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DE4111711C1 - Metallising ceramic for fuel cells - includes firing mixt. into ceramic surface of glass forming and non-oxidising metallic components - Google Patents

Metallising ceramic for fuel cells - includes firing mixt. into ceramic surface of glass forming and non-oxidising metallic components

Info

Publication number
DE4111711C1
DE4111711C1 DE19914111711 DE4111711A DE4111711C1 DE 4111711 C1 DE4111711 C1 DE 4111711C1 DE 19914111711 DE19914111711 DE 19914111711 DE 4111711 A DE4111711 A DE 4111711A DE 4111711 C1 DE4111711 C1 DE 4111711C1
Authority
DE
Germany
Prior art keywords
ceramic
glass
metallic
metallising
mixt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
DE19914111711
Other languages
German (de)
Inventor
Martin Turwitt
Thomas 5060 Bergisch Gladbach De Jansing
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Priority to DE19914111711 priority Critical patent/DE4111711C1/en
Application granted granted Critical
Publication of DE4111711C1 publication Critical patent/DE4111711C1/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5144Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the metals of the iron group
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • C04B41/88Metals

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

In a process for metallising a ceramic, a mixt. is fired into the ceramic surface, consisting of a glass-forming component and a metallic component which does not oxidise at firing temp. The metallic component is a powder contg. 0-15% Al; 0-15% W, Mo and/or Nb; 0-5% Y, Ti and/or Ce; 0-3% Si, Mn and/or C; 15-25% Cr; remainder Ni and/or Fe and/or Co, and impurities. USE/ADVANTAGE - Fuel cells, resistant to H and O at temps. of 1000 deg. C and above

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Metallisieren einer Keramik durch Einbrennen in die Oberfläche derselben einer Mischung aus einer metallischen, bei Brenntemperatur nicht oxidierenden und einer glasbildenden Komponente.The present invention relates to a method for Metallize a ceramic by baking it into the surface the same a mixture of a metallic, at Firing temperature non-oxidizing and a glass-forming Component.

In der DE-C 23 50 465 ist ein Verfahren beschrieben worden, bei dem pulverförmiges Molybdän und Mangan mit glasbildenden Oxiden wie Titanoxid, dreiwertigem Eisenoxid oder Siliciumoxid in die Oberfläche der Keramik eingebrannt werden. Dabei wird das Mangan zu Manganoxid umgewandelt und bildet mit den übrigen Metalloxiden eine Glasschmelze, die die Haftung zur Keramik herstellt. Demgegenüber bleibt das Molybdän in seiner metallischen Form erhalten. Hieran finden metallische Lote wie Kupfer- oder Kupfer-Silberlote ihre Haftung, mit deren Hilfe die Keramik mit metallischen Komponenten verbunden werden kann. Als spezieller Anwendungszweig wurde seinerzeit das Einlöten von Tabletten aus einer sauerstoffionenleitenden Keramik, z. B. Zirkonoxid, in metallischen Sondenrohre gesehen, die Teil einer Einrichtung zur Bestimmung der Sauerstoffkonzentration, z. B. in Brenngasen, bildeten.A process has been described in DE-C 23 50 465 in the powdered molybdenum and manganese with glass-forming Oxides such as titanium oxide, trivalent iron oxide or silicon oxide be burned into the surface of the ceramic. Doing so the manganese is converted to manganese oxide and forms with the remaining metal oxides a glass melt, which the adhesion to Manufactures ceramics. In contrast, the molybdenum remains in its preserved metallic form. This is where metallic solders like Copper or copper-silver solders their liability, with their help the ceramics are connected with metallic components can. At that time, this became a special application Soldering tablets from an oxygen ion-conducting Ceramics, e.g. B. zirconium oxide, seen in metallic probe tubes, the part of a facility for determining the Oxygen concentration, e.g. B. in fuel gases.

Ein Nachteil dieser Metallisierung ist, daß sie an Luft bereits bei Temperaturen über 400°C leicht oxidiert und unbrauchbar wird. Sie erscheint daher nicht geeignet zum Einsatz in Hochtemperaturbrennstoffzellen, die bei Temperaturen über 1000°C betrieben werden und bei deren Bau ebenfalls das Bedürfnis auftritt, keramische und metallische Komponenten durch Lötung miteinander zu verbinden. Für diesen Zweck sind bislang Metallisierungen auf Platinbasis verwendet worden, die zwar die gewünschten Eigenschaften aufweisen, für die großtechnische Anwendung jedoch zu teuer sind.A disadvantage of this metallization is that it is in air easily oxidized at temperatures above 400 ° C and becomes unusable. It therefore does not appear suitable for Use in high temperature fuel cells, which at Temperatures above 1000 ° C are operated and during their construction also the need arises, ceramic and metallic Connect components together by soldering. For this So far, platinum-based metallizations have been used  that have the desired properties for the large-scale application is too expensive.

Auch ein aus der DE-A 39 24 591 bekanntes Verfahren, bei dem eine Mischung aus je für sich hergestelltem Molybdän- und Manganpulver einer bestimmten Korngröße in ausgewählten orga­ nischen Lösungsmitteln dispergiert, als sog. "Farbe" aufge­ bracht und anschließend eingebrannt wird, läßt demgegenüber keine besseren Eigenschaften erwarten. Ein in der DE-A 31 11 808 beschriebenes Verfahren zur Metallisierung mit Hilfe einer "Paste", die aus einem hochschmelzenden Metallpulver (u. U. einer Mischung aus mehreren solchen Pulvern), einem der be­ kannten glasbildenden Stoffe, einem Binde- und einem Lösungs­ mittel besteht, geht in seinem technischen Gehalt ebenfalls nicht über den zuvor erörterten Stand der Technik hinaus.Also a method known from DE-A 39 24 591, in which a mixture of molybdenum and Manganese powder of a certain grain size in selected orga African solvents dispersed, so-called "color" brought and then burned, leaves against it do not expect better properties. One in DE-A 31 11 808 described method for metallization using a "Paste" made from a high-melting metal powder (possibly a mixture of several such powders), one of the be knew glass-forming substances, a binding and a solution medium exists, also goes in its technical content not beyond the prior art discussed previously.

Aufgabe der vorliegenden Erfindung ist es, ein kostengün­ stigeres Verfahren zum Metallisieren von Keramik anzugeben, das Metallisierungen liefert, die auch noch bei Temperaturen um 1000°C zumindest gegen die in Brennstoffzellen verwendeten Betriebsstoffe, nämlich Wasserstoff und Sauerstoff, beständig sind.The object of the present invention is a cost-effective specify process for metallizing ceramics, that delivers metallizations, even at temperatures around 1000 ° C at least against those used in fuel cells Operating materials, namely hydrogen and oxygen, resistant are.

Die Lösung dieser Aufgabe erfolgt dadurch, daß als metallische Komponente ein Pulver verwendet wird, dessen einzelne Körner eine untereinander gleiche Zusammensetzung haben vonThis object is achieved in that as a metallic Component a powder is used, the individual grains have the same composition among each other of

0-15% Aluminium;
0-15% Wolfram, Molybdän und/oder Niob;
0-5% Yttrium, Titan und/oder Cer;
0-3% Silicium, Mangan und/oder Kohlenstoff;
15-25% Chrom;
wobei der Rest neben herstellungsbedingten Verunreinigungen aus Nickel und/oder Eisen und/oder Kobalt besteht, d. h. den Eisenelementen.
0-15% aluminum;
0-15% tungsten, molybdenum and / or niobium;
0-5% yttrium, titanium and / or cerium;
0-3% silicon, manganese and / or carbon;
15-25% chromium;
the remainder, in addition to production-related impurities, consists of nickel and / or iron and / or cobalt, ie the iron elements.

Austenitische, korrosionsbeständige Stähle mit dieser Zusammensetzung sind bekannt (z. B. Werkstoff Nr. 1.4882). Sie lassen sich ohne Schwierigkeiten pulverisieren und finden in dieser Gestalt Anwendung u. a. beim Aufbringen von Korrosionsschutzschichten mittels des Plasmaspritzverfahrens.Austenitic, corrosion-resistant steels with this composition is known (e.g. material No. 1.4882). You can easily  pulverize and find application in this form u. a. when applying corrosion protection layers using the Plasma spraying process.

In besonderer Ausgestaltung der Erfindung werden als glasbildende Komponenten Aluminiumoxid, Titanoxid, Siliciumoxid und/oder Calciumoxid verwendet. Die glasbildenden Eigenschaften dieser Stoffe sind bekannt.In a special embodiment of the invention are as glass-forming components aluminum oxide, titanium oxide, Silicon oxide and / or calcium oxide used. The glass-forming Properties of these substances are known.

In weiterer Ausgestaltung der Erfindung wird die Mischung aus der metallischen und der glasbildenden Komponente durch Einmischen in einen organischen Binder (z. B. Ethylenglycol) in Pastenform überführt, was ihre praktische Handhabbarkeit verbessert.In a further embodiment of the invention, the mixture of the metallic and glass-forming components Mix in an organic binder (e.g. ethylene glycol) transferred in paste form, what their practical handling improved.

Ein Gemisch aus dem oben beschriebenen Edelstahlpulver und derartigen Glasbildnern wird in bekannter Weise auf die zu metallisierende Keramik aufgebracht (gegebenenfalls unter Zuhilfenahme eines sich unterhalb der Brenntemperatur rückstandsfrei zersetzenden Binders) und in einer feuchten Ofenatmosphäre eingebrannt.A mixture of the stainless steel powder and Such glass formers are known to the Metallizing ceramic applied (if necessary under With the help of a below the firing temperature residue-free decomposing binder) and in a moist Burnt-in atmosphere.

Claims (3)

1. Verfahren zum Metallisieren einer Keramik durch Einbrennen in die Oberfläche derselben einer Mischung aus einer metallischen, bei Brenntemperatur nicht oxidierenden und einer glasbildenden Komponente, dadurch gekennzeichnet, daß als metallische Komponente ein Pulver verwendet wird, dessen einzelne Körner eine untereinander gleiche Zusammensetzung haben von
  • a) 0-15% Aluminium,
  • b) 0-15% Wolfram, Molybdän und/oder Niob,
  • c) 0-5% Yttrium, Titan und/oder Cer,
  • d) 0-3% Silicium, Mangan und/oder Kohlenstoff,
  • e) 15-25% Chrom,
  • f) Rest neben herstellungsbedingten Verunreinigungen Nickel und/oder Eisen und/oder Kobalt.
1. A method for metallizing a ceramic by baking into the surface thereof a mixture of a metallic, non-oxidizing at firing temperature and a glass-forming component, characterized in that a powder is used as the metallic component, the individual grains of which have the same composition among themselves
  • a) 0-15% aluminum,
  • b) 0-15% tungsten, molybdenum and / or niobium,
  • c) 0-5% yttrium, titanium and / or cerium,
  • d) 0-3% silicon, manganese and / or carbon,
  • e) 15-25% chromium,
  • f) remainder in addition to manufacturing-related impurities nickel and / or iron and / or cobalt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als glasbildende Komponenten Aluminiumoxid, Titanoxid, Siliciumoxid und/oder Calciumoxid verwendet werden.2. The method according to claim 1, characterized characterized that as a glass-forming Components aluminum oxide, titanium oxide, silicon oxide and / or Calcium oxide can be used. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Mischung aus der metallischen und glasbildenden Komponente durch Einmischen in einen organischen Binder in Pastenform überführt wird.3. The method according to claim 1 or 2, characterized characterized in that the mixture of the metallic and glass-forming component by mixing in an organic binder is transferred into paste form.
DE19914111711 1991-04-10 1991-04-10 Metallising ceramic for fuel cells - includes firing mixt. into ceramic surface of glass forming and non-oxidising metallic components Expired - Fee Related DE4111711C1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19914111711 DE4111711C1 (en) 1991-04-10 1991-04-10 Metallising ceramic for fuel cells - includes firing mixt. into ceramic surface of glass forming and non-oxidising metallic components

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19914111711 DE4111711C1 (en) 1991-04-10 1991-04-10 Metallising ceramic for fuel cells - includes firing mixt. into ceramic surface of glass forming and non-oxidising metallic components

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DE4111711C1 true DE4111711C1 (en) 1993-02-04

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19749004A1 (en) * 1997-11-06 1999-05-20 Forschungszentrum Juelich Gmbh Electroconductive connection between ceramic and metallic components formed by an interposed sintered conductive paste
WO2006136610A2 (en) * 2005-06-23 2006-12-28 Colorobbia Italia S.P.A. Materials for coating ceramic bodies, processes for the preparation thereof, use thereof and ceramic articles including these materials
US20100104440A1 (en) * 2007-03-29 2010-04-29 Mitsubishi Heavy Industries, Ltd. Coating material and method of manufacturing same, coating method, and moving blade with shroud
EP3010870A1 (en) * 2013-06-05 2016-04-27 CeramTec GmbH Metal coating on ceramic substrates

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615376A (en) * 1968-11-01 1971-10-26 Gen Electric Cast nickel base alloy
DE2945688A1 (en) * 1978-11-14 1980-06-04 Onera (Off Nat Aerospatiale) METAL MULTI-PHASE SYSTEM OF THE TYPE GAMMA, GAMMA 'WITH STRUCTURAL STRENGTH IMPROVED BY NIOBIUM CARBIDE
DE3111808A1 (en) * 1980-03-31 1982-01-07 Hitachi Chemical Co., Ltd., Tokyo ELECTRICALLY CONDUCTIVE PASTE AND METHOD FOR PRODUCING ELECTRICALLY CONDUCTIVE, METALLIZED, CERAMIC MATERIALS USING THE SAME
DE3924591A1 (en) * 1988-07-28 1990-02-01 Lilliwyte Sa METHOD FOR CONNECTING A CERAMIC COMPONENT TO A METALLIC COMPONENT

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615376A (en) * 1968-11-01 1971-10-26 Gen Electric Cast nickel base alloy
DE2945688A1 (en) * 1978-11-14 1980-06-04 Onera (Off Nat Aerospatiale) METAL MULTI-PHASE SYSTEM OF THE TYPE GAMMA, GAMMA 'WITH STRUCTURAL STRENGTH IMPROVED BY NIOBIUM CARBIDE
DE3111808A1 (en) * 1980-03-31 1982-01-07 Hitachi Chemical Co., Ltd., Tokyo ELECTRICALLY CONDUCTIVE PASTE AND METHOD FOR PRODUCING ELECTRICALLY CONDUCTIVE, METALLIZED, CERAMIC MATERIALS USING THE SAME
DE3924591A1 (en) * 1988-07-28 1990-02-01 Lilliwyte Sa METHOD FOR CONNECTING A CERAMIC COMPONENT TO A METALLIC COMPONENT

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19749004A1 (en) * 1997-11-06 1999-05-20 Forschungszentrum Juelich Gmbh Electroconductive connection between ceramic and metallic components formed by an interposed sintered conductive paste
DE19749004C2 (en) * 1997-11-06 2002-04-25 Forschungszentrum Juelich Gmbh Manufacturing process for an electrically conductive connection between a ceramic and a metallic component
WO2006136610A2 (en) * 2005-06-23 2006-12-28 Colorobbia Italia S.P.A. Materials for coating ceramic bodies, processes for the preparation thereof, use thereof and ceramic articles including these materials
WO2006136610A3 (en) * 2005-06-23 2007-07-12 Colorobbia Italiana Spa Materials for coating ceramic bodies, processes for the preparation thereof, use thereof and ceramic articles including these materials
US20100104440A1 (en) * 2007-03-29 2010-04-29 Mitsubishi Heavy Industries, Ltd. Coating material and method of manufacturing same, coating method, and moving blade with shroud
EP3010870A1 (en) * 2013-06-05 2016-04-27 CeramTec GmbH Metal coating on ceramic substrates

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