EP0776985B1 - Method for applying a metallic adhesion layers for ceramic insulating layer on metallic articles - Google Patents

Method for applying a metallic adhesion layers for ceramic insulating layer on metallic articles Download PDF

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Publication number
EP0776985B1
EP0776985B1 EP96810768A EP96810768A EP0776985B1 EP 0776985 B1 EP0776985 B1 EP 0776985B1 EP 96810768 A EP96810768 A EP 96810768A EP 96810768 A EP96810768 A EP 96810768A EP 0776985 B1 EP0776985 B1 EP 0776985B1
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EP
European Patent Office
Prior art keywords
metallic
layer
binder
adhesive powder
powder
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Expired - Lifetime
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EP96810768A
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German (de)
French (fr)
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EP0776985A1 (en
Inventor
Reinhard Fried
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General Electric Switzerland GmbH
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Alstom Schweiz AG
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    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12097—Nonparticulate component encloses particles

Definitions

  • the invention relates to the field of materials technology. It relates to a method for applying a metallic Adhesive layer for thermally sprayed ceramic thermal insulation layers to be subsequently applied to this adhesive layer (TBC) on metallic components as well as a metallic adhesive layer produced by this process.
  • TBC adhesive layer
  • metal and ceramic can be different because of the different Thermal expansion coefficients not with each other connect.
  • the coated metallic Protect components from harmful thermal stresses their complete existence is important for a sufficient Component life.
  • Components coated in this way are especially in the field of combustion technology used, for example for combustion chamber parts or gas turbine blades.
  • the disadvantage of the metallic adhesive layers produced so far for ceramic thermal insulation layers is that they have insufficient roughness and therefore too little Offer form fit (undercuts) so that the layer thickness of the TBC layers is limited.
  • Layer thicknesses are known from about 0.2 to 0.4 mm, with layer thicknesses of about 0.3 mm are most common. If you are fatter, so the risk of flaking increases rapidly. Are you thinner the thermal insulation effect quickly subsides. Recent developments go there, coarser adhesive layers (approx. 0.6 mm) to inject, but the necessary positive locking is missing.
  • a roughness typical of known metallic adhesive layers is around 30 ⁇ m. Rougher the layers cannot be sprayed because of the dimension of the powder particles to be melted depending on the coating process (different spray temperatures and spray speeds) is limited to approx. 10 to 50 ⁇ m and the Flatten the liquid powder particles when they hit the substrate (cf. B. Heine: "Thermally sprayed layers", metal, 49th year, 1/1995, p.51-57).
  • the invention tries to avoid all these disadvantages. you is based on the task of a metallic adhesive layer and a method of applying this adhesive layer for ceramic Thermal insulation layers on a metallic base body too develop with which it is compared to the known state of the art Technology is possible, then ceramic thermal insulation layers thermally spraying and attaching thicker. The layers should adhere stably and insensitively to be against impact.
  • the advantages of the invention include in that with these Process adhesive layers are generated that are opposite to the State of the art are very rough.
  • the soldered or sintered Metal powder particles are very stable and positive anchoring for the TBC layer to be sprayed on so that comparatively thick, stable adherence ceramic thermal insulation layers can be generated.
  • both powders are first mixed intensively be and then this mixture on the metallic Surface of the base material is applied. This will achieved a more uniform distribution of the powder particles and also shortens the process time.
  • solder material Material such as the base material and boron-free or low-boron solders used. This reduces possible brittle phase formation.
  • the method according to the invention can be used locally for repair purposes as well as used for coating new parts become.
  • the metallic adhesive layer produced according to the invention exists depending on the process variant used from a Surface of the solder layer wetting the metallic component with spherically or sputteringly formed soldered in it Adhesive powder particles or additionally from a thin sprayed, in particular protective gas plasma sprayed layer same type of material as the adhesive powder particles or an inert gas plasma sprayed onto the surface of the metallic component Protective layer with on its surface sintered adhesive powder particles.
  • This metallic adhesive layer guarantees stable adhesion of the thermally sprayed ceramic thermal insulation layers, allows larger ones Layer thicknesses and leads to good emergency running properties.
  • the height of the adhesive powder particles is approximately as large as the layer thickness of the thermal ceramic thermal barrier coating to be sprayed on. This will the layer is almost insensitive to impact because strikes essentially be collected in a metallic way.
  • a guide vane of a gas turbine as an example of a metallic component 1 to be coated. It consists of the metallic base material (substrate) 2, in this case the alloy IN 939 with the following chemical composition: Bal. Ni; 22.5% Cr; 19.0% Co; 2.0% W; 1.0% Nb; 1.4% Ta; 3.7% Ti; 1.9% Al; 0.1 Zr; 0.01 B; 0.15 C.
  • the blade is provided with a corrosion and oxidation layer on the gas-carrying surfaces (MCrAlY, e.g. SV201473: Bal. Ni; 25% Cr; 5% Al; 2.5% Si; 0.5% Y; 1 % Ta).
  • this blade is coated on the leading edge, the pressure side of the blade and on the channel walls with an approximately 0.3 mm thick thermal insulation layer made of ytrium-stabilized zirconium oxide with the following composition: Bal. ZrO 2 incl 2.5% HfO 2 ; 7-9% Y 2 O 3 ; ⁇ 3% others.
  • the gas turbine guide vane comes after an operating time of 25,000 hours for reconditioning. It is determined that due to thermal overload and erosion at the leading edge of the sheet and on the channel wall Thermal insulation layer is no longer present (see hatched Areas in Fig. 1). Since the shovel did no further damage will not be completely re-coated for cost reasons, but a partial repair of the thermal insulation layer sought. Because of that on the above Systematically make a particularly strong attack by the TBC the TBC layer should not only be of the same thickness, but run as thick as possible.
  • the blade 1 becomes coarse in the steam jet Dirt (combustion residues) cleaned. After that deposits still adhering by means of soft sandblasting, (e.g. fine aluminum powder, 2 bar jet pressure, 20 cm distance) away. The still intact ceramic thermal insulation layer is allowed not be removed.
  • soft sandblasting e.g. fine aluminum powder, 2 bar jet pressure, 20 cm distance
  • the blade parts not to be coated are covered, for example with a sheet metal template, and the too coating surfaces are blasted (e.g. fine silicon carbide, Jet pressure 4 bar, distance 40 mm), so that any TBC residues and possible oxides are removed.
  • a sheet metal template e.g. fine silicon carbide, Jet pressure 4 bar, distance 40 mm
  • Adhesive powder 4 of the NiAl95 / 5 type is then used a pond size in the range of 100 to 200 microns over the sprinkled 3 moistened areas with the binder until about all 0.5 mm such adhesive powder particles 4 come to rest. After that the much finer solder powder 5 (particle diameter approx. 10-30 ⁇ m).
  • solder material the alloy NB 150 (Bal.Ni; 15% Cr; 3.5% B; 0.1% C) with a melting point of 1055 ° C and a soldering range of 1065 used up to 1200 ° C.
  • Weight is advantageous equal quantities of adhesive powder 4 and solder powder 5. But of course you can also use other proportions to get voted.
  • the packing density of the particles not of crucial importance because they are dense Packs are suitable, but less dense packs are also already sufficient.
  • Fig. 2 schematically shows a cross section of the different ones Layers after application.
  • the surface coated in this way can now be brought into the soldering furnace horizontally, vertically or overhead.
  • the solder 5 and the adhesive powder 4 remain in their applied position until the solder has melted and has wetted and soldered the substrate surface and the surface of the adhesive powder particles.
  • the soldering is carried out in a high vacuum oven at 5x10 -6 mbar, 1080 ° C and a holding time of 15 min.
  • Fig. 3 shows schematically a cross section of the different Layers after the soldering process.
  • Lot 5 has the one to be repaired
  • the surface is completely wetted and the adhesive powder particles 4 are soldered.
  • the surface looks metallic matt silvery shiny.
  • the diffusion zone is because of the short Soldering time and the relatively low soldering temperature only very much small.
  • the shovel is again covered with a template and with a 0.5 mm thick ceramic thermal barrier coating 6, here made of calcium-stabilized zirconium oxide (MetaCeram 28085), the zirconium oxide using a known flame spraying process is applied, provided.
  • a ceramic thermal barrier coating 6 here made of calcium-stabilized zirconium oxide (MetaCeram 28085)
  • Fig. 4 shows schematically the layer structure according to the flame spraying process.
  • the attachment of the zirconium oxide can be done with a Compare push button technology.
  • the zirconium oxide has one strong positive locking and many undercuts on the contrary to the usual adhesive geometries, which at best only have a small form fit. This is the anchor the zirconium oxide (TBC) layer on the component is very stable.
  • TBC zirconium oxide
  • Adhesive layers is therefore next to plasma spraying and detonation flame spraying as described above flame spraying is also suitable. The latter has the advantage that portable coating devices are used for this can.
  • Another advantage of the invention is the high resistance to thermal shock of layers.
  • coated metallic component 1 was then thermocycled in a hot gas stream (heating with about 50 Degrees / min gas temperature, 2 min hold at 1000 ° C, cooling with 100 degrees / s gas temperature to 500 ° C). Even after 70 cycles the shift has not yet occurred.
  • Another advantage is the excellent emergency running properties the thermal on the adhesive layer according to the invention sprayed TBC layers.
  • the ceramic layer 6 bursts, ie in in this case the zirconium oxide, only above the adhesive powder 4 from.
  • the TBC layer 6 falls between the adhesive powder particles 4 due to the large positive connection, so that the ceramic thermal barrier coating 6 at least in the thickness of Adhesive powder particles 4 (approx. 200 ⁇ m) are retained.
  • Fig. 6 shows a perspective Representation of a thermal insulation board for hot gas, which in New condition with the thickest possible thermal spray Thermal insulation layer should be provided.
  • the thermal insulation board consists of the alloy MAR M 247, the following chemical Composition: Bal. Ni; 8.2-8.6% Cr; 9.7-10.3% Co; 0.6-0.8% Mo; 9.8-10.2% W; 2.9-3.1% Ta; 5.4-5.6% Al; 0.8-1.2% Ti; 1.0-1.6% Hf; 0.14-0.16% C).
  • the metallic component 1 to be coated is included relatively coarse silicon carbide (particle diameter ⁇ 200 ⁇ m) blasted oxide-free and rough (10 to 30 ⁇ m). After that the surface to be coated, for example with a brush Spread thinly with organic binder 3. Under a trickle for coarse spherical adhesive powder 4 (SV 20 14 73 with the following chemical composition: Bal. Ni; 25% Cr; 5% Al; 2.5% Si; 0.5% Y; 1% Ta) with a grain diameter of 150 the plate 1 to be coated is moved back and forth up to 300 ⁇ m, even distribution down to the adhesive layer of the highly corrosion-resistant adhesive powder 4 has taken place. in the The individual powder particles should be 0.3 to 0.6 mm Distance from each other.
  • Amdry Alloy DF 5 which is additional to the high Cr content, a high Al content with somewhat reduced B content selected.
  • the exact composition is the following: Bal. Ni; 13% Cr; 3% Ta; 4% Al; 2.7% B; 0.02% Y. Lot 5 is also made using a suitable Spray device applied evenly to the surface to be soldered. It is also possible to mix adhesive powder 4 and solder 5 and then the mixture in one process step on the sprinkle the coated surface with the cement binder 3.
  • the soldering is carried out in a high vacuum oven at 1100 ° C and 15 min Hold time.
  • Thermal insulation layer 6 is a protective gas plasma spraying thin layer 7 (approx. 50 ⁇ m) SV 20 14 73 applied. That makes in addition to the rough anchoring option (as in the embodiment 1) additionally a fine interlocking what the adhesive strength of thick TBC layers in thermal shock further increases.
  • Fig. 7 shows schematically the formation of these layers.
  • the component coated in this way proved itself in a thermal shock test in a sand bed (1000 ° C to room temperature) as resistant to thermal shock.
  • the solder layer After a long period of operation, the solder layer is between corroded somewhat away from the large adhesive powder grains, but the The load-bearing part of the solder neck cannot be attacked by corrosion reduce significantly.
  • a cooled guide vane made of the material CM 247 LC DS (chemical composition: Ba. Ni; 8.1% Cr; 9.2% Co; 0.5% Mo; 9.5% W; 3.2% Ta; 0.7% Ti; 5.6% Al; 0.01% Zr; 0.01% B; 0.07% C; 1.4% Hf) exists, in new condition with a 0.7 to 0.8 mm thick TBC layer be provided.
  • CM 247 LC DS chemical composition: Ba. Ni; 8.1% Cr; 9.2% Co; 0.5% Mo; 9.5% W; 3.2% Ta; 0.7% Ti; 5.6% Al; 0.01% Zr; 0.01% B; 0.07% C; 1.4% Hf
  • the blade is sprayed in the entire channel area using inert gas plasma with the powder ProXon 21031 (alloy on Nickel base) about 0.2 mm thick coated (sprayed low in oxygen).
  • This powder exhibits because of its high aluminum content and chromium content an excellent oxidation and Corrosion resistance.
  • Oxidation and corrosion protection layer 8 a thin Layer Binder 3 applied.
  • the coating takes place then in a high vacuum furnace under solution annealing conditions for CM 247 LS DS (several hours at 1220 to 1250 ° C).
  • the oxidation and corrosion protection layer 8 am Base material 1.
  • Layer 8 further densifies and coarse adhesive powder particles 4 are formed by stable sintering 9 on the layer 8, which is now a Protective and adhesive layer is bound.
  • a cooled one is also intended Guide vane made of CM 247 LC DS with a thermal barrier coating be provided.
  • Lot 5 for attaching the coarse adhesive powder particles 4 from ProXon 21031 will be the same Powder CM 247 with an addition of 6% Cr; 3% Si; 2% Al and 0.5% B used. The order is made as above described, i.e. on the thin cement binder layer 3 the approximately 150 to 200 ⁇ m large adhesive powder 4 scattered and on it in abundance the solder powder 5. Then subjected the blade to a heat treatment in which the Base material 2 solution annealed and the solder 5 partially melted becomes.
  • thermal shock tests showed that the thermal insulation layer thus attached superior to a conventionally produced layer is. Even if for different reasons a piece of the TBC layer bursts off, remains between the adhesive powder particles maintain this layer and thus guarantee good emergency running properties. In contrast, bursts with conventionally coated If the TBC layer is scooped off, it remains on the substrate only minimal residues, which is by no means an insulating Feature. In addition, in this example shown that it is cheap, boron-free or almost boron-free Solder to be used as the brittle phase formation with W-borides is hardly possible.
  • the Base material 2 is MAR M 247, NB 150 was used as lot 5 and the adhesive powder particles 4 are made of NiA195 / 5.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Coating By Spraying Or Casting (AREA)
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Abstract

A method of applying a metallic bonding layer for thermally sprayed ceramic heat insulating layers (6) on metallic components involves (a) applying a binder onto the degreased and oxide-free metallic surface of the substrate material (2); (b) applying metallic bonding powder (4) uniformly onto the binder; (c) applying solder powder (5), of smaller particle size than the bonding powder (4), uniformly onto the binder; and (d) drying the binder and heat treating to effect soldering. In an alternative method, an oxidation and corrosion resistant layer is produced on the cleaned metallic surface by gas-shielded plasma spraying prior to step (a), the bonding powder is a coarse powder having the same composition as this oxidation and corrosion resistant layer, step (c) is omitted and step (d) comprises drying the binder and then heat treating (solution annealing) to form a sintered bond between the metallic component and the oxidation and corrosion resistant layer and between the oxidation and corrosion resistant layer and the bonding powder. Also claimed are metallic bonding layers produced by the above methods.

Description

Technisches GebietTechnical field

Die Erfindung bezieht sich auf das Gebiet der Werkstofftechnik. Sie betrifft ein Verfahren zur Aufbringung einer metallischen Haftschicht für anschliessend auf diese Haftschicht aufzubringende thermisch gespritzte keramische Wärmedämmschichten (TBC) auf metallische Bauteile sowie eine nach diesem Verfahren hergestellte metallische Haftschicht.The invention relates to the field of materials technology. It relates to a method for applying a metallic Adhesive layer for thermally sprayed ceramic thermal insulation layers to be subsequently applied to this adhesive layer (TBC) on metallic components as well as a metallic adhesive layer produced by this process.

Stand der TechnikState of the art

Normalerweise lassen sich Metall und Keramik wegen der unterschiedlichen Wärmesausdehnungskoeffizienten nicht miteinander verbinden.Usually, metal and ceramic can be different because of the different Thermal expansion coefficients not with each other connect.

Bekannt ist, dass zur Lösung dieses Problemes eine duktile Zwischenschicht zwischen die zu verbindenden Teile gebracht wird, welche die Differenzdehnungen bei unterschiedlichen Temperaturen elastisch-plastisch ausgleicht (vgl. W. J. Brindley, R. A. Miller: "TBcs for better engine efficiency", Nasa Lewis Research Center Cleveland, Advanced Materials & Progress 8/1989, S.29-33). Diese als Haftschichten bezeichnete Zwischenschichten werden üblicherweise mittels bekannter Flammspritzverfahren, Plasmaspritzverfahren oder Detonationsspritzverfahren aufgebracht. Sie ermöglichen eine metallurgisch-mechanische Bindung an das metallische Bauteil und eine rein mechanische Bindung der ebenfalls thermisch gespritzten Keramikschicht an die Haftschicht, wobei diese Verbindung ausgesprochen schlagempfindlich und thermoschockempfindlich ist.It is known that a ductile solution to this problem Intermediate layer brought between the parts to be connected which is the differential expansion at different Temperature-elastic compensates (cf. W. J. Brindley, R.A. Miller: "TBcs for better engine efficiency", Nasa Lewis Research Center Cleveland, Advanced Materials & Progress 8/1989, pp.29-33). These referred to as adhesive layers Interlayers are usually known by means of Flame spraying process, plasma spraying process or detonation spraying process upset. They enable a metallurgical-mechanical Binding to the metallic component and a purely mechanical binding of the also thermally sprayed Ceramic layer to the adhesive layer, this connection extremely sensitive to impact and thermal shock is.

Da die keramischen Wärmedämmschichten die beschichteten metallischen Bauteile vor schädlichen Wärmespannungen schützen, ist deren lückenloses Vorhandensein wichtig für eine ausreichende Lebensdauer der Bauteile. Derartig beschichtete Bauteile werden insbesondere im Gebiet der Verbrennungstechnik eingesetzt, beispielsweise für Brennkammerteile oder Gasturbinenschaufeln.Since the ceramic thermal insulation layers the coated metallic Protect components from harmful thermal stresses their complete existence is important for a sufficient Component life. Components coated in this way are especially in the field of combustion technology used, for example for combustion chamber parts or gas turbine blades.

Der Nachteil der bisher erzeugten metallischen Haftschichten für keramische Wärmedämmschichten besteht darin, dass sie eine ungenügende Rauhigkeit aufweisen und damit zu wenig Formschluss (Hinterschneidungen) bieten, so dass die Schichtdicke der TBC-Schichten begrenzt ist. Bekannt sind Schichtdicken von ca. 0,2 bis 0,4 mm, wobei Schichtdicken von etwa 0,3 mm am häufigsten anzutreffen sind. Sind sie dicker, so steigt die Gefahr des Abplatzens rapide an. Sind sie dünner, so lässt die Wärmedämmwirkung schnell nach. Neuere Entwicklungen gehen zwar dahin, gröbere Haftschichten (ca. 0,6 mm) zu spritzen, jedoch fehlt der nötige Formschluss.The disadvantage of the metallic adhesive layers produced so far for ceramic thermal insulation layers is that they have insufficient roughness and therefore too little Offer form fit (undercuts) so that the layer thickness of the TBC layers is limited. Layer thicknesses are known from about 0.2 to 0.4 mm, with layer thicknesses of about 0.3 mm are most common. If you are fatter, so the risk of flaking increases rapidly. Are you thinner the thermal insulation effect quickly subsides. Recent developments go there, coarser adhesive layers (approx. 0.6 mm) to inject, but the necessary positive locking is missing.

Eine für bekannte metallische Haftschichten typische Rauhigkeit (Unterschied Spitze-Tal) liegt bei etwa 30 µm. Rauher können die Schichten nicht gespritzt werden, da die Dimension der aufzuschmelzenden Pulverteilchen je nach Beschichtungsverfahren (unterschiedliche Spritztemperaturen und Spritzgeschwindigkeiten) auf ca. 10 bis 50 µm begrenzt ist und die flüssigen Pulverteilchen beim Auftreffen auf das Substrat abflachen (vgl. B. Heine: "Thermisch gespritzte Schichten", Metall, 49. Jahrgang, 1/1995, S.51-57). A roughness typical of known metallic adhesive layers (Difference between peak and valley) is around 30 µm. Rougher the layers cannot be sprayed because of the dimension of the powder particles to be melted depending on the coating process (different spray temperatures and spray speeds) is limited to approx. 10 to 50 µm and the Flatten the liquid powder particles when they hit the substrate (cf. B. Heine: "Thermally sprayed layers", metal, 49th year, 1/1995, p.51-57).

Einer naheliegenden Abhilfe mittels gröberem Aufrauhen durch Sandstrahlen bzw. mittels Veränderung der Flammspritzparameter sind aber Grenzen gesetzt. Beispielsweise kann durch Niedergeschwindigkeitsflammenspritzen zwar die Schichtdicke der TBC-Keramikschicht erhöht werden, aber derartige Schichten halten keinen Thermoschock aus.An obvious remedy by roughening through Sandblasting or by changing the flame spray parameters but there are limits. For example, by low speed flame spraying the layer thickness of the TBC ceramic layer can be increased, but such layers cannot withstand thermal shock.

Rauhgewindedrehen oder Einfräsen von Nuten in die zu beschichtenden Oberflächen, wie von B. Heine in o.g. Artikel zur Haftungsförderung bei angestrebten Schichtdicken von grösser 1 mm angegeben werden, sind aufwendig und lassen sich bei komplizierter geometrischer Werstückform nur schwer realisieren.Turning rough threads or milling grooves into those to be coated Surfaces as described by B. Heine in the above. items to promote adhesion with target layer thicknesses of specified greater than 1 mm are complex and can be difficult to realize with a complicated geometric workpiece shape.

Darstellung der ErfindungPresentation of the invention

Die Erfindung versucht, all diese Nachteile zu vermeiden. Ihr liegt die Aufgabe zugrunde, eine metallische Haftschicht und ein Verfahren zur Aufbringung dieser Haftschicht für keramische Wärmedämmschichten auf einem metallischen Grundkörper zu entwickeln, mit dem es gegenüber dem bekannten Stand der Technik möglich ist, anschliessend keramische Wärmedämmschichten grösserer Dicke thermisch zu spritzen und zu befestigen. Dabei sollen die Schichten stabil haften und unempfindlich gegen Schlageinwirkung sein.The invention tries to avoid all these disadvantages. you is based on the task of a metallic adhesive layer and a method of applying this adhesive layer for ceramic Thermal insulation layers on a metallic base body too develop with which it is compared to the known state of the art Technology is possible, then ceramic thermal insulation layers thermally spraying and attaching thicker. The layers should adhere stably and insensitively to be against impact.

Erfindungsgemäss wird dies bei einem Verfahren zur Aufbringung einer metallischen Haftschicht mit Formschluss und Hinterschneidungen für anschliessend auf diese Haftschicht aufzubringende thermisch gespritzte keramische Wärmedämmschichten auf metallische Bauteile, wobei die zu beschichtende Oberfläche in einem ersten Verfahrensschritt gereinigt wird, so dass eine fett- und oxidfreie metallische Oberfläche vorliegt, dadurch erreicht,

  • a) dass in einem zweiten Verfahrensschritt ein Binder auf die metallische Oberfläche aufgebracht wird,
  • b) dass in einem dritten Verfahrensschritt auf den Binder gleichmässig metallisches Haftpulver und Lotpulver, welches eine geringere Teilchengrösse als das Haftpulver aufweist, aufgebracht werden, und
  • c) dass nach Trocknung des Binders eine Wärmebehandlung zwecks Lötung erfolgt.
    • According to the invention, this is the case with a method for applying a metallic adhesive layer with positive locking and undercuts for thermally sprayed ceramic thermal insulation layers to be subsequently applied to metallic components, the surface to be coated being cleaned in a first process step, so that a grease and oxide-free metallic surface is present, achieved by
  • a) that a binder is applied to the metallic surface in a second process step,
  • b) in a third process step, metallic adhesive powder and solder powder, which has a smaller particle size than the adhesive powder, are applied uniformly to the binder, and
  • c) that after the binder has dried, a heat treatment is carried out for the purpose of soldering.

    • Erfindungsgemäss wird dies bei einem Verfahren zur Aufbringung einer metallischen Haftschicht mit Formschluss und Hinterschneidungen fur anschliessend auf diese Haftschicht aufzubringende thermisch gespritzte keramische Wärmedämmschichten auf metallische Bauteile, wobei die zu beschichtende Oberfläche in einem ersten Verfahrensschritt gereinigt wird, so dass eine fett- und oxidfreie metallische Oberfläche vorliegt, und in einem zweiten Verfahrensschritt mittels Schutzgasplasmaspritzen eine oxidations- und korrosionsfeste Schicht auf der metallischen Oberfläche erzeugt wird, dadurch erreicht,

  • a) dass in einem dritten Verfahrensschritt ein Binder auf die oxidations- und korrosionsfeste Schicht aufgebracht wird,
  • b) dass auf den Binder gleichmässig ein grobes Haftpulver der gleichen Zusammensetzung wie die oxidations- und korrosionsfeste Schicht aufgebracht wird, und
  • c) dass nach Trocknung des Binders eine Wärmebehandlung (Lösungsglühen) zwecks Bildung einer Sinterverbindung zwischen dem metallischen Bauteil und der Schicht bzw. zwischen der Schicht und dem Haftpulver erfolgt.
    • According to the invention, this is the case with a method for applying a metallic adhesive layer with positive locking and undercuts for thermally sprayed ceramic thermal insulation layers to be subsequently applied to metallic components, the surface to be coated being cleaned in a first process step, so that a grease and oxide-free metallic surface is present, and in a second process step using protective gas plasma spraying, an oxidation and corrosion-resistant layer is produced on the metallic surface,
  • a) that a binder is applied to the oxidation and corrosion-resistant layer in a third process step,
  • b) that a coarse adhesive powder of the same composition as the oxidation and corrosion resistant layer is applied uniformly to the binder, and
  • c) that after the binder has been dried, a heat treatment (solution annealing) is carried out to form a sintered connection between the metallic component and the layer or between the layer and the adhesive powder.

    • Die Vorteile der Erfindung bestehen u.a. darin, dass mit diesen Verfahren Haftschichten erzeugt werden, die gegenüber dem Stand der Technik sehr rauh sind. Die aufgelöteten bzw. angesinterten Metallpulverteilchen stellen dabei sehr stabile und formschlüssige Verankerungen für die aufzuspritzende TBC-Schicht dar, so dass vergleichsweise dicke, stabil haftende keramische Wärmedämmschichten erzeugt werden können. The advantages of the invention include in that with these Process adhesive layers are generated that are opposite to the State of the art are very rough. The soldered or sintered Metal powder particles are very stable and positive anchoring for the TBC layer to be sprayed on so that comparatively thick, stable adherence ceramic thermal insulation layers can be generated.

    Es ist besonders zweckmässig, wenn anstelle des zeitlich nacheinander erfolgenden Aufbringens des metallischen Haftpulvers und des Lotpulvers beide Pulver zunächst intensiv gemischt werden und danach dieses Gemisch auf die metallische Oberfläche des Grundmaterials aufgebracht wird. Dadurch wird eine gleichmässigere Verteilung der Pulverteilchen erreicht und ausserdem die Verfahrenszeit verkürzt.It is particularly useful if instead of the time successive application of the metallic adhesive powder and of the solder powder, both powders are first mixed intensively be and then this mixture on the metallic Surface of the base material is applied. This will achieved a more uniform distribution of the powder particles and also shortens the process time.

    Ferner ist es vorteilhaft, wenn nach erfolgter Lötung zusätzlich auf die Haftschicht eine dünne Schicht des Haftpulvers mittels Spritzverfahren, beispielsweise Schutzgasplasmaspritzen, aufgetragen wird. Das ergibt zwischen der groben Verankerungsmöglichkeit zusätzlich die Möglichkeit einer feinen Verzahnung, was die Haftfestigkeit von dicken TBC-Schichten unter Thermoschockbedingungen weiter steigert.It is also advantageous if after soldering has been carried out additionally a thin layer of the adhesive powder on the adhesive layer by means of spraying processes, for example protective gas plasma spraying, is applied. This results in between the rough anchoring option additionally the possibility of a fine Interlocking what the adhesive strength of thick TBC layers increases further under thermal shock conditions.

    Schliesslich werden mit Vorteil als Lotmaterial artgleiches Material wie das Grundmaterial und borfreie bzw. borarme Lote verwendet. Dadurch wird eine mögliche Sprödphasenbildung verringert.Finally, it is advantageous to use the same kind of solder material Material such as the base material and boron-free or low-boron solders used. This reduces possible brittle phase formation.

    Das erfindungsgemässe Verfahren kann sowohl örtlich für Reperaturzwecke als auch zur Beschichtung von Neuteilen verwendet werden.The method according to the invention can be used locally for repair purposes as well as used for coating new parts become.

    Die erfindungsgemäss hergestellte metallische Haftschicht besteht je nach angewandter Verfahrensvariante aus einer die Oberfläche des metallischen Bauteiles benetzenden Lotschicht mit darin fest verlöteten sphärisch oder spratzig ausgebildeten Haftpulverteilchen oder zusätzlich aus einer dünnen gespritzten, insbesondere schutzgasplasmagespritzten Schicht aus artgleichem Material wie die Haftpulverteilchen oder aus einer auf die Oberfläche des metallischen Bauteiles schutzgasplasmagespritzten Schutzschicht mit an deren Oberfläche angesinterten Haftpulverteilchen. Diese metallische Haftschicht garantiert ein stabiles Haften der thermisch gespritzten keramischen Wärmedämmschichten, erlaubt grössere Schichtdicken und führt zu guten Notlaufeigenschaften.The metallic adhesive layer produced according to the invention exists depending on the process variant used from a Surface of the solder layer wetting the metallic component with spherically or sputteringly formed soldered in it Adhesive powder particles or additionally from a thin sprayed, in particular protective gas plasma sprayed layer same type of material as the adhesive powder particles or an inert gas plasma sprayed onto the surface of the metallic component Protective layer with on its surface sintered adhesive powder particles. This metallic adhesive layer guarantees stable adhesion of the thermally sprayed ceramic thermal insulation layers, allows larger ones Layer thicknesses and leads to good emergency running properties.

    Es ist ausserdem vorteilhaft, wenn die Höhe der Haftpulverteilchen etwa so gross ist wie die Schichtdicke der thermisch aufzuspritzenden keramischen Wärmedämmschicht. Dadurch wird die Schicht nahezu schlagunempfindlich, weil Schläge im Wesentlichen metallisch aufgefangen werden.It is also advantageous if the height of the adhesive powder particles is approximately as large as the layer thickness of the thermal ceramic thermal barrier coating to be sprayed on. This will the layer is almost insensitive to impact because strikes essentially be collected in a metallic way.

    Kurze Beschreibung der ZeichnungBrief description of the drawing

    In der Zeichnung sind mehrere Ausführungsbeispiele der Erfindung dargestellt.In the drawing are several embodiments of the invention shown.

    Es zeigen:

    Fig. 1
    eine perspektivische Darstellung einer zu beschichtenden Leitschaufel;
    Fig. 2
    einen schematischen Querschnitt durch die verschiedenen Schichten nach dem Applizieren;
    Fig. 3
    einen schematischen Querschnitt durch die verschiedenen Schichten nach dem Löten;
    Fig. 4
    einen schematischen Querschnitt durch die verschiedenen Schichten nach dem Flammspritzen der keramischen Wärmedämmschicht;
    Fig. 5
    einen schematischen Querschnitt durch die verschiedenen Schichten nach TBC-Beschichtung und seitlicher Druckbeanspruchung;
    Fig. 6
    eine perspektivische Darstellung einer zu beschichtenden Wärmedämmplatte;
    Fig. 7
    einen schematischen Querschnitt durch die verschiedenen Schichten nach dem Löten und Flammspritzen der Haftschicht;
    Fig. 8
    einen schematischen Querschnitt durch die verschiedenen Schichten eines weiteren Ausführungsbeispieles (angesintertes Haftpulver);
    Fig. 9
    ein Schliffbild einer metallischen Probe mit aufgelöteter Haftschicht.
    Show it:
    Fig. 1
    a perspective view of a guide vane to be coated;
    Fig. 2
    a schematic cross section through the different layers after application;
    Fig. 3
    a schematic cross section through the different layers after soldering;
    Fig. 4
    a schematic cross section through the different layers after flame spraying the ceramic thermal barrier coating;
    Fig. 5
    a schematic cross section through the different layers after TBC coating and lateral pressure;
    Fig. 6
    a perspective view of a thermal insulation panel to be coated;
    Fig. 7
    a schematic cross section through the different layers after soldering and flame spraying the adhesive layer;
    Fig. 8
    a schematic cross section through the different layers of another embodiment (sintered adhesive powder);
    Fig. 9
    a micrograph of a metallic sample with soldered adhesive layer.

    Es sind nur die für das Verständnis der Erfindung wesentlichen Elemente gezeigt.It is only essential for understanding the invention Elements shown.

    Weg zur Ausführung der ErfindungWay of carrying out the invention

    Nachfolgend wird die Erfindung anhand von mehreren Ausführungsbeispielen und der Figuren 1 bis 9 näher erläutert.The invention is described below using several exemplary embodiments and Figures 1 to 9 explained in more detail.

    In Fig. 1 ist eine Leitschaufel einer Gasturbine als Beispiel für ein zu beschichtendes metallisches Bauteil 1 dargestellt. Sie besteht aus dem metallischen Grundmaterial (Substrat) 2, in diesem Falle aus der Legierung IN 939 der folgenden chemischen Zusammensetzung: Bal. Ni; 22,5% Cr; 19,0% Co; 2,0% W; 1,0% Nb; 1,4% Ta; 3,7% Ti; 1,9% Al; 0,1 Zr; 0,01 B; 0,15 C. Die Schaufel ist auf den gasführenden Flächen mit einer Korrosions- und Oxidationsschicht versehen (MCrAlY, z.B. SV201473: Bal. Ni; 25% Cr; 5% Al; 2,5% Si; 0,5% Y; 1% Ta). Ausserdem ist diese Schaufel auf der Eintrittskante, der Druckseite des Blattes und auf den Kanalwänden mit einer ca. 0,3 mm dicken keramischen Wärmedämmschicht aus Ytrium-stabilisiertem Zirkonoxid folgender Zusammensetzung beschichtet: Bal. ZrO2 incl 2,5% HfO2; 7-9% Y2O3; <3% andere.1 shows a guide vane of a gas turbine as an example of a metallic component 1 to be coated. It consists of the metallic base material (substrate) 2, in this case the alloy IN 939 with the following chemical composition: Bal. Ni; 22.5% Cr; 19.0% Co; 2.0% W; 1.0% Nb; 1.4% Ta; 3.7% Ti; 1.9% Al; 0.1 Zr; 0.01 B; 0.15 C. The blade is provided with a corrosion and oxidation layer on the gas-carrying surfaces (MCrAlY, e.g. SV201473: Bal. Ni; 25% Cr; 5% Al; 2.5% Si; 0.5% Y; 1 % Ta). In addition, this blade is coated on the leading edge, the pressure side of the blade and on the channel walls with an approximately 0.3 mm thick thermal insulation layer made of ytrium-stabilized zirconium oxide with the following composition: Bal. ZrO 2 incl 2.5% HfO 2 ; 7-9% Y 2 O 3 ; <3% others.

    Nach einer Betriebszeit von 25 000 Stunden kommt die Gasturbinenleitschaufel zur Rekonditionierung. Dabei wird festgestellt, dass durch thermische Überbeanspruchung und Erosion an der Eintrittskante des Blattes und auf der Kanalwand die Wärmedämmschicht nicht mehr vorhanden ist (vgl. schraffierte Bereiche in Fig. 1). Da die Schaufel keine weiteren Schäden aufweist, wird aus Kostengründen keine totale Neubeschichtung, sondern eine partielle Reparatur der Wärmedämmschicht angestrebt. Auf Grund dessen, dass an den oben beschriebenen Stellen systematisch ein besonders starker Angriff der TBC erfolgt, sollte die TBC-Schicht nicht nur in gleicher Stärke, sondern möglichst dicker ausgeführt werden.The gas turbine guide vane comes after an operating time of 25,000 hours for reconditioning. It is determined that due to thermal overload and erosion at the leading edge of the sheet and on the channel wall Thermal insulation layer is no longer present (see hatched Areas in Fig. 1). Since the shovel did no further damage will not be completely re-coated for cost reasons, but a partial repair of the thermal insulation layer sought. Because of that on the above Systematically make a particularly strong attack by the TBC the TBC layer should not only be of the same thickness, but run as thick as possible.

    Das gelingt mit dem erfindungsgemässen Verfahren, bei dem die keramische Schicht flexibler an das metallische Substrat 2 gebunden wird durch Gradieren des Übergangs Metall-Keramik unter Verwendung einer speziellen Haftschicht.This is achieved with the method according to the invention, in which the ceramic layer more flexible to the metallic substrate 2 is bound by grading the transition from metal to ceramic using a special adhesive layer.

    Zunächst wird die Schaufel 1 im Wasserdampfstrahl von grobem Schmutz (Verbrennungsrückstände) gereinigt. Danach werden noch anhaftende Ablagerungen mittels weichem Sandstrahlen, (z.B. feines Aluminiumpulver, 2 bar Strahldruck, 20 cm Abstand) entfernt. Dabei darf die noch intakte keramische Wärmedämmschicht nicht abgetragen werden.First, the blade 1 becomes coarse in the steam jet Dirt (combustion residues) cleaned. After that deposits still adhering by means of soft sandblasting, (e.g. fine aluminum powder, 2 bar jet pressure, 20 cm distance) away. The still intact ceramic thermal insulation layer is allowed not be removed.

    Nun werden die nicht zu beschichtenden Schaufelteile abgedeckt, beispielsweise mit einer Blechschablone, und die zu beschichtenden Flächen werden blankgestrahlt (z.B. feines Siliziumcarbid, Strahldruck 4 bar, Abstand 40 mm), so dass jegliche TBC-Reste und eventuelle Oxide entfernt werden.Now the blade parts not to be coated are covered, for example with a sheet metal template, and the too coating surfaces are blasted (e.g. fine silicon carbide, Jet pressure 4 bar, distance 40 mm), so that any TBC residues and possible oxides are removed.

    Die so gereinigten, metallischen, sauberen, fett- und oxidfreien Oberflächen werden nun mit Hilfe eines Pinsels, Tupfers oder Sprayers dünn mit einem für die Lotpastenherstellung üblichen organischen Binder 3, sogenanntem Zement, beschichtet. Danach wird Haftpulver 4 des Typs NiAl95/5 mit einer Teichengrösse im Bereich von 100 bis 200 µm über die mit dem Binder 3 befeuchteten Stellen gestreut, bis etwa alle 0,5 mm solche Haftpulverteilchen 4 zu liegen kommen. Danach wird in gleicher Weise das viel feinere Lotpulver 5 (Teilchendurchmesser ca. 10-30 µm) gestreut. Als Lotmaterial wird die Legierung NB 150 (Bal. Ni; 15% Cr; 3,5% B; 0,1% C) mit einem Schmelzpunkt von 1055°C und einem Lötbereich von 1065 bis 1200°C verwendet. Vorteilhaft sind dabei etwa gewichtsmässig gleichgrosse Mengen von Haftpulver 4 und Lotpulver 5. Aber selbstverständlich können auch andere Mengenverhältnisse gewählt werden. Dabei ist die Packungsdichte der Teilchen nicht von ausschlaggebender Bedeutung, denn es sind dichte Packungen geeignet, aber auch weniger dichte Packungen sind schon ausreichend.The cleaned, metallic, clean, fat and oxide free Surfaces are now using a brush, swab or sprayers thin with one for solder paste production usual organic binder 3, so-called cement, coated. Adhesive powder 4 of the NiAl95 / 5 type is then used a pond size in the range of 100 to 200 microns over the sprinkled 3 moistened areas with the binder until about all 0.5 mm such adhesive powder particles 4 come to rest. After that the much finer solder powder 5 (particle diameter approx. 10-30 µm). As solder material the alloy NB 150 (Bal.Ni; 15% Cr; 3.5% B; 0.1% C) with a melting point of 1055 ° C and a soldering range of 1065 used up to 1200 ° C. Weight is advantageous equal quantities of adhesive powder 4 and solder powder 5. But of course you can also use other proportions to get voted. The packing density of the particles not of crucial importance because they are dense Packs are suitable, but less dense packs are also already sufficient.

    Der Binder 3 trocknet nach kurzer Zeit (ca. 15 min) und hält das Haftpulver 4 und das Lot 5 fest auf dem Substrat 2. Fig. 2 zeigt schematisch einen Querschnitt der verschiedenen Schichten nach dem Applizieren.The binder 3 dries after a short time (approx. 15 min) and holds the adhesive powder 4 and the solder 5 firmly on the substrate 2. Fig. 2 schematically shows a cross section of the different ones Layers after application.

    Die so beschichtete Fläche kann nun horizontal, senkrecht oder über Kopf in den Lötofen gebracht werden. Das Lot 5 und das Haftpulver 4 bleiben an ihrem applizierten Platz, bis das Lot aufgeschmolzen ist und die Substratoberfläche und die Oberfläche der Haftpulverteilchen benetzt und verlötet hat. Die Lötung erfolgt in einem Hochvakuumofen bei 5x10-6 mbar, 1080°C und einer Haltezeit von 15 min.The surface coated in this way can now be brought into the soldering furnace horizontally, vertically or overhead. The solder 5 and the adhesive powder 4 remain in their applied position until the solder has melted and has wetted and soldered the substrate surface and the surface of the adhesive powder particles. The soldering is carried out in a high vacuum oven at 5x10 -6 mbar, 1080 ° C and a holding time of 15 min.

    Fig. 3 zeigt schematisch einen Querschnitt der verschiedenen Schichten nach dem Lötvorgang. Das Lot 5 hat die zu reparierende Fläche gänzlich benetzt und die Haftpulverteilchen 4 sind fest verlötet. Die Oberfläche sieht metallisch matt silbrig glänzend aus. Die Diffusionszone ist wegen der kurzen Lötzeit und der relativ niedrigen Löttemperatur nur sehr klein.Fig. 3 shows schematically a cross section of the different Layers after the soldering process. Lot 5 has the one to be repaired The surface is completely wetted and the adhesive powder particles 4 are soldered. The surface looks metallic matt silvery shiny. The diffusion zone is because of the short Soldering time and the relatively low soldering temperature only very much small.

    Nach dem Aufbringen der erfindungsgemässen metallischen Haftschicht wird die Schaufel wiederum mit einer Schablone abgedeckt und mit einer 0,5 mm dicken keramischen Wärmedämmschicht 6, hier aus Calzium-stabilisierten Zirkonoxid (MetaCeram 28085), wobei das Zirkonoxid mittels bekanntem Flammspritzverfahren aufgebracht wird, versehen. After application of the metallic adhesive layer according to the invention the shovel is again covered with a template and with a 0.5 mm thick ceramic thermal barrier coating 6, here made of calcium-stabilized zirconium oxide (MetaCeram 28085), the zirconium oxide using a known flame spraying process is applied, provided.

    Fig. 4 zeigt schematisch den Schichtaufbau nach dem Flammspritzverfahren.Fig. 4 shows schematically the layer structure according to the flame spraying process.

    Die Befestigung des Zirkonoxides lässt sich in etwa mit einer Druckknopftechnik vergleichen. Das Zirkonoxid weist einen starken Formschluss und viele Hinterschneidungen auf im Gegensatz zu bisher üblichen Haftgeometrien, welche bestenfalls nur einen kleinen Formschluss aufweisen. Damit ist die Verankerung der Zirkonoxid(TBC)-Schicht auf dem Bauteil sehr stabil. Für das Aufspritzen der TBC-Schichten auf die erfindungsgemässen Haftschichten ist somit neben dem Plasmaspritzen und dem Detonationsflammspritzen wie oben beschrieben auch das Flammspritzen geeignet. Letzteres hat den Vorteil, dass dafür transportable Beschichtungsgeräte eingesetzt werden können.The attachment of the zirconium oxide can be done with a Compare push button technology. The zirconium oxide has one strong positive locking and many undercuts on the contrary to the usual adhesive geometries, which at best only have a small form fit. This is the anchor the zirconium oxide (TBC) layer on the component is very stable. For spraying the TBC layers onto those according to the invention Adhesive layers is therefore next to plasma spraying and detonation flame spraying as described above flame spraying is also suitable. The latter has the advantage that portable coating devices are used for this can.

    Ein weiterer Vorteil der Erfindung besteht in der hohen Thermoschockunempfindlichkeit der Schichten. Das gemäss o.b. Verfahren beschichtete metallische Bauteil 1 wurde anschliessend in einem Heissgasstrom thermozykliert (Aufheizen mit etwa 50 Grad/min Gastemperatur, 2 min Halten bei 1000°C, Abkühlen mit 100 Grad/s Gastemperatur auf 500°C). Selbst nach 70 Zyklen ist noch keine Ablösung der Schicht aufgetreten.Another advantage of the invention is the high resistance to thermal shock of layers. According to the above method coated metallic component 1 was then thermocycled in a hot gas stream (heating with about 50 Degrees / min gas temperature, 2 min hold at 1000 ° C, cooling with 100 degrees / s gas temperature to 500 ° C). Even after 70 cycles the shift has not yet occurred.

    Ein anderer Vorteil besteht in den hervorragenden Notlaufeigenschaften der auf die erfindungsgemässe Haftschicht thermisch gespritzen TBC-Schichten. Bei Schlag- bzw. seitlicher Druckbeanspruchung platzt die keramische Schicht 6, also in diesem Falle das Zirkonoxid, nur oberhalb des Haftpulvers 4 ab. Zwischen den Haftpulverteilchen 4 fällt die TBC-Schicht 6 aufgrund des grossen Formschlusses nicht heraus, so dass die keramische Wärmedämmschicht 6 mindestens in der Dicke der Haftpulverteilchen 4 (ca. 200 µm) erhalten bleibt. Dies ist schematisch in Fig. 5 dargestellt. Dieses Ergebnis berechtigt zu der Annahme, dass sowohl die Eintrittskante als auch die Kanalwand der reparierten Leitschaufel dem Abtrag der Wärmedämmschicht länger widerstehen kann als die dünnere und weniger verankerte originale Wärmedämmschicht. Mit diesem Ausführungsbeispiel ist die prinzipielle Eignung der grob gelöteten Haftschichten für die Aufbringung thermisch gespritzter Wärmedämmschichten nachgewiesen. Bei der Verwendung der miteinander kombinierten Materialien ist darauf zu achten, dass die Oxidations- und Korrosionsfestigkeit von Haftpulver, Lot und Haftschicht möglichst grösser sind als die entsprechenden Werte des Grundmaterials.Another advantage is the excellent emergency running properties the thermal on the adhesive layer according to the invention sprayed TBC layers. In the case of striking or side The ceramic layer 6 bursts, ie in in this case the zirconium oxide, only above the adhesive powder 4 from. The TBC layer 6 falls between the adhesive powder particles 4 due to the large positive connection, so that the ceramic thermal barrier coating 6 at least in the thickness of Adhesive powder particles 4 (approx. 200 µm) are retained. This is schematically shown in Fig. 5. This result is justified assuming that both the leading edge and the Channel wall of the repaired guide vane to remove the thermal insulation layer can withstand longer than the thinner and less anchored original thermal insulation layer. With this embodiment is the basic suitability of the roughly soldered Adhesive layers for the application of thermally sprayed thermal insulation layers proven. When using the with each other Combined materials must be ensured that the Oxidation and corrosion resistance of adhesive powder, solder and Adhesive layer are as large as possible than the corresponding ones Basic material values.

    In den Fig. 6 und 7 ist ein zweites Ausführungsbeispiel der Erfindung dargestellt. Fig. 6 zeigt in einer perspektivischen Darstellung eine Wärmedämmplatte zur Heissgasführung, die im Neuzustand mit einer möglichst dicken thermisch gespritzen Wärmedämmschicht versehen werden soll. Die Wärmedämmplatte besteht aus der Legierung MAR M 247, die folgende chemische Zusammensetzung aufweist: Bal. Ni; 8,2-8,6% Cr; 9,7-10,3% Co; 0,6-0,8% Mo; 9,8-10,2% W; 2,9-3,1% Ta; 5,4-5,6% Al; 0,8-1,2% Ti; 1,0-1,6% Hf; 0,14-0,16% C).6 and 7 is a second embodiment of the Invention shown. Fig. 6 shows a perspective Representation of a thermal insulation board for hot gas, which in New condition with the thickest possible thermal spray Thermal insulation layer should be provided. The thermal insulation board consists of the alloy MAR M 247, the following chemical Composition: Bal. Ni; 8.2-8.6% Cr; 9.7-10.3% Co; 0.6-0.8% Mo; 9.8-10.2% W; 2.9-3.1% Ta; 5.4-5.6% Al; 0.8-1.2% Ti; 1.0-1.6% Hf; 0.14-0.16% C).

    Zunächst wird das zu beschichtende metallische Bauteil 1 mit relativ groben Siliziumcarbid (Partikeldurchmesser <200 µm) oxidfrei und rauh gestrahlt (10 bis 30 µm). Danach wird die zu beschichtende Oberfläche beispielsweise mit einem Pinsel dünn mit organischem Binder 3 bestrichen. Unter einer Rieselvorrichtung für grobes sphärisches Haftpulver 4 (SV 20 14 73 mit folgender chemischer Zusammensetzung: Bal. Ni; 25% Cr; 5% Al; 2,5% Si; 0,5% Y; 1% Ta) mit einem Korndurchmesser von 150 bis 300 µm wird die zu beschichtende Platte 1 hin- und herbewegt, bis auf der Klebeschicht eine gleichmässige Verteilung des hoch korrosionsfesten Haftpulvers 4 stattgefunden hat. Im Mittel sollten die einzelnen Pulverteilchen 0,3 bis 0,6 mm Abstand voneinander haben. Durch elekrostatische Aufladung ist es möglich, dass mehrere der Haftpulverteilchen 4 aneinander zu liegen kommen, was aber für ihre Funktion keinen Nachteil hat. Als Lot wird Amdry Alloy DF 5, welches zusätzlich zum hohen Cr-Gehalt einen hohen Al-Gehalt bei etwas reduziertem B-Gehalt aufweist, gewählt. Die genaue Zusammensetzung ist folgende: Bal. Ni; 13% Cr; 3% Ta; 4% Al; 2,7% B; 0,02% Y. Das Lot 5 wird ebenfalls mittels einer geeigneten Rieselvorrichtung gleichmässig auf die zu lötende Fläche aufgebracht. Es ist auch möglich, Haftpulver 4 und Lot 5 zu mischen und dann das Gemisch in einem Verfahrensschritt auf die mit dem Zement-Binder 3 eingestrichene Fläche aufzustreuen.First, the metallic component 1 to be coated is included relatively coarse silicon carbide (particle diameter <200 µm) blasted oxide-free and rough (10 to 30 µm). After that the surface to be coated, for example with a brush Spread thinly with organic binder 3. Under a trickle for coarse spherical adhesive powder 4 (SV 20 14 73 with the following chemical composition: Bal. Ni; 25% Cr; 5% Al; 2.5% Si; 0.5% Y; 1% Ta) with a grain diameter of 150 the plate 1 to be coated is moved back and forth up to 300 μm, even distribution down to the adhesive layer of the highly corrosion-resistant adhesive powder 4 has taken place. in the The individual powder particles should be 0.3 to 0.6 mm Distance from each other. Through electrostatic charging it is possible for several of the adhesive powder particles 4 to come together come to rest, but none for their function Disadvantage. Amdry Alloy DF 5, which is additional to the high Cr content, a high Al content with somewhat reduced B content selected. The exact composition is the following: Bal. Ni; 13% Cr; 3% Ta; 4% Al; 2.7% B; 0.02% Y. Lot 5 is also made using a suitable Spray device applied evenly to the surface to be soldered. It is also possible to mix adhesive powder 4 and solder 5 and then the mixture in one process step on the sprinkle the coated surface with the cement binder 3.

    Die Lötung erfolgt im Hochvakuumofen bei 1100°C und 15 min Haltezeit. Vor dem anschliessenden Luftplasmaspritzen der Wärmedämmschicht 6 wird mittels Schutzgasplasmaspritzen eine dünne Schicht 7 (ca. 50 µm) SV 20 14 73 aufgetragen. Das ergibt neben der groben Verankerungsmöglichkeit (wie im Ausführungsbeispiel 1) noch zusätzlich eine feine Verzahnung, was die Haftfestigkeit von dicken TBC-Schichten im Thermoschock weiter steigert.The soldering is carried out in a high vacuum oven at 1100 ° C and 15 min Hold time. Before the subsequent air plasma spraying Thermal insulation layer 6 is a protective gas plasma spraying thin layer 7 (approx. 50 µm) SV 20 14 73 applied. That makes in addition to the rough anchoring option (as in the embodiment 1) additionally a fine interlocking what the adhesive strength of thick TBC layers in thermal shock further increases.

    Fig. 7 zeigt schematisch die Ausbildung dieser Schichten.Fig. 7 shows schematically the formation of these layers.

    Anschliessend wird mittels bekanntem Luftplasmaspritzverfahren eine 1,5 mm dicke Ytrium-stabilisierte Zirkonoxidschicht als TBC-Schicht 6 gespritzt.Then using known air plasma spraying a 1.5 mm thick ytrium-stabilized zirconium oxide layer injected as a TBC layer 6.

    Das so beschichtete Bauteil erwies sich bei einem Thermoschocktest im Sandbett (1000°C auf Raumtemperatur) als thermoschockfest.The component coated in this way proved itself in a thermal shock test in a sand bed (1000 ° C to room temperature) as resistant to thermal shock.

    Nach längerer Betriebszeit ist zwar die Lotschicht zwischen den grossen Haftpulverkörnern etwas wegkorrodiert, aber der Korrosionsangriff kann den tragenden Teil des Lothalses nicht nennenswert reduzieren.After a long period of operation, the solder layer is between corroded somewhat away from the large adhesive powder grains, but the The load-bearing part of the solder neck cannot be attacked by corrosion reduce significantly.

    In einem dritten Ausführungsbeispiel soll eine gekühlte Leitschaufel, die aus dem Material CM 247 LC DS (chemische Zusammensetzung: Ba. Ni; 8,1% Cr; 9,2% Co; 0,5% Mo; 9,5% W; 3,2% Ta; 0,7% Ti; 5,6% Al; 0,01% Zr; 0,01% B; 0,07% C; 1,4% Hf) besteht, im Neuzustand mit einer 0,7 bis 0,8 mm dicken TBC-Schicht versehen werden.In a third exemplary embodiment, a cooled guide vane, made of the material CM 247 LC DS (chemical composition: Ba. Ni; 8.1% Cr; 9.2% Co; 0.5% Mo; 9.5% W; 3.2% Ta; 0.7% Ti; 5.6% Al; 0.01% Zr; 0.01% B; 0.07% C; 1.4% Hf) exists, in new condition with a 0.7 to 0.8 mm thick TBC layer be provided.

    Dazu wird die Schaufel im ganzen Kanalbereich mittels Schutzgasplasmaspritzen mit dem Pulver ProXon 21031 (Legierung auf Nickelbasis) etwa 0,2 mm dick beschichtet (sauerstoffarm gespritzt). Dieses Pulver weist wegen seines hohen Aluminiumgehaltes und Chromgehaltes eine hervorragende Oxidations- und Korrosionsfestigkeit auf. Danach wird auf dieser rauh gespritzen Oxidations- und Korrosionschutzschicht 8 eine dünne Schicht Binder 3 aufgetragen. Darauf wird ein grobes Haftpulver 4 mit einem Teilchendurchmesser von etwa 100 bis 200 µm der gleichen Zusammensetzung gestreut. Die Beschichtung erfolgt dann im Hochvakuumofen bei Lösungsglühbedingungen für CM 247 LS DS (mehrere Stunden bei 1220 bis 1250°C). Dabei entsteht eine definierte metallurgische Bindung (Sinterverbindung 9) der Oxidations- und Korrosionsschutzschicht 8 am Grundmaterial 1. Die Schicht 8 verdichtet sich weiter und die groben Haftpulverteilchen 4 werden durch eine stabile Sinterbildung 9 auf der Schicht 8, die nunmehr gleichzeitig eine Schutz- und Haftschicht ist, gebunden.To do this, the blade is sprayed in the entire channel area using inert gas plasma with the powder ProXon 21031 (alloy on Nickel base) about 0.2 mm thick coated (sprayed low in oxygen). This powder exhibits because of its high aluminum content and chromium content an excellent oxidation and Corrosion resistance. Then it is sprayed roughly Oxidation and corrosion protection layer 8 a thin Layer Binder 3 applied. There is a rough adhesive powder on it 4 with a particle diameter of about 100 to 200 microns scattered the same composition. The coating takes place then in a high vacuum furnace under solution annealing conditions for CM 247 LS DS (several hours at 1220 to 1250 ° C). there a defined metallurgical bond (sintered connection 9) the oxidation and corrosion protection layer 8 am Base material 1. Layer 8 further densifies and coarse adhesive powder particles 4 are formed by stable sintering 9 on the layer 8, which is now a Protective and adhesive layer is bound.

    Fig. 8 verdeutlicht dies in einer schematischen Darstellung der einzelnen Schichten.8 illustrates this in a schematic representation of the individual layers.

    Danach werden die Profilsaugseite und die Bereiche der Kühlluftbohrungen der Leitschaufel abgedeckt. Die Druckseite und die Kanalwände, die mit Haftschichtpulver 4 belegt sind, werden nun mittels bekanntem Flammspritzsystem CastoDyn DS 8000 mit MetaCeram 28085 (Zirkonoxid/Calzium-stabilisiert) ca. 0,8 bis 0,7 mm dick beschichtet. Then the profile suction side and the areas of the cooling air holes the guide vane covered. The printed page and the channel walls, which are covered with adhesive layer powder 4, are now using the well-known CastoDyn DS 8000 flame spraying system with MetaCeram 28085 (zirconium oxide / calcium stabilized) approx. 0.8 coated up to 0.7 mm thick.

    Selbst nach 1000 Thermozyklen im Fliessbett (Bedingungen: 1000°C/RT/1000°C, Zykluszeit: 6min) konnte keine Beschädigung der Beschichtung festgestellt werden.Even after 1000 thermal cycles in the fluid bed (conditions: 1000 ° C / RT / 1000 ° C, cycle time: 6min) could not be damaged the coating can be determined.

    In einem vierten Ausführungsbeispiel soll ebenfalls eine gekühlte Leitschaufel aus CM 247 LC DS mit einer Wärmedämmschicht versehen werden. Als Lot 5 für die Befestigung der groben Haftpulverteilchen 4 aus ProXon 21031 wird ein artgleiches Pulver CM 247 mit einem Zusatz von 6 % Cr; 3% Si; 2% Al und 0,5% B verwendet. Der Auftrag erfolgt wie bereits oben beschrieben, d.h. auf die dünne Zement-Binder-Schicht 3 wird das etwa 150 bis 200 µm grosse Haftpulver 4 gestreut und darauf in reichlicher Menge das Lotpulver 5. Anschliessend wird die Schaufel einer Wärmebehandlung unterzogen, bei der das Grundmaterial 2 lösungsgeglüht und das Lot 5 teilweise aufgeschmolzen wird. Dabei geht sowohl die γ'-Lösung im Grundmaterial 2 vor sich als auch die feine γ'-Bildung in der Lötschicht, die in diesem Ausführungsbeispiel dicker aufgetragen wird und eine etwa 65 µm dicke Korrosions- und Oxidationsschicht bildet. Auf diese so vorbereitete Schaufeloberfläche an der Profildruckseite und den Kanalwänden wird nun mittels bekanntem Luftplasmaspritzverfahren eine ca. 0,5 bis 0,6 mm dicke Y-stabilisierte Zirkonoxid-Wärmedämmschicht aufgebracht.In a fourth exemplary embodiment, a cooled one is also intended Guide vane made of CM 247 LC DS with a thermal barrier coating be provided. As Lot 5 for attaching the coarse adhesive powder particles 4 from ProXon 21031 will be the same Powder CM 247 with an addition of 6% Cr; 3% Si; 2% Al and 0.5% B used. The order is made as above described, i.e. on the thin cement binder layer 3 the approximately 150 to 200 µm large adhesive powder 4 scattered and on it in abundance the solder powder 5. Then subjected the blade to a heat treatment in which the Base material 2 solution annealed and the solder 5 partially melted becomes. Both the γ'-solution in the base material 2 in front of it as well as the fine γ 'formation in the solder layer, the thicker applied in this embodiment and an approximately 65 µm thick corrosion and oxidation layer forms. On this prepared blade surface on the profile pressure side and the channel walls is now by means of known air plasma spraying an approx. 0.5 to 0.6 mm thick Y-stabilized zirconia thermal insulation layer applied.

    Thermoschocktests ergaben, dass die so befestigte Wärmedämmschicht einer konventionell hergestellten Schicht überlegen ist. Selbst wenn aus unterschiedlichen Gründen ein Stück der TBC-Schicht wegplatzt, bleibt zwischen den Haftpulverteilchen diese Schicht erhalten und garantiert somit gute Notlaufeigenschaften. Platzt dagegen bei konventionell beschichteten Schaufeln die TBC-Schicht ab, so verbleiben auf dem Substrat nur minimale Reste, die auf keinen Fall eine wärmedämmende Eigenschaft aufweisen. Ausserdem hat sich in diesem Beispiel gezeigt, dass es günstig ist, borfreie bzw. fast borfreie Lote zu verwenden, da die Sprödphasenbildung mit W-Boriden kaum möglich ist.Thermal shock tests showed that the thermal insulation layer thus attached superior to a conventionally produced layer is. Even if for different reasons a piece of the TBC layer bursts off, remains between the adhesive powder particles maintain this layer and thus guarantee good emergency running properties. In contrast, bursts with conventionally coated If the TBC layer is scooped off, it remains on the substrate only minimal residues, which is by no means an insulating Feature. In addition, in this example shown that it is cheap, boron-free or almost boron-free Solder to be used as the brittle phase formation with W-borides is hardly possible.

    Fig. 9 zeigt abschliessend ein Schliffbild eines mit der erfindungsgemässen Haftschicht beschichteten Plättchens. Das Grundmaterial 2 ist MAR M 247, als Lot 5 wurde NB 150 verwendet und die Haftpulverteilchen 4 bestehen aus NiA195/5.9 finally shows a micrograph of one with the one according to the invention Adhesive layer coated platelet. The Base material 2 is MAR M 247, NB 150 was used as lot 5 and the adhesive powder particles 4 are made of NiA195 / 5.

    BezugszeichenlisteReference list

    11
    zu beschichtendes metallisches Bauteilmetallic component to be coated
    22nd
    metallisches Grundmaterial (Substrat)metallic base material (substrate)
    33rd
    organischer Binderorganic binder
    44th
    HaftpulverAdhesive powder
    55
    LotLot
    66
    keramische Schicht (TBC)ceramic layer (TBC)
    77
    schutzgasplasmagespritze Haftpulverschichtprotective gas plasma syringe adhesive powder layer
    88th
    Oxidations- und KorrosionsschutzschichtOxidation and corrosion protection layer
    99
    SinterbildungSintering

    Claims (14)

    1. Process for applying a metallic adhesion layer, using a positive lock and undercuts, for thermally sprayed ceramic thermal barrier coatings (6) to metallic components (1), which coatings are to be applied subsequently to this adhesion layer, the surface which is to be coated being cleaned in a first process step, so that the metallic surface is free of grease and oxide, characterized in that
      a) a binder (3) is applied to the metallic surface of the base material (2) in a second process step,
      b) metallic adhesive powder (4) and solder powder (5), which has a smaller particle size than the adhesive powder (4), are applied uniformly to the binder (3) in a third process step, and
      c) after drying the binder (3), a heat treatment is carried out for the purpose of soldering.
    2. Process according to Claim 1, characterized in that in the third process step first the metallic adhesive powder (4) and then the solder powder (5) are applied to the binder (3).
    3. Process according to Claim 1, characterized in that in the third process step first the metallic adhesive powder (4) and the solder powder (5) are intensively mixed and then this mixture is applied to the metallic surface of the base material (2).
    4. Process for applying a metallic adhesion layer, using a positive lock and undercuts, for thermally sprayed ceramic thermal barrier coatings (6) to metallic components (1), which coatings are to be applied subsequently to this adhesion layer, the surface which is to be coated being cleaned in a first process step, so that the metallic surface is free of grease and oxide, and an oxidation- and corrosion-resistant layer (8) is produced on the metallic surface by means of protective gas plasma spraying in a second process step, characterized in that
      a) a binder (3) is applied to the oxidation- and corrosion-resistant layer (8) in a third process step,
      b) a coarse adhesive powder (4) of the same composition as the oxidation- and corrosion-resistant layer (8) is applied uniformly to the binder (3),
      c) after drying the binder (3), a heat treatment (solution annealing) is carried out for the purpose of forming a sintered join (9) between the metallic component (1) and the layer (8) and between the layer (8) and the adhesive powder (4), respectively.
    5. Process according to one of Claims 1 to 3, characterized in that a quantitative ratio by weight of adhesive powder (4) to solder powder (5) of 1:1 is used.
    6. Process according to Claim 1, characterized in that a thin layer (7) of the adhesive powder (4) is applied to the adhesion layer, after soldering has been carried out, by means of spray processes, preferably protective gas plasma spraying.
    7. Process according to Claim 1, characterized in that material of the same kind as the base material (2) is used as the solder material (5).
    8. Process according to Claim 1, characterized in that boron-free or low-boron solders (5) are used.
    9. Process according to one of Claims 1 to 8, characterized in that the process is employed for locally limited repairs.
    10. Process according to one of Claims 1 to 8, characterized in that the process is employed for coating new parts.
    11. Metallic adhesion layer for thermally sprayed ceramic thermal barrier coatings (6) on metallic components (1), which are produced using a process according to Claim 1, characterized in that the adhesion layer comprises a solder layer (5) wetting the surface of the metallic component (1) and having adhesive powder particles (4) of spherical or irregular form soldered fixedly therein.
    12. Metallic adhesion layer for thermally sprayed ceramic thermal barrier coatings (6) on metallic components (1), which are produced using a process according to Claim 6, characterized in that the adhesion layer comprises a solder layer (5) wetting the surface of the metallic component (1) and having adhesive powder particles (4) of spherical or irregular form soldered fixedly therein, and a thin sprayed, preferably protective gas plasma sprayed, layer (7) made of material of the same kind as the adhesive powder particles (4).
    13. Metallic adhesion layer for thermally sprayed ceramic thermal barrier coatings (6) on metallic components (1), which are produced using a process according to Claim 4, characterized in that the adhesion layer comprises a protective layer (8) which has been protective gas plasma sprayed on the surface of the metallic component (1) and has adhesive powder particles (4) sintered on its surface.
    14. Metallic adhesion layer according to Claim 11 or 12 or 13, characterized in that the height of the adhesive powder particles (4) corresponds to the layer thickness of the ceramic thermal barrier coating (6) which is to be sprayed on thermally.
    EP96810768A 1995-12-02 1996-11-11 Method for applying a metallic adhesion layers for ceramic insulating layer on metallic articles Expired - Lifetime EP0776985B1 (en)

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    DE19545025 1995-12-02
    DE19545025A DE19545025A1 (en) 1995-12-02 1995-12-02 Method for applying a metallic adhesive layer for ceramic thermal insulation layers on metallic components

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    EP0776985B1 true EP0776985B1 (en) 2001-12-19

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    UA42001C2 (en) 2001-10-15
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    DE19545025A1 (en) 1997-06-05
    CN1160088A (en) 1997-09-24
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    PL317298A1 (en) 1997-06-09
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    JPH09176818A (en) 1997-07-08
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    EP0776985A1 (en) 1997-06-04
    US5894053A (en) 1999-04-13

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