EP1888806A1 - Procede de production de couches etanches au gaz et de systeme de couches par pulverisation thermique - Google Patents

Procede de production de couches etanches au gaz et de systeme de couches par pulverisation thermique

Info

Publication number
EP1888806A1
EP1888806A1 EP06742367A EP06742367A EP1888806A1 EP 1888806 A1 EP1888806 A1 EP 1888806A1 EP 06742367 A EP06742367 A EP 06742367A EP 06742367 A EP06742367 A EP 06742367A EP 1888806 A1 EP1888806 A1 EP 1888806A1
Authority
EP
European Patent Office
Prior art keywords
layer
gas
starting material
tight
varied
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.)
Withdrawn
Application number
EP06742367A
Other languages
German (de)
English (en)
Inventor
Roberto Siegert
Jens-Erich DÖRING
Ralf Hansch
Detlev STÖVER
Robert Vassen
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.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
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 Forschungszentrum Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Publication of EP1888806A1 publication Critical patent/EP1888806A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
    • 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
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • 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
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing 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 invention relates to a method for producing gas-tight layers and layer systems by means of a thermal spraying method.
  • Thermal spraying is a cost effective standard process for applying functional layers to high application rate substrates.
  • the particles of the starting material are heated by the heat of a burner and at the same time accelerated in the direction of the substrate, where they impinge in at least fused state.
  • the burner In order to coat the substrate flat, the burner is usually moved at a certain speed (translation speed) over the substrate.
  • the starting material may be a powder with particle sizes from about 5 microns or a suspension or a sol, the suspension and the sol have the advantage that the solid is present in them in the form of much smaller particles. It is usually conveyed through a nozzle (injector) into the heat-affected zone.
  • any material is suitable that does not burn, does not sublime, does not dissociate and does not decompose under the heat effect of the burner.
  • the burner heats the particles with a fuel gas-oxygen flame and usually an additional compressed gas Stream supports the transport of the particles to the substrate, especially the plasma spraying has established.
  • FIG. 1 shows a schematic diagram of the plasma spraying.
  • the burner produces a plasma that both heats and accelerates the particles toward the substrate.
  • much higher temperatures are achieved than in thermal spraying, so that the plasma spraying is also suitable for refractory metals and ceramics.
  • APS atmospheric plasma spraying
  • LFPS Liquid Feedstock Plasma Spray
  • the layers are applied in the form of discrete particles, which are thrown by the plasma onto the substrate. Therefore, they do not initially have high density and, in particular, are not gas-tight. If, for example, a gas-tight layer is desired for the electrolyte layer in a fuel cell, the layer must be thermally treated.
  • the workpiece must be disadvantageously removed from the apparatus in the plasma spraying process according to the prior art and moved to another apparatus.
  • the layer system is already disadvantageously exposed to a variety of thermal cycles during its manufacture, whereby it is heavily stressed. In addition, an interruption of the manufacturing process is time-consuming and therefore expensive.
  • the object of the invention is therefore to provide a process with which layers or layer systems of at least one porous and one gas-tight layer with good
  • Adhesive properties can be easily and inexpensively manufactured.
  • gas-tight expressly also includes layers of high physical density, which however are not yet completely gastight.
  • the object of the invention is also to provide a method with which dense or gas-tight layer systems consisting of individual elements can be provided It is a further object of the invention to be able to design the porous region of the layer or of the layer system optionally with variable material properties (graduated).
  • This porous layer is sealed gastight by thermal melting.
  • the same burner used for the application of the porous layer is used as the heat source.
  • the transition from coating to sealing takes place in that the burner is unchanged continue to operate, but the supply of starting material is adjusted.
  • the formation of the gas-tight layer then takes place in that the outermost layers of the applied layer are melted or sintered by the heat coupled in by the burner. This is favored by the fact that with increasing
  • Layer thickness of the heat loss in the substrate is always lower and the temperature of the layer surface increases while maintaining burner performance: First, the heat capacity of the applied layer is always larger; On the other hand, the layer is always better insulated against the usually actively cooled substrate.
  • the workpiece temperature can also be increased by slowing down the speed at which the torch moves over the surface of the layer (translation speed). The person skilled in the art will also consider appropriate combinations of these measures.
  • this method can be used to produce gas-tight layers in which certain properties vary continuously, by varying further process parameters during the layer application and by continuously introducing the operation of the seal. This can be prevented in particular that the gas-tight seal from the actual functional layer flakes off.
  • a gas-tight layer can be applied to a porous layer.
  • further porous layers can be applied, even with completely different starting materials. This is necessary, for example, for the production of a complete fuel cell structure consisting of a porous anode, a gas-tight electrolyte and a porous cathode.
  • a typical fuel cell structure includes, among others, yttria-stabilized zirconia.
  • Figure 2 Layer consisting of a framework of dense material, in the pores sponge-like structures are embedded.
  • FIG. 3 Layer with segmentation cracks
  • Figure 4 Layer system of a porous and a gas-tight layer
  • suspension plasma spraying is advantageously used as a plasma spraying process.
  • the solids content of the suspension can be continuously regulated during the layer application.
  • suspension plasma spraying expressly also includes the use of a sol that is a colloidal suspension of the particles of the starting material in a solvent.
  • the injection rate of the starting material into the plasma or the temperature at the location of the layer application can be varied.
  • FIG. 2 shows scanning electron micrographs of such a layer.
  • the width of the partial images A and B corresponds in each case to approximately 11.3 ⁇ m.
  • both dense regions (i) and (ii) due to completely molten particles and spongy structures (iii) are visible.
  • the pore size of the sponge-like structures is well below 1 ⁇ m with a low total local density.
  • a functional layer with such a microstructure can be used, for example, as a filter structure, as a thermal barrier coating or as a nano-granular hard material layer, which can be used, for example, as a cutting material, or else as an anti-adhesive coating.
  • the injection rate of the starting material into the plasma is advantageously selected such that only part of the starting material is completely melted and remains there permanently as a scaffold of dense material after impacting the substrate.
  • such an injection rate (about 5 m / s) is relatively low compared to the velocity of the plasma.
  • a further phase of very small (50 to about 300 nm), not completely melted particles is first reflected on the substrate and stored in the sequence only at a later date as a sponge-like structure in the pores of the already applied to the substrate dense material one. Success depends on the achieved penetration depth in the plasma, but the technically accessible parameter over which it can be varied, the injection rate of the starting material in the plasma.
  • the injection speed required for achieving a given penetration depth depends on further conditions of the specific apparatus, in particular on the plasma torch used and the temperature distribution of the plasma supplied by it.
  • a person skilled in the art can, with knowledge of the above-mentioned technical teaching, determine the injection rate suitable for given given conditions by a reasonable number of tests.
  • the suspension used for plasma spraying should have a solids content of not more than 25% by weight.
  • Figure 3 shows cross sections of layers produced according to the invention: above with a crack density of about 5 cracks / mm, with as starting material for spraying a
  • Suspension was used; below, a layer applied on a substrate made of V2A steel with a crack density of more than 10 cracks / mm (marked area), using as starting material a sol.
  • the width of the upper partial image corresponds to about 880 ⁇ m and the width of the lower partial image to about 840 ⁇ m.
  • Such functional layers are characterized by a particularly high mechanical strength. They can be used for example as thermal barrier coatings for thermally highly stressed components.
  • the temperature prevailing at the location of the layer application is increased in such a way that interlamellar grain growth with good interlamellar adhesion takes place in the applied layer: the grain growth can occur as a result of the stress reduction only perpendicular to the lamellae and thus forms the segmentation cracks.
  • the rate of injection of the starting material into the plasma is increased so much that the particles of the starting material completely melt.
  • the density of the segmentation cracks can be adjusted via the solids content of the suspension used (typically between 1 and 20% by weight); a lower solids content produces a higher crack density.
  • FIG. 4 shows a transverse section of a yttrium-stabilized zirconium oxide (YSZ) layer system produced according to the invention.
  • the width of the upper partial image corresponds to about 345 ⁇ m and the width of the lower partial image to about 170 ⁇ m.
  • the layer system consists of a 150 ⁇ m thick layer with segmentation cracks on a thermally insulating material (epoxy resin), followed by a further 41.56 by using a sol as starting material (consisting of 5 to 20% by weight solids, with isopropanol as solvent) ⁇ m thick gas-tight layer was applied.
  • a sol as starting material consististing of 5 to 20% by weight solids, with isopropanol as solvent
  • Such layer systems can, for. B. in fuel cell structures or as membrane or filter structures.
  • the distance to the workpiece should be as low as possible, so that the layer can melt due to the high surface temperature and the small particle size. No more than 5 * 10 '4 grams of SoI per second should be injected into the plasma.
  • the substrate to which such layers are applied may have a roughness in a wide range of about 1-6 microns, with the area below 2 microns offering advantages in layer adhesion.
  • titanium oxide, mullite, WC / Co and cermets can also be applied in the form of such layer systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

L'invention concerne un procédé de production de couches étanches au gaz et de systèmes de couches par un procédé de pulvérisation thermique. On commence par appliquer une couche par pulvérisation thermique à l'aide d'un chalumeau puis on la soumet à un retraitement thermique avec le même chalumeau. Ce procédé continu permet une production simple et économique de couches étanches au gaz et de systèmes de couches ayant de bonnes propriétés d'adhérence. Puisqu'il est possible d'introduire une couche étanche au gaz dans des emplacements quelconques d'un système de couches, ce procédé convient particulièrement à la production de structures cellules de combustible.
EP06742367A 2005-05-30 2006-05-23 Procede de production de couches etanches au gaz et de systeme de couches par pulverisation thermique Withdrawn EP1888806A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005025054A DE102005025054A1 (de) 2005-05-30 2005-05-30 Verfahren zur Herstellung gasdichter Schichten und Schichtsysteme mittels thermischem Spritzen
PCT/DE2006/000886 WO2006128424A1 (fr) 2005-05-30 2006-05-23 Procede de production de couches etanches au gaz et de systeme de couches par pulverisation thermique

Publications (1)

Publication Number Publication Date
EP1888806A1 true EP1888806A1 (fr) 2008-02-20

Family

ID=36741441

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06742367A Withdrawn EP1888806A1 (fr) 2005-05-30 2006-05-23 Procede de production de couches etanches au gaz et de systeme de couches par pulverisation thermique

Country Status (3)

Country Link
EP (1) EP1888806A1 (fr)
DE (1) DE102005025054A1 (fr)
WO (1) WO2006128424A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006062378A1 (de) * 2006-12-22 2008-06-26 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verfahren zur Herstellung einer elektrochemischen Funktionsstruktur und Funktionsstruktur
DE102008007870A1 (de) * 2008-02-06 2009-08-13 Forschungszentrum Jülich GmbH Wärmedämmschichtsystem sowie Verfahren zu seiner Herstellung
US20120177908A1 (en) * 2010-07-14 2012-07-12 Christopher Petorak Thermal spray coatings for semiconductor applications
DE102014222686A1 (de) * 2014-11-06 2016-05-12 Siemens Aktiengesellschaft Doppellagige Wärmedämmschicht durch unterschiedliche Beschichtungsverfahren
JP6908973B2 (ja) * 2016-06-08 2021-07-28 三菱重工業株式会社 遮熱コーティング、タービン部材、ガスタービン、ならびに遮熱コーティングの製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2237588A1 (fr) * 1995-11-13 1997-05-22 The University Of Connecticut Produits nanostructures pour pulverisation a chaud
US6447848B1 (en) * 1995-11-13 2002-09-10 The United States Of America As Represented By The Secretary Of The Navy Nanosize particle coatings made by thermally spraying solution precursor feedstocks
DE19542808A1 (de) * 1995-11-16 1996-08-14 Siemens Ag Verfahren zum Beschichten eines Substrats
DE19608719A1 (de) * 1996-03-06 1997-09-11 Deutsche Forsch Luft Raumfahrt Verfahren zur Herstellung von Formteilen
US20040018409A1 (en) * 2002-02-28 2004-01-29 Shiqiang Hui Solid oxide fuel cell components and method of manufacture thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006128424A1 *

Also Published As

Publication number Publication date
WO2006128424A1 (fr) 2006-12-07
DE102005025054A1 (de) 2006-12-07

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