, wenn A' = Ba, und C' = SrO + BaO, wenn A' = Sr und A" = Ba und wenn A' = Ba und A" = Sr, (ii) 20 bis 35 Gew.-% B2O3, (iii) 2 bis 15 Gew.-% SiO2, und (iv) 0,5 bis 6,5 Gew.-% ZnO. Das Verfahren hat die Herstellung elektrischer Widerstandselemente durch Herstellung einer Paste aus der vorstehenden leitfähigen Komponente und Bindemittelkomponente unter Zusatz eines organischen Trägermittels.The invention includes a composition for making electrical resistance elements. This composition contains an electrically conductive component and a binder component. The electrically conductive component contains a noble metal oxide of the general formula A'l-xA "xB'l-yB" yO3. There are: A '= Sr or Ba. If A '= Sr, then A "is one or more elements from the group Ba, La, Y, Ca and Na; if A' = Ba, then A" is one or more elements from the group Sr, La, Y, Ca and Na. B '= Ru. B "is one or more of the elements from the group Ti, Cd, Zr, V and Co. Furthermore, the following applies: O <× <0.2 and O <y <0.2. The binder component contains: (i) 40 to 75 % By weight C ', where C' = SrO if A '= Sr, C' = BaO if A '= Ba, and C' = SrO + BaO if A '= Sr and A "= Ba and if A '= Ba and A "= Sr, (ii) 20 to 35% by weight B2O3, (iii) 2 to 15% by weight SiO2, and (iv) 0.5 to 6.5% by weight ZnO. The method has the production of electrical resistance elements by producing a paste from the above conductive component and binder component with the addition of an organic carrier.

Description

Die vorliegende Erfindung betrifft Zusammensetzungen zur Herstellung elektrischer Widerstandselemente und Verfahren zur Herstellung der Widerstandselemente.The present invention relates to compositions for producing electrical resistance elements and methods for producing the resistance elements.

Elektrische Widerstandselemente, die aus bestimmten Zusammensetzungen hergestellt sind, sind besonders nützlich zur Erzeugung von Mikrominiatur-Schaltkreisen für die elektronische Industrie, wobei die elektronischen Elemente (oder Pasten) im Siebdruckverfahren auf Substrate gedruckt werden.Electrical resistance elements made from certain compositions are particularly useful for creating micro-miniature circuits for the electronics industry, where the electronic elements (or pastes) are screen printed onto substrates.

Das US-Patent 3 304 199 beschreibt ein elektrisches Widerstandselement, das zusammengesetzt ist aus einer Mischung von Ru02 oder Ir02 und Bleiborosilikatglas. Die Mischung wird vereinigt mit einem Trägermittel, z. B. einem organischen Siebdruckmittel, wie in Aceton-Toluol gelöste Äthylcellulose. Die resultierende Mischung, die das Trägermittel enthält, wird auf ein elektrisch nichtleitendes Substrat aufgebracht und dann in Luft eingebrannt.US Pat. No. 3,304,199 describes an electrical resistance element which is composed of a mixture of Ru0 2 or Ir0 2 and lead borosilicate glass. The mixture is combined with a carrier, e.g. B. an organic screen printing agent, such as ethyl cellulose dissolved in acetone-toluene. The resulting mixture, which contains the carrier, is applied to an electrically non-conductive substrate and then baked in air.

Das US-Patent 3 324 049 beschreibt ein Cermet-Widerstandsmaterial, das 40 bis 99 Gew.-% eines Bleiborosilikatglases, 0,5 bis 20 Gew.-% eines Edelmetalles, wie Ag, Au, Pd, Pt, Rh, Ir, Os oder Ru und 0,5 bis 40 Gew.-% MnO2 oder Cu0 enthält. Das resultierende Widerstandsmaterial wird dann in Luft eingebrannt.US Pat. No. 3,324,049 describes a cermet resistance material which contains 40 to 99% by weight of a lead borosilicate glass, 0.5 to 20% by weight of a noble metal, such as Ag, Au, Pd, Pt, Rh, Ir, Os or Ru and 0.5 to 40 wt .-% MnO 2 or Cu0 contains. The resulting resistance material is then burned in air.

Das US-Patent 3 655 440 betrifft eine Widerstandszusammensetzung, die RuO2, IrO2 oder PdO, ein glasiges Bleiborosilikat-Bindemittel und ein elektrisch nichtleitendes, Kristallwachstum steuerndes Mittel enthält, z. B. A103, das submikron kleine Inertteilchen enthält. Eine solche Widerstandszusammensetzung wird in Luft bei 975 bis 1025° C während einer Zeit von 45 Minuten bis 1 Stunde eingebrannt.U.S. Patent 3,655,440 relates to a resistance composition containing RuO 2 , IrO 2 or PdO, a glassy lead borosilicate binder and an electrically non-conductive crystal growth control agent, e.g. B. A10 3 , which contains submicron small inert particles. Such a resistance composition is baked in air at 975 to 1025 ° C for 45 minutes to 1 hour.

Das US-Patent 3 682 840 betrifft elektrische Widerstandszusammensetzungen, enthaltend Bleiruthenat und Mischungen daraus mit Ru02 in Verbindung mit Bleiborosilikat-Bindemittel.The US Patent 3,682,840 relates to electrical resistance compositions containing lead ruthenate and mixtures thereof with Ru0 2 in conjunction with lead borosilicate binder.

Das US-Patent 4 065 743 betrifft einen glasigen Schmelz(Enamel)-Widerstand, der eine Glasfritte und elektrisch leitfähige Teilchen enthält. Solche elektrisch leitfähigen Teilchen enthalten Zinnoxid und Tantaloxid.U.S. Patent 4,065,743 relates to a glassy enamel resistor containing a glass frit and electrically conductive particles. Such electrically conductive particles contain tin oxide and tantalum oxide.

Das US-Patent 4 101 708 ist auf eine druckbare Zusammensetzung aus feinteiligem Pulver in einem inerten flüssigen Trägermittel gerichtet zur Herstellung von Filmwiderständen, die auf einem dielektrischen Substrat haften; solche Zusammensetzungen enthalten RuO2, ein PbO enthaltendes Glas, Nb205, CaF2 und ein inertes Trägermittel.U.S. Patent 4,101,708 is directed to a printable composition of finely divided powder in an inert liquid vehicle for making film resistors that adhere to a dielectric substrate; such compositions contain RuO 2 , a glass containing PbO, Nb 2 0 5 , CaF 2 and an inert carrier.

Die deutsche Patentschrift 21 15 814 betrifft eine Widerstandspaste zum Einbrennen auf Keramik in Luft. Diese Widerstandspaste enthält BaRuO3, SrRu03 und CaRu03 in einem Bleiborosilikatglas.German patent specification 21 15 814 relates to a resistance paste for baking on ceramics in air. This resistance paste contains BaRuO 3 , SrRu0 3 and CaRu0 3 in a lead borosilicate glass.

Es wurden auch Widerstandszusammensetzungen hergestellt, die Ag-Pd und/oder PdO, RuO2, Ir02 und die sogenannten "du Pont"-Pyrochlor-Verbindungen benutzen. Die Pyrochlor-Strukturen sind komplexe Oxide der allgemeinen Formel A2B2O6-7, wobei das große Kation A in achtfacher Koordination und das kleine Kation B in oktaedrischer Koordination vorliegen. Ihr Erfolg beruht hauptsächlich auf ihrer Stabilität in veränderbaren Atmosphären (reduzierend) und ihrer Fähigkeit, durch Vielfachsubstitution von Elementen ihre elektrischen Eigenschaften zu ändern. Beispiele von Pyrochlor-Uerbindungen, die speziell in diesen Zusammensetzungen benutzt werden und in den US-Patenten 3 553 109, 3 560 410 und 3 583 931 (alle diese Patente umfassen Bleiborosilikat-Bindemittel) diskutiert wurden, enthalten Bi2Ru2O7 und Pb2Ru2O7-x, wobei 0 < x < 1 ist.Resistance compositions were also made using Ag-Pd and / or PdO, RuO 2 , Ir0 2 and the so-called "du Pont" pyrochlore compounds. The pyrochlore structures are complex oxides of the general formula A 2 B 2 O 6-7 , with the large cation A in eightfold coordination and the small cation B in octahedral coordination. Their success is mainly due to their stability in changeable atmospheres (reducing) and their ability to change their electrical properties through multiple substitution of elements. Examples of pyrochlore compounds that are specifically used in these compositions and discussed in U.S. Patents 3,553,109, 3,560,410 and 3,583,931 (all of which patents include lead borosilicate binders) include Bi 2 Ru 2 O 7 and Pb 2 Ru 2 O 7-x , where 0 <x <1.

Die spezifischen Widerstände von verschiedenen Edelmetall-Oxiden (primär Pyrochlor-Verbindungen und einige Perowskite) wurden von K. Bube in Proceedings of Inter. Microel. Symp., Okt.30./ Nov. 1., 1972, Washington, D. C., ISHM, tabellarisch wie folgt zusammengestellt:

Figure imgb0001
Figure imgb0002
 The specific resistances of various noble metal oxides (primarily pyrochlore compounds and some perovskites) were described by K. Bube in Proceedings of Inter. Microel. Symp., Oct. 30 / Nov. 1, 1972, Washington, DC, ISHM, tabulated as follows:
Figure imgb0001
Figure imgb0002

Die Perowskit-Kristallstruktur wurde beschrieben von U. M. Goldsmith, Skrifter Norske Videnskaps - Akad., Oslo, I: Mat. Naturv.Kl. 2:8 (1926). In der Perowskit-Zusammensetzung ABO3 liegt das A-Kation in zwölffacher Koordination mit Sauerstoff und das kleinere B-Kation in oktaedrischer Koordination vor. Die Perowskit-Struktur besitzt hohe Gitter-Energie und ist im allgemeinen eine sehr stabile Struktur.The perovskite crystal structure was described by UM Goldsmith, Skrifter Norske Videnskaps - Akad., Oslo, I: Mat. Naturv.Kl. 2: 8 (1926). In the perovskite composition ABO 3 , the A cation is in twelve coordination with oxygen and the smaller B cation is in octahedral coordination. The perovskite structure has high lattice energy and is generally a very stable structure.

Widerstandszusammensetzungen wurden im Siebdruck-Verfahren aufgebracht, die ein Einbrennen in oxidierender Atmosphäre (Luft) erfordern, welches die Benutzung von teuren Edelmetallen, wie Au, Ag, Pt und Pd notwendig macht. Das weniger teure Kupfer konnte nicht verwendet werden, weil Kupfer leicht oxidiert. Dementsprechend besteht eine Notwendigkeit für eine stabile kupferkompatible Widerstandszusammensetzung, die in einer nicht oxidierenden Atmosphäre, wie z. B. SLicktoff, aufgebrannt werden könnte.Resistance compositions have been applied by screen printing, which require a baking in an oxidizing atmosphere (air), which necessitates the use of expensive precious metals such as Au, Ag, Pt and Pd. The less expensive copper could not be used because copper oxidizes easily. Accordingly, there is a need for a stable copper-compatible resistor composition that can be used in a non-oxidizing atmosphere, such as. B. SLicktoff, could be burned.

Typische, früher verwendete Widerstandszusammensetzungen benutzen Bleiborosilikatglas-Bindemittel. Nach dem Einbrennen in Luft zersetzt sich in den Widerstandszusammensetzungen, die z. B. Strontiumruthenat in einem Bleiborosilikat-Bindemittel enthalten, das Strontiumruthenat zu Strontiumoxid, welches sich in dem Bindemittel löst, und Rutheniumoxid. Bei der vorliegenden Erfindung, wenn z. B. Strontiumruthenat in einem Strontiumborosilikat-Bindemittel unter Stickstoff eingebrannt wird, findet keine Zersetzung der elektrisch leitfähigen Komponente statt, d. h. das Strontiumruthenat bleibt unverändert.Typical resistance compositions used previously use lead borosilicate glass binders. After baking in air, it decomposes in the resistance compositions, e.g. B. strontium ruthenate in a lead borosilicate binder, the strontium ruthenate to strontium oxide, which dissolves in the binder, and ruthenium oxide. In the present invention, when e.g. B. strontium ruthenate is stoved in a strontium borosilicate binder under nitrogen, there is no decomposition of the electrically conductive component, i. H. the strontium ruthenate remains unchanged.

Zusammenfassung der ErfindungSummary of the invention

Es ist eine Aufgabe der vorliegenden Erfindung, eine stabile kupferkompatible Widerstandszusammensetzung bereitzustellen, die in nicht oxidierender Atmosphäre eingebrannt werden kann.It is an object of the present invention to provide a stable copper compatible resistor composition that can be baked in a non-oxidizing atmosphere.

Eine andere Aufgabe der vorliegenden Erfindung ist es, ein Dickfilm-Widerstandssystem bereitzustellen, welches eine Reproduzierbarkeit der Eigenschaften und eine verminderte Verarbeitungsempfindlichkeit besitzt.Another object of the present invention is to provide a thick film resistor system which has property reproducibility and reduced processing sensitivity.

Die vorliegende Erfindung betrifft eine Zusammensetzung zur Herstellung eines elektrischen Widerstands elementes, die aus einer elektrisch leitfähigen Komponente und einem Bindemittel zusammengesetzt ist.The present invention relates to a composition for producing an electrical resistance element, which is composed of an electrically conductive component and a binder.

Die elektrisch leitende Komponente enthält ein Edelmetalloxid der Formel A' 1-xA" xB', 1-yB"yO3,

  • wobei A' = Sr oder Ba mit der Maßgabe, daß wenn A' = Sr, dann ist A" ein odcr mehrere Elemente aus der Gruppe Ba, La, Y, Ca und Na und wenn A' = Ba, dann ist A" ein oder mehrere Elemente aus der Gruppe Sr, La, Y, Ca und Na
  • B' = Ru
  • B" = eines oder mehrere der Elemente aus der Gruppe Ti, Cd, Zr, V und Co und
  • 0 < x < 0,2 und
  • 0<y<0,2 ist.
The electrically conductive component contains a noble metal oxide of the formula A ' 1-x A " x B', 1-y B" y O 3 ,
  • where A '= Sr or Ba with the proviso that if A' = Sr, then A "is one or more elements from the group Ba, La, Y, Ca and Na and if A '= Ba, then A" is one or more elements from the group Sr, La, Y, Ca and Na
  • B '= Ru
  • B "= one or more of the elements from the group Ti, Cd, Zr, V and Co and
  • 0 <x <0.2 and
  • 0 <y <0.2.

Die Bindemittelkomponente enthält:

  • (i) 40 bis 75 Gew.-% C', wobei C' = SrO ist, wenn A' = Sr ist;
    • C' = BaO, wenn A' = Ba ist und C' = Sr0 + BaO, wenn A' = Sr ist und A" = Ba ist oder wenn A' = Ba und A" = Sr ist.
  • (ii) 20 bis 35 Gew.-% B2O3
  • (iii) 2 bis 15 Gew.-% SiO2 und
  • (iv) 0,5 bis 6,5 Gew.-% ZnO.
The binder component contains:
  • (i) 40 to 75% by weight of C ', where C' = SrO when A '= Sr;
    • C '= BaO when A' = Ba and C '= Sr0 + BaO when A' = Sr and A "= Ba or when A '= Ba and A" = Sr.
  • (ii) 20 to 35 wt% B 2 O 3
  • (iii) 2 to 15 wt% SiO 2 and
  • (iv) 0.5 to 6.5 wt% ZnO.

Die vorliegende Erfindung betrifft auch ein Verfahren zur Herstellung eines elektrischen Widerstandselementes durch Erzeugen der vorbeschriebenen Zusammensetzung, Anpasten dieser Zusammensetzung mit einem organischen Trägermittel, Aufbringen der Paste im Siebdruckverfahren auf ein Substrat und Einbrennen.The present invention also relates to a method for producing an electrical resistance element by producing the above-described composition, pasting this composition with an organic carrier, applying the paste by screen printing to a substrate and baking.

Dabei kann die Bindemittelkomponente auch 0,1 bis 2,5 Gew.-% Al2O3 enthalten.The binder component can also contain 0.1 to 2.5% by weight of Al 2 O 3 .

Die Bindemittelkomponente kann weiterhin 0,1 bis 1,5 Gew.-% eines oder mehrerer der folgenden Oxide enthalten:
Bi203, CuO, MgO, Nb2O5.The binder component may further contain 0.1 to 1.5% by weight of one or more of the following oxides:
Bi203, CuO, MgO, Nb 2 O 5 .

Die Bindemittelkomponente kann auch noch weiterhin 0,1 bis 1,5 Gew.-% TiO2 oder NaF enthalten. Gegebenenfalls kann die Bindemittelkomponente auch noch 5 bis 15 Gew.-% Ca0 enthalten.The binder component can also still contain 0.1 to 1.5% by weight of TiO 2 or NaF. If necessary, the Binder component also contain 5 to 15 wt .-% Ca0.

Detaillierte Beschreibung der ErfindungDetailed description of the invention

Die Zusammensetzung zur Herstellung elektrischer Widerstandselemente gemäß der vorliegenden Erfindung enthält eine elektrisch leitfähige Metalloxid-Perowskitkomponente und eine Glasbindemittelkomponente.The composition for manufacturing electrical resistance elements according to the present invention contains an electrically conductive metal oxide perovskite component and a glass binder component.

Die elektrisch leitfähige Komponente wird durch die Formel A'1-xA"xB'1-yB"yO3 dargestellt, wobei

  • A' = Sr oder Ba mit der Maßgabe, daß wenn A' = Sr, dann ist A" ein oder mehrere Elemente aus der Gruppe Ba, La, Y, Ca und Na und wenn A' = Ba, dann ist A" ein oder mehrere Elemente aus der Gruppe Sr, La, Y, Ca und Na,
  • B' = Ru
  • B" = eines oder mehrere der Elemente aus der Gruppe Ti, Cd, Zr, V und Co und
  • 0<x<0,2 und
  • 0<y<0,2 ist.
  • Bevorzugte Kombinationen von B'1 -y B" Y umfassen Ru0, 8Ti0,2
  • und Ru0,9 Ti0,1.
The electrically conductive component is represented by the formula A ' 1-x A " x B' 1-y B" y O 3 , where
  • A '= Sr or Ba with the proviso that if A' = Sr, then A "is one or more elements from the group Ba, La, Y, Ca and Na and if A '= Ba, then A" is one or several elements from the group Sr, La, Y, Ca and Na,
  • B '= Ru
  • B "= one or more of the elements from the group Ti, Cd, Zr, V and Co and
  • 0 <x <0.2 and
  • 0 <y <0.2.
  • Preferred combinations of B '1-y B "Y include Ru 0, 8 Ti 0.2
  • and Ru 0.9 Ti 0.1 .

Bevorzugte elektrisch leitfähige Komponenten umfassen SrRu0.8. Ti0,2O3, SrRu0 3 und SrRu0,9Ti0,1O3. Kombinationen dieser Komponenten können ebenfalls benutzt werden, wie z. B. SrRuO3 + SrRu0,8Ti0,2O3 oder SrRu0 3 + SrRu0,9Ti0,1O3. Andere nicht einschränkend zu behandelnde Beispiele für die leitfähigen Komponenten umfassen SrRu0,95C d0,05O3, Sr0,90Na0,10RuO3, Sr0,90y0,10RuO3, Sr0,80Na0,10La0,10RuO3 und SrRu0,8RuTi0,2O3/ SrRu0 3, SrRu0,8Zr0,2O3, SrRu0,9Zr0,1O3, SrRu0,75V0,25O3 und SrRu0,8Co0,2O3.Preferred electrically conductive components include SrRu 0.8 . Ti 0.2 O 3 , S r R u 0 3 and SrRu 0.9 Ti 0.1 O 3 . Combinations of these components can also be used, such as. B. SrRuO 3 + SrRu 0.8 Ti 0.2 O 3 or S r Ru0 3 + SrRu 0.9 Ti 0.1 O 3 . Other non-limiting examples of the conductive components include SrRu 0.95 C d 0.05 O 3 , Sr 0.90 Na 0.10 RuO 3 , Sr 0.90 y 0.10 RuO 3 , Sr 0.80 Na 0.10 La 0.10 RuO 3 and SrRu 0.8 RuTi 0.2 O 3 / SrRu0 3 , SrRu 0.8 Zr 0.2 O 3 , SrRu 0.9 Zr 0.1 O 3 , SrRu 0.75 V 0.25 O 3 and SrRu 0.8 Co 0.2 O 3 .

Die Formel A'1-xA"xB'1-yB"yO3 kann durch teilweise Substitution von A, B oder A und B (A = A'+A"; B = B'+B") geändert werden, wie oben beschrieben und durch Benutzung anderer Substitutionen. Nicht einschränkende Beispiele von Substitutionen (basierend auf den Ionenradien und der Wertigkeit) von A und B sind folgende:

Figure imgb0003
The formula A ' 1-x A " x B' 1-y B" y O 3 can be changed by partial substitution of A, B or A and B (A = A '+ A "; B = B' + B") as described above and using other substitutions. Non-limiting examples of substitutions (based on ionic radii and valency) of A and B are as follows:
Figure imgb0003

Die Bindemittelkomponente der vorliegenden Erfindung besitzt als Hauptbestandteile C', d. h. SrO oder BaO oder Sr0 + BaO, und B2O3, SiO2 und Zn0 in den folgenden Mengen:

Figure imgb0004
The main components of the binder component of the present invention are C ', ie SrO or BaO or Sr0 + BaO, and B 2 O 3 , SiO 2 and Zn0 in the following amounts:
Figure imgb0004

Zusätzlich kann die Bindemittelkomponente noch ein oder mehrere der folgenden Bestandteile umfassen:

Figure imgb0005
In addition, the binder component can also comprise one or more of the following constituents:
Figure imgb0005

Nicht einschränkende Beispiele von bevorzugten Zusammensetzungen der Bindemittelkomponente umfassen die folgenden:

Figure imgb0006
Figure imgb0007
 Nonlimiting examples of preferred compositions of the binder component include the following:
Figure imgb0006
Figure imgb0007

Beispiele anderer, nicht einschränkender Zusammensetzungen der Bindemittelkomponente umfassen die folgenden:

Figure imgb0008
Examples of other, non-limiting compositions of the binder component include the following:
Figure imgb0008

Das Gewichts-%-Verhältnis von Bindemittelkomponente / elektrisch leitfähiger Komponente kann variieren von 25 bis 75 Gew.-% Bindemittelkomponente/75 bis 25 Gew.-% elektrisch leitfähige Komponente, d. h. die Bindemittelkomponente kann z. B. 30, 35, 40, 50, 60, 65 oder 70 Gew.-% betragen.The weight% ratio of binder component / electrically conductive component can vary from 25 to 75% by weight of binder component / 75 to 25% by weight of electrically conductive component, i. H. the binder component can e.g. B. 30, 35, 40, 50, 60, 65 or 70 wt .-%.

Die Bindemittelkomponente und die elektrisch leitfähige Komponente werden mit einem geeigneten "organischen Trägermittel" vermischt. Ein organisches Trägermittel ist ein Medium, welches sich bei einer relativ niedrigen Temperatur (ungefähr 400 bis 500° C) verflüchtigt, ohne eine Reduktion anderer Pastenkomponenten zu verursachen. Ein organisches Trägermittel dient als Übertragungsmittel für das Siebdrucken. Ein organisches Trägermittel für die Benutzung in der vorliegenden Erfindung ist vorzugsweise ein Harz, z. B. ein Acrylsäureesterharz, vorzugsweise ein Isobutylmethacrylat, und ein Lösungsmittel, z. B. ein Alkohol, vorzugsweise Tridecylalkohol ("TDA"). Das Harz kann irgendein Polymer sein, welches bei oder unterhalb 400° C in Stickstoff depolymerisiert. Andere Lösungsmittel, die verwendet werden können, sind Terpineol oder "TEXANOL" der Firma Eastman Kodak. Das Lösungsmittel zur Benutzung der vorliegenden Erfindung kann irgendein Lösungsmittel sein, welches das betreffende Harz löst und welches einen geeigneten Dampfdruck aufweist, der im Einklang mit dem nachfolgenden Mahlen und Siebdrucken steht. In bevorzugter Ausführungsform besteht das organische Trägermittel aus 10 bis 30 Gew.-% Isobutylmethacrylat und 90 bis 70 Gew.-% TDA.The binder component and the electrically conductive component are mixed with a suitable "organic carrier" mixed. An organic vehicle is a medium that volatilizes at a relatively low temperature (approximately 400 to 500 ° C) without causing a reduction in other paste components. An organic carrier serves as a transfer medium for screen printing. An organic vehicle for use in the present invention is preferably a resin, e.g. B. an acrylic ester resin, preferably an isobutyl methacrylate, and a solvent, e.g. B. an alcohol, preferably tridecyl alcohol ("TDA"). The resin can be any polymer that depolymerizes in nitrogen at or below 400 ° C. Other solvents that can be used are Terpineol or "TEXANOL" from Eastman Kodak. The solvent for use in the present invention may be any solvent which dissolves the resin in question and which has an appropriate vapor pressure consistent with the subsequent milling and screen printing. In a preferred embodiment, the organic carrier consists of 10 to 30% by weight of isobutyl methacrylate and 90 to 70% by weight of TDA.

Die Bindemittelkomponente, die elektrisch leitfähige Komponente und das organische Trägermittel werden gemischt und im Siebdruck- verfahren auf den Kupferanschluß auf ein geeignetes Substrat, z. B. aus 96 % Al2031 im Siebdruckverfahren aufgebracht und dann in einer Stickstoffatmosphäre bei einer Temperatur von z. B. 900° C eine geeignete Zeit, z. B. 7 Minuten, eingebrannt. Zur Bereitung der Zusammensetzung für die Herstellung elektrischer Widerstandselemente gemäß der vorliegenden Erfindung werden die elektrisch leitfähige Komponente, die Bindemittelkomponente und das organische Trägermittel zusammengebracht zur Bildung einer Paste. Die Paste wird dann zu der für die Siebdrucktechnik erforderlichen Feinheit gemahlen.The binder component, the electrically conductive component and the organic carrier are mixed and screen printed onto the copper connection on a suitable substrate, eg. B. from 96% Al 2 0 31 by screen printing and then in a nitrogen atmosphere at a temperature of z. B. 900 ° C a suitable time, e.g. B. 7 minutes, baked. To prepare the composition for the manufacture of electrical resistance elements according to the present invention, the electrically conductive component, the binder component and the organic carrier are brought together to form a paste. The paste is then ground to the fineness required for the screen printing technique.

Es wird angenommen, daß die Bindemittelkomponente (Glasmatrix) der vorliegenden Erfindung die Zersetzung der elektrisch leitfähigen Komponente während des Einbrennens verhindert, d. h. die Kristallstruktur (physikalisch) und die chemische Zusammensetzung der elektrisch leitfähigen Komponente bleiben stabil und unverändert während des Einbrennens.It is believed that the binder component (glass matrix) of the present invention prevents decomposition of the electrically conductive component during baking, i.e. H. the crystal structure (physical) and the chemical composition of the electrically conductive component remain stable and unchanged during baking.

BeispieleExamples Beispiel 1: Bindemittel-HerstellungExample 1: Binder production

Das Bindemittel wird synthetisiert unter Benutzung von analysenreinen Materialien, wobei jedes in Oxidform vorliegt mit Ausnahme der Strontium-, Barium- und Kupfer-Verbindungen, die als Carbonate vorliegen. Wenn die Zusammensetzung angesetzt wird, dann werden die einzelnen Komponente eingewogen und 1 Stunde lang homogenisiert in einem V-Mischer (welches ein Trockenmischverfahren ist). Nachdem das Mischen fertig ist, werden die homogenisierten Pulver in einen Cyanit-Tiegel gebracht, in dem sie dann anschließend geschmolzen werden. Die Bindemittel werden 1 Stunde lang bei 600° C vorerhitzt und dann in einen anderen Ofen überführt, in dem sie dann geschmolzen werden in einem Temperaturbereich von 1100 bis 1300° C während einer Zeit von 1 bis 1,5 Stunden. Das geschmolzene Material wird bei Schmelztemperatur aus dem Ofen genommen und in eine Wanne aus rostfreiem Stahl, die mit deionisiertem Wasser gefüllt ist, abgegossen. Sobald die Schmelze mit dem Wasser in Berührung kommt, findet eine Verfestigung und ein Zerfall in Glasbröckchen statt (wobei die Größe oder die thermische Spannung vorgegeben wird). Das deionisierte Wasser wird dekantiert und das Glas danach in eine keramische Kugelmühle mit Mahlzylindern aus Aluminiumoxid unter Zusatz von Isobutylalkohol gegeben. Die Gläser werden 24 Stunden gemahlen und dann naß gesiebt durch ein 200 mesh-Sieb. Nach dem Trocknen in einem explosionssicheren Konvektionsofen bei Raumtemperatur sind die Pulver fertig zur Charakterisierung und zum Einbringen in die Widerstandspaste. Die Teilchengröße der Pulver beträgt 1 bis 2 µm. Die so hergestellten Bindemittelkomponenten sind dann solche, wie sie oben als Zusammensetzungen I, II und III angegeben sind. Die Erweichungspunkte für die Zusammensetzungen I, II und III wurden mit 625° C, 635° C und 660° C ermittelt. Andere Zusammensetzungen der Bindemittelkomponente, die entsprechend dem Beispiel 1 hergestellt sind, sind folgende:

Figure imgb0009
The binder is synthesized using analytical grade materials, each in the oxide form except for the strontium, barium and copper compounds which are present as carbonates. When the composition is made up, the individual components are weighed and homogenized for 1 hour in a V-mixer (which is a dry mixing process). After mixing is complete, the homogenized powders are placed in a cyanite crucible, where they are then melted. The binders are preheated at 600 ° C for 1 hour and then transferred to another oven where they are then melted in a temperature range of 1100 to 1300 ° C for a period of 1 to 1.5 hours. The molten material is removed from the furnace at the melting temperature and poured into a stainless steel tub filled with deionized water. As soon as the melt comes into contact with the water, it solidifies and disintegrates into glass fragments (the size or the thermal stress being specified). The deionized water is decanted and the glass is then placed in a ceramic ball mill with grinding cylinders made of aluminum oxide with the addition of isobutyl alcohol. The jars are ground for 24 hours and then wet sieved through a 200 mesh screen. After drying In an explosion-proof convection oven at room temperature, the powders are ready for characterization and for incorporation in the resistance paste. The particle size of the powder is 1 to 2 µm. The binder components thus produced are then those as stated above as compositions I, II and III. The softening points for compositions I, II and III were determined to be 625 ° C, 635 ° C and 660 ° C. Other binder component compositions made according to Example 1 are as follows:
Figure imgb0009

Beispiel 2: Herstellung der elektrisch leitfähigen KomponenteExample 2: Production of the electrically conductive component

Die elektrisch leitfähigen Komponenten werden bereitet durch Ansetzen der entsprechenden Verbindung (z. B. SrRu03), Berechnen der äquimolaren Menge von z. B. SrCO3 und RuO2, die gewogen werden müssen, um die Stöchlometrie sicherzustellen und letztendlich Wiegen der einzelnen Komponenten. Korrekturfaktoren für den Ru-Metallgehalt, den Wassergehalt und andere flüchtige Komponenten, die beim Glühen bei 600° C verlorengehen, sind ebenfalls in die Berechnung eingeschlossen. Ein ähnlicher Korrekturfaktor für den Glühverlust wurde ebenfalls in die Berechnung für die Gewichte der anderen Komponenten einbezogen, sofern notwendig. Das RuO2 hat eine Oberfläche von mehr als 70 m2/g, während die anderen Bestandteile eine Oberfläche von weniger als 5 m2/g haben. Die gewogenen Ausgangsmaterialien werden in einer Keramikkugelmühle mit Aluminiumoxid-Mahl-Einrichtungen 2 Stunden lang zusammen mit deionisiertem Wasser gemahlen, also einem Naß-Mahlverfahren unterworfen. Nach 2 Stunden wird die homogenisierte Aufschlämmung in Tröge aus rostfreiem Stahl gegossen und 24 Stunden bei 80° C getrocknet. Die getrocknete Mischung wird vor Kalzinierung durch ein 80 mesh-Sieb gesiebt.The electrically conductive components are prepared by attaching the appropriate connection (e.g. SrRu03), calculating the equimolar amount of e.g. B. SrCO 3 and RuO 2 , which must be weighed to ensure the stoichlometry and ultimately weighing the individual components. Correction factors for the Ru metal content, water content and other volatile components that are lost when annealing at 600 ° C are also included in the calculation. A similar one Correction factor for the loss on ignition was also included in the calculation for the weights of the other components, if necessary. The RuO 2 has a surface area of more than 70 m 2 / g, while the other components have a surface area of less than 5 m 2 / g. The weighed starting materials are ground in a ceramic ball mill with aluminum oxide grinding devices for 2 hours together with deionized water, that is to say subjected to a wet grinding process. After 2 hours, the homogenized slurry is poured into stainless steel troughs and dried at 80 ° C for 24 hours. The dried mixture is sieved through an 80 mesh screen before calcination.

Die gesiebten Pulver werden in Tiegel aus hochreinem Aluminiumoxid (Reinheit 99,8 %) kalziniert, wobei dieser Schritt genau mikroprozessorgeregelt durchgeführt wird. Die Aufheiz- und Abkühlungsgeschwindigkeiten sind an sich nicht kritisch, sie betragen allgemein 500° C/Std. Die Haltezeiten bei den betreffenden Temperaturen (von 800 bis 1200° C, abhängend von der Verbindung) variieren zwischen 1 und 2 Stunden. Nach Beendigung der Kalzinierung werden die Pulver in einer Sweeco-Schwingmühle 2 Stunden gemahleri. Dies ist ein Hochenergie-Mahlverfahren, bei dem Aluminiumoxid-Mahlmittel und Isopropylalkohol benutzt werden. Die Perowskite werden naß gesiebt (200 mesh) am Ende der Mahlstufe, bei Zimmertemperatur in einem Konvektionsofen (explosionssicher) getrocknet und für die Charakterisierung und die Einbringung in die Widerstandspaste vorbereitet.The sieved powders are calcined in crucibles made of high-purity aluminum oxide (purity 99.8%), this step being carried out precisely with microprocessor control. The heating and Abkühlun sgeschwindigkeiten g are not critical per se, they are generally from 500 ° C / hr. The holding times at the relevant temperatures (from 800 to 1200 ° C, depending on the connection) vary between 1 and 2 hours. After the calcination is complete, the powders are ground in a Sweeco vibratory mill for 2 hours. This is a high energy milling process using alumina milling media and isopropyl alcohol. The perovskites are sieved wet (200 mesh) at the end of the grinding stage, dried at room temperature in a convection oven (explosion-proof) and prepared for characterization and incorporation in the resistance paste.

Die elektrisch leitfähigen Komponenten, die nach dem vorbeschriebenen Verfahren hergestellt wurden, enthalten folgendes:

Figure imgb0010
The electrically conductive components, which were produced according to the above-described method, contain the following:
Figure imgb0010

Beispiel 3: Kombination von Bindemittelkomponenten elektrisch leitfähigen KomponentenExample 3: Combination of binder components of electrically conductive components

Die Bindemittelkomponenten, die in Übereinstimmung mit dem Beispiel 1 hergestellt werden, werden mit elektrisch leitfähigen Komponenten, die nach Beispiel 2 hergestellt werden, kombiniert zusammen mit einem organischen Trägermittel. Als organisches Trägermittel wird "ACRYLOID" B67, ein Harz (ein Isobutylmethacrylat) der Firma Rohm & Haas, Philadelphia, Pennsylvania, und Tridecylalkohol ("TDA") im Gewichtsverhältnis 30 : 70 verwendet.The binder components made in accordance with Example 1 are combined with electrically conductive components made in Example 2 together with an organic carrier. "ACRYLOID" B67, a resin (an isobutyl methacrylate) from Rohm & Haas, Philadelphia, Pennsylvania, and tridecyl alcohol ("TDA") in a weight ratio of 30:70 is used as the organic carrier.

Die betreffenden Bindemittelkomponenten, die elektrisch leitfähigen Komponenten und das organische Trägermittel werden gewogen, um die gewünschte Pastenmischung herzustellen. Der Gehalt an Feststoffen (Bindemittel + elektrisch leitfähige Phase) wird bei 70 Gew.-%, bezogen auf das Gesamt-Pastengewicht, gehalten. Die Paste wird in einer Drei-Rollen-Mühle zu einer Feinheit von 10 µm gemahlen. Widerstandsprüfmuster werden im Siebdruckverfahren mit den folgenden Druck-Dicken aufgebracht: naß 29 bis 32 µm; gebrannt 10 bis 13 µm. Die Pasten werden dann entweder durch ein 325 mesh-Sieb mit 0,6 mil-emulsion oder durch ein 280 mesh-Sieb mit einer 0,5 mil-emulsion gedruckt. Die feuchten Drucke werden 5 bis 10 Minuten bei 150° C vor dem Einbrennen aetrocknet.The relevant binder components, the electrically conductive components and the organic carrier are weighed to produce the desired paste mixture. The solids content (binder + electrically conductive phase) is kept at 70% by weight, based on the total paste weight. The paste is ground in a three-roller mill to a fineness of 10 µm. Resistance test samples are screen printed with the following printing thicknesses: wet 29 to 32 µm; fired 10 to 13 µm. The pastes are then either mil emulsion or through a 325 mesh screen with 0, 6 printed through a 280 mesh screen with a 0.5 mil emulsion. The damp prints are dried for 5 to 10 minutes at 150 ° C before baking.

Das Einbrennprofil war abhängig von der Zusammensetzung der Bindemittelkomponente, z. B. wurden Pasten, die die Zusammensetzung I enthielte bei 850° C eingebrannt, während Pasten, die die Zusammensetzung II oder III enthielten, bei 900° C eingebrannt wurden. Die 850°C-Profillänge betrug 58 Minuten von 100° C zu 100° C, d. h. vom Ofeneingang bis zum Ofenausgang. Die Aufheizgeschwindigkeit betrug 45° C pro Minute, die Abkühlgeschwindigkeit 60° C pro Minute, und die Verweilzeit bei der Höchsttemperatur betrug 10 Minuten. Das 900°C-Profil hatte eine Dauer von 55 Minuten von 100° C zu 100° C, eine Aufheizgeschwindigkeit von 50° C pro Minute und eine Abkühlgeschwindigkeit von 60° C pro Minute, die Verweilzeit bei der Höchsttemperatur variierte zwischen 5 und 14 Minuten.The stoving profile was dependent on the composition of the binder component, e.g. For example, pastes containing Composition I were baked at 850 ° C, while pastes containing Composition II or III were baked at 900 ° C. The 850 ° C profile length was 58 minutes from 100 ° C to 100 ° C, i.e. H. from the furnace entrance to the furnace exit. The heating rate was 45 ° C per minute, the cooling rate 60 ° C per minute, and the residence time at the maximum temperature was 10 minutes. The 900 ° C profile had a duration of 55 minutes from 100 ° C to 100 ° C, a heating rate of 50 ° C per minute and a cooling rate of 60 ° C per minute, the residence time at the maximum temperature varied between 5 and 14 minutes .

Verschiedene Kombinationen der oben beschriebenen Bindemittelkomponenten und elektrisch leitfähigen Komponenten zur Herstellung von Widerstandselementen und die resultierenden Eigenschaften nach dem Einbrennen in Stickstoff werden in den nachfolgenden Tabellen 9 und 10 wiedergegeben. Für Tabelle 9 wurde ein Einbrennen bei 850° C unter Stickstoff verwendet.Various combinations of the binder components described above and electrically conductive components for the production of resistance elements and the resulting properties after baking in nitrogen are given in Tables 9 and 10 below. For Table 9, baking at 850 ° C under nitrogen was used.

Besonders bewährt haben sich die nachfolgend aufgeführten drei Zusammensetzungen der Bindemittelkomponente, die durch die angegebenen Gewichtsprozente gekennzeichnet sind:

  • 1. Bindemittelkomponente aus 51,7 Gew.-% SrO, 30,0 Gew.-% B2O5, 10,5 Gew.-% SiO2, 1,1 Gew.-% Al2O3, 3,4 Gew.-% ZnO, 0,5 Gew.-% Bi2O3, 0,6 Gew.-% CuO, 0,7 Gew.-% MgO, 0,5 Gew.-% Nb2O5, 0,5 Gew.-% Ti02 und 0,5 Gew.-% NaF,
  • 2. Bindeniittelkomponente aus 55,2 Gew.-% SrO, 30 Gew.-% B2O3, 7,0 Gew.-% Si02, 1,1 Gew.-% A1203, 3,4 Gew.-% ZnO, 0,5 Gew.-% Bi2O3, 0,6 Gew.-% CuO, 0,7 Gew.-% MgO, 0,5 Gew.-% Nb2O5, 0,5 Gew.-% TiO2 und 0,5 Gew.-% NaF,
  • 3. Bindemittelkomponente aus 56,6 Gew.-% SrO, 30,1 Gew.-% B2O3, 7,1 Gew.-% SiO2, 0,5 Gew.-% A1203, 3,4 Gew.-% ZnO, 0,5 Gew.-% Bi2O3, 0,6 Gew.-% CuO, 0,7 Gew.-% MgO und 0,5 Gew.-% Nb2O3.
    Figure imgb0011
    Figure imgb0012
    Figure imgb0013
    Figure imgb0014
The three compositions of the binder component listed below, which are characterized by the weight percentages given, have proven particularly useful:
  • 1. binder component of 51.7 wt .-% SrO, 30.0 wt .-% B 2 O 5, 10, 5 wt .-% SiO 2, 1.1 wt .-% Al 2 O 3, 3.4 % By weight ZnO, 0.5% by weight Bi 2 O 3 , 0.6% by weight CuO, 0.7% by weight MgO, 0.5% by weight Nb 2 O 5 , 0, 5% by weight Ti0 2 and 0.5% by weight NaF,
  • 2. Binder component composed of 55.2% by weight of SrO, 30% by weight of B 2 O 3 , 7.0% by weight of SiO 2 , 1.1% by weight of A1203, 3.4% by weight of ZnO , 0.5% by weight Bi 2 O 3 , 0.6% by weight CuO, 0.7% by weight MgO, 0.5% by weight Nb 2 O 5 , 0.5% by weight TiO 2 and 0.5% by weight NaF,
  • 3. Binder component composed of 56.6% by weight of SrO, 30.1% by weight of B 2 O 3 , 7.1% by weight of SiO 2 , 0.5% by weight of A1203, 3.4% by weight % ZnO, 0.5 wt .-% of Bi 2 O 3, 0, 6 wt .-% CuO, 0.7 wt .-% MgO and 0.5 wt .-% of Nb 2 O 3.
    Figure imgb0011
    Figure imgb0012
    Figure imgb0013
    Figure imgb0014

Claims (13)

1. Zusammensetzung zur Herstellung elektrischer Widerstandselemente, die eine elektrisch leitfähige Komponente (a) und eine Bindemittelkomponente (b) enthält, dadurch gekennzeichnet, daß die elektrisch leitfähige Komponente (a) ein Edelmetalloxid der allgemeinen Formel A'1-xA"xB'1-yB"yO3 ist, wobei A' = Sr oder Ba, mit der Maßgabe, daß wenn A' = Sr, dann ist A" eines oder mehrere der Elemente aus der Gruppe Ba, La, Y, Ca und Na, und wenn A' = Ba, dann ist A" eines oder mehrere der Elemente aus der Gruppe Sr, La, Y, Ca und Na B' = Ru B'' = eines oder mehrere der Elemente aus der Gruppe Ti, Cd, Zr, V und Co ist, und wobei 0 < x < 0,2 und 0 < y < 0,2 ist, und daß die Bindemittelkomponente (b) (i) 40 bis 75 Gew.-% C' , wobei C' = SrO, wenn A' = Sr ist C' = BaO, wenn A' = Ba ist und C' = SrO + BaO, wenn A' = Sr und A'' = Ba oder wenn A' = Ba und A" = Sr sind (ii) 20 bis 35 Gew.-% B2O3 (iii) 2 bis 15 Gew.-% SiO2 und (iv) 0,5 bis 6,5 Gew.-% ZnO. enthält. 1. Composition for the production of electrical resistance elements, which contains an electrically conductive component (a) and a binder component (b), characterized in that the electrically conductive component (a) is a noble metal oxide of the general formula A ' 1-x A " x B' 1-y B " y O 3 , where A '= Sr or Ba, with the proviso that if A '= Sr, then A "is one or more of the elements from the group Ba, La, Y, Ca and Na, and if A '= Ba, then A "is one or more of the elements from the group Sr, La, Y, Ca and Na B '= Ru B '' = one or more of the elements from the group Ti, Cd, Zr, V and Co, and where 0 <x <0.2 and 0 <y <0.2, and that the binder component (b) (i) 40 to 75% by weight of C ', where C' = SrO if A '= Sr C' = BaO if A '= Ba and C' = SrO + BaO if A '= Sr and A '' = Ba or when A '= Ba and A "= Sr (ii) 20 to 35 wt% B 2 O 3 (iii) 2 to 15 wt% SiO 2 and (iv) 0.5 to 6.5 wt% ZnO. contains. 2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Bindemittelkomponente zusätzlich 0,1 bis 2,5 Gew.-% Al2O3 enthält.2. Composition according to claim 1, characterized in that the binder component additionally contains 0.1 to 2.5 wt .-% Al 2 O 3 . 3. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß C' 42 bis 58 Gew.-% beträgt, B203 in einer Menge von 27 bis 31 Gew.-%, SiO2 in einer Menge von 7 bis 11 Gew.-% und Zn0 in einer Menge von 2 bis 4 Gew.-% enthalten sind.3. Composition according to claim 1, characterized in that C 'is 42 to 58 wt .-%, B 2 0 3 in an amount of 27 to 31 wt .-%, SiO 2 in an amount of 7 to 11 wt .-% % and Zn0 are contained in an amount of 2 to 4 wt .-%. 4. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Bindemittelkomponente zusätzlich 0,1 bis 1,5 % eines oder mehrerer der Oxide der Gruppe Bi203, CuO, Mg0 und Nb2O5 enthält.4. Composition according to claim 1, characterized in that the binder component additionally contains 0.1 to 1.5% of one or more of the oxides of the group Bi 2 0 3 , CuO, Mg0 and Nb 2 O 5 . 5. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Bindemittelkomponente zusätzlich 0,1 bis 1,5 Gew.-% TiO2 oder NaF enthält.5. Composition according to claim 1, characterized in that the binder component additionally contains 0.1 to 1.5 wt .-% TiO 2 or NaF. 6. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Bindemittelkomponente zusätzlich 5 bis 15 Gew.-% Ca0 enthält.6. Composition according to claim 1, characterized in that the binder component additionally contains 5 to 15 wt .-% Ca0. 7. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die elektrisch leitfähige Komponente aus einem der folgenden Oxide besteht: SrRu03, SrRu0,8Ti0,2O3, SrRu0,9Ti0,1O3, SrRu0,95C d0,05O3, Sr0,9Ba0,1RuO3, Sr0,9Y0,1RuO3, Sr0,8Na0,1La0,1RuO3, SrRu0,8Zr0,2O3, SrRu0,9Zr0,1O3, SrRu0,75V0,25O3, SrRu0,8Co0,2O3 und SrRu0,8Ti0,1Zr0,1O3.7. The composition according to claim 1, characterized in that the electrically conductive component consists of one of the following oxides: SrRu0 3 , SrRu 0.8 Ti 0.2 O 3 , SrRu 0.9 Ti 0.1 O 3 , SrRu 0, 95 C d 0.05 O 3 , Sr 0.9 Ba 0.1 RuO 3 , Sr 0.9 Y 0.1 RuO 3 , Sr 0.8 Na 0.1 La 0.1 RuO 3 , SrRu 0.8 Zr 0.2 O 3 , SrRu 0.9 Zr 0.1 O 3 , SrRu 0.75 V 0.25 O 3 , SrRu 0.8 Co 0.2 O 3 and SrRu 0.8 Ti 0.1 Zr 0 , 1 O 3 . 8. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß sie ein organisches Trägermittel enthält, vorzugsweise eine Mischung aus einem Acrylsäureesterharz und einem Alkohol, insbesondere Isobutylmethacrylat und Tridecylalkohol.8. The composition according to claim 1, characterized in that it contains an organic carrier, preferably a mixture of an acrylic acid ester resin and an alcohol, in particular isobutyl methacrylate and tridecyl alcohol. 9. Verfahren zur Herstellung eines elektrischen Widerstandselements durch Aufdrucken einer Paste und Einbrennen dieser Paste auf einem Substrat, dadurch gekennzeichnet, daß eine elektrisch leitfähige Komponente (a), die ein Edelmetalloxid der allgemeinen Formel A'1-xA"xB'1-yB" y0 3 ist, wobei A' = Sr oder Ba, mit der Maßgabe, daß wenn A' = Sr, dann ist A" eines oder mehrere der Elemente aus der Gruppe Ba, La, Y, Ca und Na, und wenn A' = Ba, dann ist A" eines oder mehrere der Elemente aus der Gruppe Sr, La, Y, Ca und Na B' = Ru B" = eines oder mehrere der Elemente aus der Gruppe Ti, Cd, Zr, V und Co ist, und wobei 0 < x < 0,2 und 0 < y < 0,2 ist und eine Bindemittelkomponente (b), die (i) 40 bis 75 Gew.-% C', wobei C' = SrO, wenn A' = Sr ist C' = BaO, wenn A' = Ba ist und C' = SrO + BaO, wenn A' = Sr und A" = Ba oder wenn A' = Ba und A'' = Sr sind (ii) 20 bis 35 Gew.-% B2 0 3 (iii) 2 bis 15 Gew.-% SiO2 und (iv) 0,5 bis 6,5 Gew.-% Zn0 enthält
mit einem organischen Trägermittel zu einer Paste vermischt diese Paste im Siebdruckverfahren auf ein Substrat aufgedruckt und leitend eingebrannt wird. 9. A method for producing an electrical resistance element by printing a paste and baking this paste on a substrate, characterized in that an electrically conductive component (a) which is a noble metal oxide of the general formula A ' 1-x A " x B' 1- y B "y 0 3 , where A '= Sr or Ba, with the proviso that if A '= Sr, then A "is one or more of the elements from the group Ba, La, Y, Ca and Na, and if A '= Ba, then A "is one or more of the elements from the group Sr, La, Y, Ca and Na B '= Ru B "= one or more of the elements from the group Ti, Cd, Zr, V and Co, and wherein 0 <x <0.2 and 0 <y <0.2 and a binder component (b) which (i) 40 to 75 wt% C ', where C '= SrO when A' = Sr C '= BaO if A' = Ba and C '= SrO + BaO if A' = Sr and A "= Ba or if A '= Ba and A''= Sr are (ii) 20 to 35% by weight of B 2 0 3 (iii) 2 to 15 wt% SiO 2 and (iv) contains 0.5 to 6.5 wt% Zn0
mixed with an organic carrier to form a paste, this paste is screen printed onto a substrate and conductively baked. 10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß die Paste vor dem Aufdrucken im Siebdruckverfahren gemahlen wird.10. The method according to claim 9, characterized in that the paste is ground before printing in the screen printing process. 11. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß die Paste auf einen Kupferanschluß aufgedruckt vird.11. The method according to claim 9, characterized in that the paste is printed on a copper connection. 12. Verfahren nach Anspruch 9 oder 11, dadurch gekennzeichnet, daß als Substrat ein Al2O3- Substrat verwendet wird.12. The method according to claim 9 or 11, characterized in that an Al 2 O 3 substrate is used as the substrate. 13. Verfahren nach einem oder mehreren der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Paste in einer Stickstoffatmosphäre eingebrannt wird.13. The method according to one or more of claims 1 to 12, characterized in that the paste is baked in a nitrogen atmosphere.
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