WO2004063110A2 - Glass-ceramic material and method of making - Google Patents

Glass-ceramic material and method of making Download PDF

Info

Publication number
WO2004063110A2
WO2004063110A2 PCT/US2003/041230 US0341230W WO2004063110A2 WO 2004063110 A2 WO2004063110 A2 WO 2004063110A2 US 0341230 W US0341230 W US 0341230W WO 2004063110 A2 WO2004063110 A2 WO 2004063110A2
Authority
WO
WIPO (PCT)
Prior art keywords
joint
solid
mol
component
recited
Prior art date
Application number
PCT/US2003/041230
Other languages
French (fr)
Other versions
WO2004063110A3 (en
WO2004063110B1 (en
Inventor
Dong-Sang Kim
Kerry D. Meinhardt
Bradley R. Johnson
Michael J. Schweiger
Original Assignee
Battelle Memorial Institute
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 Battelle Memorial Institute filed Critical Battelle Memorial Institute
Priority to CA002512083A priority Critical patent/CA2512083A1/en
Priority to EP03800164A priority patent/EP1578700A2/en
Priority to JP2004566596A priority patent/JP2006512275A/en
Priority to AU2003299892A priority patent/AU2003299892A1/en
Publication of WO2004063110A2 publication Critical patent/WO2004063110A2/en
Publication of WO2004063110A3 publication Critical patent/WO2004063110A3/en
Publication of WO2004063110B1 publication Critical patent/WO2004063110B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
    • C04B37/005—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of glass or ceramic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
    • C04B37/025—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of glass or ceramic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/04—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with articles made from glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0282—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286—Processes for forming seals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
    • C04B2235/365—Borosilicate glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/10—Glass interlayers, e.g. frit or flux
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the ' present invention is a glass ceramic material and method of making, specifically for use in electrochemical devices such as fuel cells, gas sensors, oxygen or hydrogen pumps/separators, or for sealing any material with a thermal expansion coefficient similar to the seal material.
  • solid electrolyte or “solid oxide ion conducting electrolyte” are interchangable.
  • joint includes the term “seal” because, in this glass-ceramic field, the “seal” joins at least two parts. However, the “joint” may be intermittent thereby not serving as a "seal”.
  • Ceramic materials are being used more often from automobile turbochargers to experimental fuel cells.
  • solid oxide ion conducting electrolytes are useful for oxygen separation and high temperature fuel cells.
  • sealing In a planar design, a gas-tight seal must bond the components together and prevent the mixing of the gas species on both sides of the solid oxide ion conducting electrolyte.
  • a limited number of materials are suitable as a solid oxide ion conducting electrolyte.
  • the most commonly used materials are yttria stabilized zirconia (YSZ), doped ceria, doped bismuth oxide and doped lanthanum gallate.
  • the thermal expansion coefficient (TEC) of these materials can range from 10.1 x 10 " 6 to 14.3 x 10 "6 °C “1 depending on the type of dopant and concentration. Of particular interest are materials having a TEC of 12 x 10 "6 °C "1 or greater.
  • the operating temperature can also range from 700°C to 1000°C depending upon which material is chosen as the electrolyte.
  • the seal material must be tailored to match the electrolyte thermal expansion, maintain a gas tight seal at temperatures ranging from 200 °C to 1200 °C, and not have detrimental chemical interactions with the fuel cell components.
  • the seal material must also be stable at the operating temperature (800-1000°C) for extended periods of time (>9,000 hr) and be electrically insulating. For a solid oxide fuel cell, the seal must be able to survive extremely reducing environments.
  • Borosilicate glasses and glass ceramics have also been considered as potential seal materials. These glasses have been investigated by C. G ⁇ nther et al 2 and K.L. Ley et al 3 for use in solid oxide fuel cells. However, boron will react with a humidified hydrogen atmosphere to form the gaseous species B 2 (OH) 2 and B 2 (OH) 3 at the operating temperature 2 . Therefore, any high boron seal may corrode in a humidified hydrogen environment over time. Glasses with B 2 O 3 as the only glass former have showed up to a 20% weight loss in the humidified hydrogen environment and extensive interactions with fuel cell component materials both in air and wet fuel gas. 1
  • Silica-based glasses and glass-ceramics offer the most promise. They typically have a higher chemical resistance and show minimal interaction with the fuel cell component materials. 1 Unfortunately, these glasses tend to have thermal expansions below the range needed for a sealing material.
  • the present invention is a glass-ceramic compound and method of making that are useful in joining or sealing ceramic components to other ceramic components, to glass components, to metal components, or to combinations thereof (e.g., cermet components). More specifically, the present invention is useful for joining/sealing in an electrochemical cell having at least one solid electrolyte having a first and second side exposed to first and second gas species respectively. The seal is necessary for separating the first and second gas species.
  • the glass-ceramic compound contains at least four metal oxides, M1-M2- M3-M4.
  • M1 is BaO, SrO, CaO, MgO, or combinations thereof.
  • M2 is AI 2 O 3 and is present in the compound in an amount from 2 to 15 mol%.
  • M3 is SiO 2 with up to 50 mol% B 2 O 3 .
  • M4 is either between 0.1 - 7.5 mol% a metal oxide selected from the group of La 2 O 3 , Y2O3, Nd2O3 or combinations thereof, or between 0.1 and 7.5 mol% K 2 O.
  • the composition contain an additional 0.1 to 3 mol %CuO as a wetting agent to assist the bonding of the glass.
  • the compound substantially matches a coefficient of thermal expansion of the solid ceramic component and at least one other solid component that is either ceramic, metal, or a combination thereof, when those components are selected as having a coefficient of expansion in the crystalline phase of 12 or greater 12 x 10 "6 °C "1 as measured from 25 °C to 1000 °C.
  • a series of glass ceramics in the M1- AI 2 O 3 -M3-M4 system can be used to join or seal both tubular and planar ceramic solid oxide fuel cells, oxygen electrolyzers, thermal barrier coatings, as a protective coating for metal substrates used as supports for catalytic particles used for high temperature catalytic reactions, for high temperature super-alloy applications, where it is desirable to coat metal parts with a ceramic material to improve their oxidation resistance,.and in membrane reactors for the production of syngas, commodity chemicals and other products. For high temperature super-alloy applications, it is often necessary to coat metal parts with a ceramic material to improve their oxidation resistance.
  • thermal barrier coatings are used in the areospace industry for coating turbine blades and other components.
  • multi-layered coatings are used to address issues of oxygen diffusion as well as thermal expansion mis-match.
  • the present invention is well suited for this application.
  • High temperature catalytic reactions also require the use of protective coatings for metal surfaces.
  • Thin metal substrates are often used as supports for catalytic particles, however at elevated temperatures and pressures, they oxidize and crumble.
  • a protective oxide coating applied to thin metal foils could be used to prolong their life, and could be cheaper and easier to manufacture than an all-ceramic part. These oxide surfaces then become the substrate that holds catalytic particles.
  • the present invention is well suited to be used in this manner.
  • the present invention is further well suited for sealing glass material surfaces also, such as those utilized in the lighting industry.
  • High performance, special application light bulbs require glass to metal seals in order to provide a joint between the filament and the glass bulb.
  • Some of the gasses in these light bulbs are highly corrosive, and since the bulbs get very hot, there are thermal expansion mis-match issues between the electrical contacts for the filament and the glass wall, creating a common failure site for these bulbs.
  • the present invention is well suited to solve this problem.
  • M4 is the maintaining of a substantially constant coefficient of thermal expansion from the glass to crystalline phase.
  • the present invention is a glass-ceramic compound and method of making the glass-ceramic compound.
  • the present invention is useful for joining or sealing between at least two solid ceramic parts, for example a seal in an electrochemical cell having at least one solid electrolyte having a first and second side exposed to first and second gas species respectively.
  • the present invention is also useful for joining or sealing between a solid ceramic component and a metal component or a cermet component. The seal is necessary for separating the first and second gas species during operation, usually at elevated temperatures.
  • the present invention includes a joint between a solid ceramic component and at least one other solid component that is preferably a solid ceramic component, a metal component, or a combination thereof such as a cermet component.
  • the joint has at least four metal oxides of M1-M2-M3-M4.
  • M1 is BaO, SrO, CaO, MgO, or combinations thereof.
  • M2 is AI 2 O 3 .
  • M3 is SiO with up to 50 mol% B 2 O 3 .
  • M4 is either between 0.1 - 7.5 mol% a metal oxide selected from the group of La 2 O 3 , Y 2 O 3 , Nd 2 O 3 or combinations thereof, or between 0.1 and 7.5 mol% K 2 O.
  • the composition contain an additional 0.1 to 3 mol %CuO, which has been shown to provide good wetting, and therefore assists with bonding, while improving, or at a minimum not degrading, the TEC over time.
  • the joint substantially matches a coefficient of thermal expansion of the components comprising the joint.
  • the coefficient of thermal expansion of the joint is 12 x 10 "6 °C "1 or greater as measured from 25 °C to 1000 °C.
  • composition of the joint/seal is preferably in the range wherein M1 is present in an amount from about 20 mol% to about 55 mol%, AI 2 O 3 is present in an amount from about 2 mol% to about 15 mol%, and M3 is present in an amount from about 40 mol% to about 70 mol%.
  • M4 is either between 0.1 - 7.5 mol% a metal oxide selected from the group of La 2 O 3 , Y 2 O 3 , Nd 2 O 3 or combinations thereof, or between 0.1 and 7.5 mol% K 2 O.
  • the composition contain an additional 0.1 to 3 mol %CuO for its wetting properties.
  • substantially the same coefficient of thermal expansion is herein defined as the coefficient of thermal expansion of the seal material within about 30%, preferably within about 16%, more preferably within about 5% of the sealed material.
  • the joint may be used in an electrochemical test cell to join an oxygen ion pump and a test material.
  • the joint may be used in an oxygen generator or a fuel cell to join an oxygen ion conducting electrolyte, for example a zirconia electrolyte, and an interconnect, for example manganite, chromite, metal, and combinations thereof.
  • an oxygen ion conducting electrolyte for example a zirconia electrolyte
  • an interconnect for example manganite, chromite, metal, and combinations thereof.
  • preferred applications are those where electrical resistance is desired, such as solid oxide fuel cells.
  • preferred applications are those where electrical resistance is not critical, such as oxygen generators.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Electrochemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Fuel Cell (AREA)
  • Ceramic Products (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

The present invention is a glass-ceramic material and method of making useful for joining a solid ceramic component and at least one other solid component. The material is a blend of M1-M2-M3-M4, wherein M1 is BaO, SrO, CaO, MgO, or combinations thereof, M2 is Al2O3, present in the blend in an amount from 2 to 15 mol%, M3 is SiO2 with up to 50 mol% B203 and a metal oxide selected from the group of La2O3, Y2O3, Nd2O3 or combinations thereof, or between 0.1 and 7.5 mol% K2O. In the case of a metal oxide from the group La2O3, Y2O3, Nd2O3 or combinations thereof, it is preferred that the composition contain an additional 0.1 to 3 mol %CuO. In all cases, the glass ceramic material in a crystalline phase substantially matches a coefficient of thermal expansion of solid electrolytes having a thermal expansion coefficient of 12 x 10-6 °C-1 as measured from 25 °C to 1000 °C, and does not degrade with repeated heat cycling. According to the present invention, the series of glass ceramics in the M1-Al2O3-M3-M4 system can be used to join or seal both tubular and planar solid oxide fuel cells, oxygen electrolyzers, and membrane reactors for the production of syngas, commodity chemicals and other products.

Description

GLASS-CERAMIC MATERIAL AND METHOD OF MAKING
This invention was made with Government support under Contract DE-AC0676RLO1830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
This application is a continuation-in-part of application serial number 09/562,583 filed May 1 , 2000 which is in turn a continuation-in-part of application serial number 09/365,343 filed July 30, 1999, now US Patent No. 6,430,966.
FIELD OF THE INVENTION
The' present invention is a glass ceramic material and method of making, specifically for use in electrochemical devices such as fuel cells, gas sensors, oxygen or hydrogen pumps/separators, or for sealing any material with a thermal expansion coefficient similar to the seal material.
As used herein, the terms "solid electrolyte" or "solid oxide ion conducting electrolyte" are interchangable.
As used herein, the term "joint" includes the term "seal" because, in this glass-ceramic field, the "seal" joins at least two parts. However, the "joint" may be intermittent thereby not serving as a "seal".
BACKGROUND OF THE INVENTION
Ceramic materials are being used more often from automobile turbochargers to experimental fuel cells. However, there remains the problem of joining and/or sealing ceramic components to other ceramic components, to metal components, or to combinations thereof (e.g., cermet components) such that the joint maintains integrity during operation. For example, solid oxide ion conducting electrolytes are useful for oxygen separation and high temperature fuel cells. Although many technical challenges of their development have been overcome, there remains the problem of sealing. In a planar design, a gas-tight seal must bond the components together and prevent the mixing of the gas species on both sides of the solid oxide ion conducting electrolyte.
A limited number of materials are suitable as a solid oxide ion conducting electrolyte. The most commonly used materials are yttria stabilized zirconia (YSZ), doped ceria, doped bismuth oxide and doped lanthanum gallate. The thermal expansion coefficient (TEC) of these materials can range from 10.1 x 10" 6 to 14.3 x 10"6 °C"1 depending on the type of dopant and concentration. Of particular interest are materials having a TEC of 12 x 10"6 °C"1 or greater. The operating temperature can also range from 700°C to 1000°C depending upon which material is chosen as the electrolyte. Therefore, the seal material must be tailored to match the electrolyte thermal expansion, maintain a gas tight seal at temperatures ranging from 200 °C to 1200 °C, and not have detrimental chemical interactions with the fuel cell components. In addition, the seal material must also be stable at the operating temperature (800-1000°C) for extended periods of time (>9,000 hr) and be electrically insulating. For a solid oxide fuel cell, the seal must be able to survive extremely reducing environments.
Various efforts to seal solid oxide ion conducting devices have been made with varying degrees of success. Silica, boron, and phosphate-based glasses and glass-ceramics have been evaluated as a sealing material1"4 for solid oxide fuel cells. Experiments conducted by P.H. Larsen et al1 have shown major problems with glasses purely based on phosphate as the glass former. At temperature, the phosphate volatilized and reacted with the anode to form nickel phosphide and zirconiumoxyphosphate. Additionally, these phosphate glasses usually crystallized to form meta- or pyrophosphates, which exhibited low stability in a humidified fuel gas at the operating temperature.
Borosilicate glasses and glass ceramics have also been considered as potential seal materials. These glasses have been investigated by C. Gϋnther et al2 and K.L. Ley et al3 for use in solid oxide fuel cells. However, boron will react with a humidified hydrogen atmosphere to form the gaseous species B2(OH)2 and B2(OH)3 at the operating temperature2. Therefore, any high boron seal may corrode in a humidified hydrogen environment over time. Glasses with B2O3 as the only glass former have showed up to a 20% weight loss in the humidified hydrogen environment and extensive interactions with fuel cell component materials both in air and wet fuel gas.1
Silica-based glasses and glass-ceramics offer the most promise. They typically have a higher chemical resistance and show minimal interaction with the fuel cell component materials.1 Unfortunately, these glasses tend to have thermal expansions below the range needed for a sealing material.
At the operating temperature, most glasses will crystallize with time. Therefore, it is critical to have a glass composition in which the thermal expansion coefficient after crystallization is compatible with the solid oxide ion conducting electrolyte. Once the glass is fully crystallized, it is typically very stable over time. In addition, crystallized glasses tend to be stronger mechanically at operating temperature, improving-seal performance.
One further difficulty that has been encountered by those having skill in the art is a tendency for the TEC of glasses to lessen over time.
Hence, there is a need in the art for a sealing material that can operate at an operating temperature up to about 900°C, has a TEC of 12 x 10"6 °C"1 or greater in the crystalline phase which does not degrade over time, and has no detrimental chemical interactions with the components.
BACKGROUND BIBLIOGRAPHY
1 . P.H. Larsen, C. Bagger, M. Mogensen and J.G. Larsen, Proc. 4th Int. Symp. Solid Oxide Fuel Cells, Volume 95-1 , 1995, pp.69-78. 2. C. Gϋnther, G. Hofer and W. Kleinlein, Proc. 5th Int. Symp. Solid Oxide Fuel Cells, Volume 97-18, 1997, pp.746-756.
3. K.L. Ley, M. Krumpelt, R. Kumar, J. H. Meiser, and I. Bloom, J. Mat. Res., Vol. 1 1 , No. 6, (1996) pp. 1489-1493.
4. Yoshinori Sakaki, Masatoshi Hattori, Yoshimi Esaki, Satoshi Ohara, Takehisa Fukui, Kaseki Kodera, Yukio Kubo, Proc. 5th Int. Symp. Solid Oxide Fuel
Cells, Volume 97-18, 1997, pp.652-660. SUMMARY OF THE INVENTION
The present invention is a glass-ceramic compound and method of making that are useful in joining or sealing ceramic components to other ceramic components, to glass components, to metal components, or to combinations thereof (e.g., cermet components). More specifically, the present invention is useful for joining/sealing in an electrochemical cell having at least one solid electrolyte having a first and second side exposed to first and second gas species respectively. The seal is necessary for separating the first and second gas species.
The glass-ceramic compound contains at least four metal oxides, M1-M2- M3-M4. M1 is BaO, SrO, CaO, MgO, or combinations thereof. M2 is AI2O3 and is present in the compound in an amount from 2 to 15 mol%. M3 is SiO2 with up to 50 mol% B2O3. M4 is either between 0.1 - 7.5 mol% a metal oxide selected from the group of La2O3, Y2O3, Nd2O3 or combinations thereof, or between 0.1 and 7.5 mol% K2O. In the case of a metal oxide from the group La O3ι Y2O3, Nd2O3 or combinations thereof, it is preferred that the composition contain an additional 0.1 to 3 mol %CuO as a wetting agent to assist the bonding of the glass.
The compound substantially matches a coefficient of thermal expansion of the solid ceramic component and at least one other solid component that is either ceramic, metal, or a combination thereof, when those components are selected as having a coefficient of expansion in the crystalline phase of 12 or greater 12 x 10"6 °C"1 as measured from 25 °C to 1000 °C.
According to the present invention, a series of glass ceramics in the M1- AI2O3-M3-M4 system can be used to join or seal both tubular and planar ceramic solid oxide fuel cells, oxygen electrolyzers, thermal barrier coatings, as a protective coating for metal substrates used as supports for catalytic particles used for high temperature catalytic reactions, for high temperature super-alloy applications, where it is desirable to coat metal parts with a ceramic material to improve their oxidation resistance,.and in membrane reactors for the production of syngas, commodity chemicals and other products. For high temperature super-alloy applications, it is often necessary to coat metal parts with a ceramic material to improve their oxidation resistance. For example, thermal barrier coatings are used in the areospace industry for coating turbine blades and other components. Typically, multi-layered coatings are used to address issues of oxygen diffusion as well as thermal expansion mis-match. The present invention is well suited for this application. High temperature catalytic reactions also require the use of protective coatings for metal surfaces. Thin metal substrates are often used as supports for catalytic particles, however at elevated temperatures and pressures, they oxidize and crumble. A protective oxide coating applied to thin metal foils could be used to prolong their life, and could be cheaper and easier to manufacture than an all-ceramic part. These oxide surfaces then become the substrate that holds catalytic particles. The present invention is well suited to be used in this manner.
The present invention is further well suited for sealing glass material surfaces also, such as those utilized in the lighting industry. High performance, special application light bulbs require glass to metal seals in order to provide a joint between the filament and the glass bulb. Some of the gasses in these light bulbs are highly corrosive, and since the bulbs get very hot, there are thermal expansion mis-match issues between the electrical contacts for the filament and the glass wall, creating a common failure site for these bulbs. The present invention is well suited to solve this problem.
Applications of the present invention using metal oxide selected from the group of La2O3, Y2O3, Nd O3 or combinations thereof are particularly suited for uses where electrical resistance is desired, solid oxide fuel cells, while applications of the present invention using K2O are particularly suited for applications where electrical resistance is not paramount, such as oxygen sensors.
It is an object of the present invention to provide a compound useful for joining or sealing a solid electrolyte or a solid oxide ion conducting electrolyte. An advantage of a joint/seal made with the compound of M1-AI2O3-M3-
M4 is the maintaining of a substantially constant coefficient of thermal expansion from the glass to crystalline phase. The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following description.
DESCRIPTION OF THE PREFERRED EMBODIMENT(S) The present invention is a glass-ceramic compound and method of making the glass-ceramic compound. The present invention is useful for joining or sealing between at least two solid ceramic parts, for example a seal in an electrochemical cell having at least one solid electrolyte having a first and second side exposed to first and second gas species respectively. The present invention is also useful for joining or sealing between a solid ceramic component and a metal component or a cermet component. The seal is necessary for separating the first and second gas species during operation, usually at elevated temperatures.
The present invention includes a joint between a solid ceramic component and at least one other solid component that is preferably a solid ceramic component, a metal component, or a combination thereof such as a cermet component. The joint has at least four metal oxides of M1-M2-M3-M4. M1 is BaO, SrO, CaO, MgO, or combinations thereof. M2 is AI2O3. M3 is SiO with up to 50 mol% B2O3. M4 is either between 0.1 - 7.5 mol% a metal oxide selected from the group of La2O3, Y2O3, Nd2O3 or combinations thereof, or between 0.1 and 7.5 mol% K2O. In the case of a metal oxide from the group La2O3, Y2O3, Nd2O3 or combinations thereof, it is preferred that the composition contain an additional 0.1 to 3 mol %CuO, which has been shown to provide good wetting, and therefore assists with bonding, while improving, or at a minimum not degrading, the TEC over time. The joint substantially matches a coefficient of thermal expansion of the components comprising the joint. The coefficient of thermal expansion of the joint is 12 x 10"6 °C"1 or greater as measured from 25 °C to 1000 °C. The composition of the joint/seal is preferably in the range wherein M1 is present in an amount from about 20 mol% to about 55 mol%, AI2O3 is present in an amount from about 2 mol% to about 15 mol%, and M3 is present in an amount from about 40 mol% to about 70 mol%. M4 is either between 0.1 - 7.5 mol% a metal oxide selected from the group of La2O3, Y2O3, Nd2O3 or combinations thereof, or between 0.1 and 7.5 mol% K2O. In the case of a metal oxide from the group La2O3, Y2O3, Nd2O3 or combinations thereof, it is preferred that the composition contain an additional 0.1 to 3 mol %CuO for its wetting properties. Substantially the same coefficient of thermal expansion is herein defined as the coefficient of thermal expansion of the seal material within about 30%, preferably within about 16%, more preferably within about 5% of the sealed material.
The joint may be used in an electrochemical test cell to join an oxygen ion pump and a test material. In addition, the joint may be used in an oxygen generator or a fuel cell to join an oxygen ion conducting electrolyte, for example a zirconia electrolyte, and an interconnect, for example manganite, chromite, metal, and combinations thereof. For those aspects of the invention utilizing a metal oxide from the group of La2O3| Y2O3, Nd2O3 or combinations thereof, preferred applications are those where electrical resistance is desired, such as solid oxide fuel cells. For those aspects of the invention utilizing K2O, preferred applications are those where electrical resistance is not critical, such as oxygen generators.
An experiment was conducted to demonstrate the glass-ceramic materials of the present invention. Glasses were fabricated having the compositions shown in table 1 : Table 1
Figure imgf000009_0001
The glasses of Table 1 were then tested to determine their coefficient of thermal expansion both before and after crystallization, and before and after repeated thermal cycling. The results are given below in table 2, where TEC x 10"6 °C"1 as measured from 25 °C to 1000 °C.
Figure imgf000009_0002
As shown in Table 2, all of the glasses met the criteria of having a TEC of 12 x 10"6 °C"1 or greater as measured from 25 °C to 1000 °C. Each of the glasses where then tested to determine whether the TEC after crystallization would decrease after repeated thermal cycling. It was determined that in each case, the TEC of the example glasses would withstand repeated thermal cycling and remain at or above 12 x 10"6 °C"1 as measured from 25 °C to 1000 °C.
CLOSURE
While a preferred embodiment of the present invention has been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims are therefore intended to cover all such changes and modifications as fall within the true spirit and scope of the invention.

Claims

CLAIMS We claim:
1. A joint between a solid ceramic component and at least one other solid component, said joint comprising: at least four metal oxides of M1-M2-M3 combined together wherein M1 is selected from the group consisting of BaO, SrO, CaO, MgO, and combinations thereof, M2 is AI2O3 wherein M2 is present in an amount from 2 to 15 mol%- M3 is SiO2 with up to 50 mol % of B2O3, and M4 is K2O wherein M4 is present in an amount between 0.1 and 7.5 mol % said joint substantially matching a coefficient of thermal expansion of said solid ceramic component and said at least one other solid component.
2. The joint as recited in claim 1 , wherein said at least one other solid component is ceramic.
3. The joint as recited in claim 1, wherein said at least one other solid component is metal.
4. The joint as recited in claim 1, wherein said at least one other solid component is cermet.
4. The joint as recited in claim 1, wherein said at least one other solid component is glass.
6. The joint as recited in claim 1 that is a seal.
7. The joint as recited in claim 1 wherein said coefficient of thermal expansion after crystallization that is greater than 12 x 10"6 °C"1 as measured from 25 °C to 1000 °C.
8. A joint between a solid ceramic component and at least one other solid component, said joint comprising: at least four metal oxides of M1-M2-M3 combined together wherein M1 is selected from the group consisting of BaO, SrO, CaO, MgO, and combinations thereof, M2 is AI2O3 wherein M2 is present in an amount from 2 to 15 mol%, M3 is SiO2 with up to 50 mol % of B2O3, and M4 is a metal oxide ' 5 selected from the group of La2O3, Y2O3, Nd2O3 or combinations thereof , said joint substantially matching a coefficient of thermal expansion of said solid ceramic component and said at least one other solid component.
9. The joint as recited in claim 8, wherein said at least one other solid 10 component is ceramic.
10. The joint as recited in claim 8, wherein said at least one other solid component is metal.
15 11. The joint as recited in claim 8, wherein said at least one other solid component is cermet.
12. The joint as recited in claim 8, wherein said at least one other solid component is glass. 0
13. The joint as recited in claim 8 that is a seal.
14. The joint as recited in claim 8 wherein said coefficient of thermal expansion after crystallization that is greater than 12 x 10"6 °C"1 as measured
25 from 25 °C to 1000 °C.
15. The method as recited in claim 8, wherein said solid ceramic component and said at least one other solid component are an oxygen ion conductor and an interconnect in a solid oxide fuel cell.
30
16. The joint as recited in claim 8, wherein said solid ceramic component and said at least one other solid component are an oxygen ion conductor and an interconnect in an oxygen generator.
17. The joint as recited in claim 8, wherein said joint further comprises between 0.1 and 3% CuO.
PCT/US2003/041230 2003-01-03 2003-12-23 Glass-ceramic material and method of making WO2004063110A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002512083A CA2512083A1 (en) 2003-01-03 2003-12-23 Glass-ceramic material and method of making
EP03800164A EP1578700A2 (en) 2003-01-03 2003-12-23 Glass-ceramic material and method of making
JP2004566596A JP2006512275A (en) 2003-01-03 2003-12-23 Glass ceramic material and manufacturing method thereof
AU2003299892A AU2003299892A1 (en) 2003-01-03 2003-12-23 Glass-ceramic material and method of making

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US33629703A 2003-01-03 2003-01-03
US10/336,297 2003-01-03

Publications (3)

Publication Number Publication Date
WO2004063110A2 true WO2004063110A2 (en) 2004-07-29
WO2004063110A3 WO2004063110A3 (en) 2004-10-21
WO2004063110B1 WO2004063110B1 (en) 2004-12-09

Family

ID=32710932

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/041230 WO2004063110A2 (en) 2003-01-03 2003-12-23 Glass-ceramic material and method of making

Country Status (5)

Country Link
EP (1) EP1578700A2 (en)
JP (1) JP2006512275A (en)
AU (1) AU2003299892A1 (en)
CA (1) CA2512083A1 (en)
WO (1) WO2004063110A2 (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7581765B2 (en) 2005-11-17 2009-09-01 Air Products And Chemicals, Inc. Seal assembly for materials with different coefficients of thermal expansion
JP2009533310A (en) * 2006-04-11 2009-09-17 コーニング インコーポレイテッド Glass ceramic seals for use in solid oxide fuel cells
US7781120B2 (en) * 2007-05-16 2010-08-24 Corning Incorporated Thermo-mechanical robust solid oxide fuel cell device assembly
US7968200B2 (en) 2008-02-25 2011-06-28 Noritake Co., Ltd Ceramic product and ceramic member bonding method
US8354202B2 (en) 2007-12-21 2013-01-15 Saint-Gobain Ceramics & Plastics, Inc. Multilayer glass-ceramic seals for fuel cells
CN102906046A (en) * 2010-04-01 2013-01-30 法国原子能及替代能源委员会 Glass-ceramic compositions for joints of appliances operating at high temperatures, and assembly method using said compositions
US9627109B2 (en) 2013-09-20 2017-04-18 Schott Corporation Feed-through element for harsh environments
WO2017112677A1 (en) * 2015-12-21 2017-06-29 Praxair Technology, Inc. Apparatus including a ceramic component, a metal component, and a glass sealing material and a process of forming the apparatus
US9776153B2 (en) 2013-10-07 2017-10-03 Praxair Technology, Inc. Ceramic oxygen transport membrane array reactor and reforming method
US9839899B2 (en) 2013-04-26 2017-12-12 Praxair Technology, Inc. Method and system for producing methanol using an integrated oxygen transport membrane based reforming system
US9938146B2 (en) 2015-12-28 2018-04-10 Praxair Technology, Inc. High aspect ratio catalytic reactor and catalyst inserts therefor
US9938145B2 (en) 2013-04-26 2018-04-10 Praxair Technology, Inc. Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system
US9969645B2 (en) 2012-12-19 2018-05-15 Praxair Technology, Inc. Method for sealing an oxygen transport membrane assembly
US10005664B2 (en) 2013-04-26 2018-06-26 Praxair Technology, Inc. Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source
US10010876B2 (en) 2016-11-23 2018-07-03 Praxair Technology, Inc. Catalyst for high temperature steam reforming
CN108285357A (en) * 2017-12-15 2018-07-17 福建省德化青江商贸有限公司 A kind of glass-ceramic cup processing technology
US10118823B2 (en) 2015-12-15 2018-11-06 Praxair Technology, Inc. Method of thermally-stabilizing an oxygen transport membrane-based reforming system
US10441922B2 (en) 2015-06-29 2019-10-15 Praxair Technology, Inc. Dual function composite oxygen transport membrane
CN110342915A (en) * 2019-08-01 2019-10-18 电子科技大学 A kind of high thermal expansion calcium borosilicate base ceramic packaging material and preparation method thereof
US10822234B2 (en) 2014-04-16 2020-11-03 Praxair Technology, Inc. Method and system for oxygen transport membrane enhanced integrated gasifier combined cycle (IGCC)
US11052353B2 (en) 2016-04-01 2021-07-06 Praxair Technology, Inc. Catalyst-containing oxygen transport membrane
CN113185127A (en) * 2021-04-20 2021-07-30 西北工业大学 Ca-Ti-Y-Al-Si-O microcrystalline glass solder and glass packaging method for end port of nuclear cladding tube
US11136238B2 (en) 2018-05-21 2021-10-05 Praxair Technology, Inc. OTM syngas panel with gas heated reformer

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100905217B1 (en) 2007-11-21 2009-07-01 명지대학교 산학협력단 A sealing materials contained alumina particle for solid oxide fuel cell
ES2411079T3 (en) 2008-04-07 2013-07-04 Topsoe Fuel Cell A/S Stacking of solid oxide fuel cells, process for preparing it and using an e glass in it
JP7096648B2 (en) * 2016-06-29 2022-07-06 株式会社オハラ Optical glass, preforms and optical elements
CN111423119A (en) * 2020-04-26 2020-07-17 佛山科学技术学院 High-temperature-resistant glaze

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060423A (en) * 1976-07-27 1977-11-29 General Electric Company High-temperature glass composition
FR2538370A1 (en) * 1982-12-28 1984-06-29 Ceraver Vitreous ceramic materials, process for the manufacture of such materials and application of the latter to adhesive bonding of ceramic articles
US4746578A (en) * 1984-01-09 1988-05-24 Ngk Spark Plug Co., Ltd. Glaze compositions for ceramic substrates
EP0351097A1 (en) * 1988-07-12 1990-01-17 THORN EMI plc An arc tube for a discharge lamp
DE19857057C1 (en) * 1998-12-10 2000-04-13 Fraunhofer Ges Forschung Use of an alkali-free silicon, magnesium and heavy alkaline earth metal oxide mixture as a high thermal expansion coefficient glass-ceramic joint material, especially for high temperature fuel cells
US6430966B1 (en) * 1999-07-30 2002-08-13 Battelle Memorial Institute Glass-ceramic material and method of making
WO2002094727A1 (en) * 2001-05-08 2002-11-28 Forschungszentrum Jülich GmbH Glass solder materials as jointing materials for use at high temperatures, production and use thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60155550A (en) * 1984-01-24 1985-08-15 Ngk Spark Plug Co Ltd Glaze composition for ceramic substrate
JPH0651579B2 (en) * 1986-07-25 1994-07-06 日本電気硝子株式会社 Magnetic head sealing glass
JPS63170241A (en) * 1987-01-08 1988-07-14 Toshiba Glass Co Ltd Glass composition for sealing
JP2000260007A (en) * 1999-03-04 2000-09-22 Matsushita Electric Ind Co Ltd Sealing glass for magnetic head and magnetic head using the same
EP1200371B1 (en) * 1999-07-30 2006-01-04 Battelle Memorial Institute Glass-ceramic joining material and method of joining

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060423A (en) * 1976-07-27 1977-11-29 General Electric Company High-temperature glass composition
FR2538370A1 (en) * 1982-12-28 1984-06-29 Ceraver Vitreous ceramic materials, process for the manufacture of such materials and application of the latter to adhesive bonding of ceramic articles
US4746578A (en) * 1984-01-09 1988-05-24 Ngk Spark Plug Co., Ltd. Glaze compositions for ceramic substrates
EP0351097A1 (en) * 1988-07-12 1990-01-17 THORN EMI plc An arc tube for a discharge lamp
DE19857057C1 (en) * 1998-12-10 2000-04-13 Fraunhofer Ges Forschung Use of an alkali-free silicon, magnesium and heavy alkaline earth metal oxide mixture as a high thermal expansion coefficient glass-ceramic joint material, especially for high temperature fuel cells
US6430966B1 (en) * 1999-07-30 2002-08-13 Battelle Memorial Institute Glass-ceramic material and method of making
WO2002094727A1 (en) * 2001-05-08 2002-11-28 Forschungszentrum Jülich GmbH Glass solder materials as jointing materials for use at high temperatures, production and use thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SOHN S-B ET AL: "Stable sealing glass for planar solid oxide fuel cell" JOURNAL OF NON-CRYSTALLINE SOLIDS, NORTH-HOLLAND PHYSICS PUBLISHING. AMSTERDAM, NL, vol. 297, no. 2-3, February 2002 (2002-02), pages 103-112, XP004335399 ISSN: 0022-3093 *

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7581765B2 (en) 2005-11-17 2009-09-01 Air Products And Chemicals, Inc. Seal assembly for materials with different coefficients of thermal expansion
JP2009533310A (en) * 2006-04-11 2009-09-17 コーニング インコーポレイテッド Glass ceramic seals for use in solid oxide fuel cells
EP2171784B1 (en) * 2007-05-16 2019-08-07 Corning Incorporated Thermo-mechanical robust solid oxide fuel cell device assembly
CN101682045B (en) * 2007-05-16 2014-07-02 康宁股份有限公司 Thermo-mechanical robust solid oxide fuel cell device assembly
US7781120B2 (en) * 2007-05-16 2010-08-24 Corning Incorporated Thermo-mechanical robust solid oxide fuel cell device assembly
US8354202B2 (en) 2007-12-21 2013-01-15 Saint-Gobain Ceramics & Plastics, Inc. Multilayer glass-ceramic seals for fuel cells
US7968200B2 (en) 2008-02-25 2011-06-28 Noritake Co., Ltd Ceramic product and ceramic member bonding method
US8431227B2 (en) 2008-02-25 2013-04-30 Noritake Co., Ltd Ceramic product and ceramic member bonding method
CN102906046A (en) * 2010-04-01 2013-01-30 法国原子能及替代能源委员会 Glass-ceramic compositions for joints of appliances operating at high temperatures, and assembly method using said compositions
US9969645B2 (en) 2012-12-19 2018-05-15 Praxair Technology, Inc. Method for sealing an oxygen transport membrane assembly
US9938145B2 (en) 2013-04-26 2018-04-10 Praxair Technology, Inc. Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system
US9839899B2 (en) 2013-04-26 2017-12-12 Praxair Technology, Inc. Method and system for producing methanol using an integrated oxygen transport membrane based reforming system
US10005664B2 (en) 2013-04-26 2018-06-26 Praxair Technology, Inc. Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source
US9627109B2 (en) 2013-09-20 2017-04-18 Schott Corporation Feed-through element for harsh environments
US9741463B2 (en) 2013-09-20 2017-08-22 Schott Corporation GTMS connector for oil and gas market
US9818500B2 (en) 2013-09-20 2017-11-14 Schott Corporation Feed-through element for harsh environments
US9776153B2 (en) 2013-10-07 2017-10-03 Praxair Technology, Inc. Ceramic oxygen transport membrane array reactor and reforming method
US10822234B2 (en) 2014-04-16 2020-11-03 Praxair Technology, Inc. Method and system for oxygen transport membrane enhanced integrated gasifier combined cycle (IGCC)
US10441922B2 (en) 2015-06-29 2019-10-15 Praxair Technology, Inc. Dual function composite oxygen transport membrane
US10118823B2 (en) 2015-12-15 2018-11-06 Praxair Technology, Inc. Method of thermally-stabilizing an oxygen transport membrane-based reforming system
WO2017112677A1 (en) * 2015-12-21 2017-06-29 Praxair Technology, Inc. Apparatus including a ceramic component, a metal component, and a glass sealing material and a process of forming the apparatus
US9938146B2 (en) 2015-12-28 2018-04-10 Praxair Technology, Inc. High aspect ratio catalytic reactor and catalyst inserts therefor
US11052353B2 (en) 2016-04-01 2021-07-06 Praxair Technology, Inc. Catalyst-containing oxygen transport membrane
US10010876B2 (en) 2016-11-23 2018-07-03 Praxair Technology, Inc. Catalyst for high temperature steam reforming
CN108285357A (en) * 2017-12-15 2018-07-17 福建省德化青江商贸有限公司 A kind of glass-ceramic cup processing technology
US11136238B2 (en) 2018-05-21 2021-10-05 Praxair Technology, Inc. OTM syngas panel with gas heated reformer
CN110342915A (en) * 2019-08-01 2019-10-18 电子科技大学 A kind of high thermal expansion calcium borosilicate base ceramic packaging material and preparation method thereof
CN113185127A (en) * 2021-04-20 2021-07-30 西北工业大学 Ca-Ti-Y-Al-Si-O microcrystalline glass solder and glass packaging method for end port of nuclear cladding tube

Also Published As

Publication number Publication date
JP2006512275A (en) 2006-04-13
AU2003299892A8 (en) 2004-08-10
CA2512083A1 (en) 2004-07-29
EP1578700A2 (en) 2005-09-28
WO2004063110A3 (en) 2004-10-21
WO2004063110B1 (en) 2004-12-09
AU2003299892A1 (en) 2004-08-10

Similar Documents

Publication Publication Date Title
CA2380101C (en) Glass-ceramic joining material and method of joining
WO2004063110A2 (en) Glass-ceramic material and method of making
US6532769B1 (en) Glass-ceramic joint and method of joining
Ley et al. Glass-ceramic sealants for solid oxide fuel cells: Part I. Physical properties
US5453331A (en) Compliant sealants for solid oxide fuel cells and other ceramics
JP6456458B2 (en) Glassy or at least partially crystallized fusing material, joint joint, barrier layer and layer system comprising this fusing material and incorporation into this component
CA2537513C (en) Advanced mica based seal and method for making and using
US8354202B2 (en) Multilayer glass-ceramic seals for fuel cells
US7399720B1 (en) Glass and glass-ceramic sealant compositions
WO1996005626A9 (en) Compliant sealants for solid oxide fuel cells and other ceramics
US20110200909A1 (en) Thin, fine grained and fully dense glass-ceramic seal for sofc stack
Reis et al. Designing sealing glasses for solid oxide fuel cells
Ohara et al. A new sealant material for solid oxide fuel cells using glass-ceramic
KR20090029381A (en) Manufacture of sealing gasket with glass and fiber compound for solid oxide fuel cell
Bieberle GLASS SEALS A. BIEBERLE, LJ GAUCKLER
Wei Sealing glass-ceramics for solid oxide fuel cell
Larsen et al. Stacking of planar SOFCs
Kueper et al. Sealant materials for solid oxide fuels and other high-temperature ceramics
Myles Principal Investigators Co-Investigators METC Project Manager
Parihar High temperature seals for solid oxide fuel cells

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
B Later publication of amended claims

Effective date: 20041008

WWE Wipo information: entry into national phase

Ref document number: 2003800164

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2512083

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2004566596

Country of ref document: JP

WWP Wipo information: published in national office

Ref document number: 2003800164

Country of ref document: EP