CA2837415C - Method for applying a protective layer, component coated with a protective layer, and gas turbine comprising such a component - Google Patents
Method for applying a protective layer, component coated with a protective layer, and gas turbine comprising such a component Download PDFInfo
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- CA2837415C CA2837415C CA2837415A CA2837415A CA2837415C CA 2837415 C CA2837415 C CA 2837415C CA 2837415 A CA2837415 A CA 2837415A CA 2837415 A CA2837415 A CA 2837415A CA 2837415 C CA2837415 C CA 2837415C
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- layer
- diffusion layer
- diffusion
- protective layer
- bond
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000011241 protective layer Substances 0.000 title claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 105
- 238000009792 diffusion process Methods 0.000 claims abstract description 54
- 239000012720 thermal barrier coating Substances 0.000 claims abstract description 26
- 239000010953 base metal Substances 0.000 claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 17
- 208000035874 Excoriation Diseases 0.000 claims abstract description 12
- 238000005299 abrasion Methods 0.000 claims abstract description 12
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 230000003628 erosive effect Effects 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 238000007750 plasma spraying Methods 0.000 claims abstract description 8
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims abstract description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims description 9
- 230000003746 surface roughness Effects 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007751 thermal spraying Methods 0.000 claims description 3
- 238000010285 flame spraying Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010290 vacuum plasma spraying Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910006020 NiCoAl Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 1
- RLQJEEJISHYWON-UHFFFAOYSA-N flonicamid Chemical compound FC(F)(F)C1=CC=NC=C1C(=O)NCC#N RLQJEEJISHYWON-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
- F01D5/288—Protective coatings for blades
-
- 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
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/48—Aluminising
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
-
- 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
-
- 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
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
-
- 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
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
-
- 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
- C23C4/134—Plasma 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
-
- 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
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
Abstract
The invention is directed to a method for applying a protective layer with a component part coated with a protective layer and gas turbine with a component part of this type. In the method, a MCrAlY-based bond layer (12) is applied to a base metal (11), the bond layer (12) is coated by overaluminizing with an Al diffusion layer (14), the Al diffusion layer (14) is subjected to abrasion treatment so that an outer build-up layer (14.2) is removed from the Al diffusion layer (14), and a ceramic thermal barrier coating (13) of yttria partially stabilized zirconia is applied to the remaining Al diffusion layer (14) so that a protective layer is produced which is resistant to high-temperature degradation by corrosion and erosion. According to the invention, the method achieves a protective layer with a good resistance to thermal fatigue and can nevertheless be carried out in a simple manner. This is achieved inter alia in that the ceramic thermal barrier coating (13) is applied to the remaining Al diffusion layer (14) by air plasma spraying.
Description
METHOD FOR APPLYING A PROTECTIVE LAYER, COMPONENT COATED WITH A
PROTECTIVE LAYER, AND GAS TURBINE COMPRISING SUCH A COMPONENT
The invention is directed to a method for applying a protective layer to a base metal and to a component part coated with a protective layer of this kind for use in a hot gas region of a gas turbine, and to a gas turbine with a component part of this kind.
A method of the type mentioned above is known, e.g., from EP 1 637 622 Al.
In modern gas turbines, the surfaces in the hot gas region are provided almost entirely with coatings. The blades of rear turbine rows may be excepted in some cases.
The thermal barrier coatings (TBCs) used for this purpose serve to lower the material temperature of cooled component parts. In this way, the life of the component parts can be prolonged, cooling air can be saved, or the gas turbines can be operated at higher input temperatures.
Thermal barrier coating systems are always formed of a metallic bond layer which is diffusion bonded to the base material (base metal) and a ceramic layer on top of the bond layer; this ceramic layer has poor thermal conductivity and provides the actual barrier against heat flow and protects the base metal against high-temperature degradation by corrosion and erosion. The generally accepted ceramic material for the thermal barrier coating is zirconium oxide partially stabilized with approximately 7 weight percent of yttrium oxide (the international acronym for yttria partially stabilized zirconia is YPSZ).
Thermal barrier coatings are divided into two different categories depending on the method of application.
A first category consists of thermal barrier coatings which are vapor deposited by electron beam physical vapor deposition methods (EB-PVD methods). When certain deposition conditions are maintained, these thermal barrier coatings have a columnar, strain-tolerant structure and therefore provide a particularly good resistance to thermal cycle fatigue (TCF). In the associated methods for applying the thermal barrier coating, the thermal barrier coating is chemically bonded to a layer of pure alumina (Thermally Grown Oxide, TGO) which is formed by the bond layer during application thereof and subsequently during service through the formation of an alumina-zirconia mixture. On the one hand, this method imposes particular demands for the oxide growth on the bond layer, but on the other hand it ensures an especially strong bond.
PROTECTIVE LAYER, AND GAS TURBINE COMPRISING SUCH A COMPONENT
The invention is directed to a method for applying a protective layer to a base metal and to a component part coated with a protective layer of this kind for use in a hot gas region of a gas turbine, and to a gas turbine with a component part of this kind.
A method of the type mentioned above is known, e.g., from EP 1 637 622 Al.
In modern gas turbines, the surfaces in the hot gas region are provided almost entirely with coatings. The blades of rear turbine rows may be excepted in some cases.
The thermal barrier coatings (TBCs) used for this purpose serve to lower the material temperature of cooled component parts. In this way, the life of the component parts can be prolonged, cooling air can be saved, or the gas turbines can be operated at higher input temperatures.
Thermal barrier coating systems are always formed of a metallic bond layer which is diffusion bonded to the base material (base metal) and a ceramic layer on top of the bond layer; this ceramic layer has poor thermal conductivity and provides the actual barrier against heat flow and protects the base metal against high-temperature degradation by corrosion and erosion. The generally accepted ceramic material for the thermal barrier coating is zirconium oxide partially stabilized with approximately 7 weight percent of yttrium oxide (the international acronym for yttria partially stabilized zirconia is YPSZ).
Thermal barrier coatings are divided into two different categories depending on the method of application.
A first category consists of thermal barrier coatings which are vapor deposited by electron beam physical vapor deposition methods (EB-PVD methods). When certain deposition conditions are maintained, these thermal barrier coatings have a columnar, strain-tolerant structure and therefore provide a particularly good resistance to thermal cycle fatigue (TCF). In the associated methods for applying the thermal barrier coating, the thermal barrier coating is chemically bonded to a layer of pure alumina (Thermally Grown Oxide, TGO) which is formed by the bond layer during application thereof and subsequently during service through the formation of an alumina-zirconia mixture. On the one hand, this method imposes particular demands for the oxide growth on the bond layer, but on the other hand it ensures an especially strong bond.
- 2 -A second category includes thermal barrier coatings which are sprayed on thermally (usually by air plasma spraying [APS]). These thermal barrier coatings have a porosity of between approximately 10 and 25 volume percent depending on the desired layer thickness and stress distribution. Due to the fact that the ceramic layer is bonded to the bond layer mechanically in this case, the bond layer is deliberately in rough condition when sprayed in order to maximize the interface and, therefore, the adhesive forces. A certain chemical bonding is brought about through TGO formation only after a long period of service. This application method is relatively simple resulting in relatively favorable coating costs.
It is the object of the invention to further develop a method of applying a protective layer in such a way that a good resistance to thermal fatigue is achieved in the protective layer while still allowing the method to be carried out in a simple manner.
In accordance with one aspect of the present invention, there is provided a method for applying a protective layer which is resistant to high-temperature degradation by corrosion and erosion to a base metal (11), wherein a MCrA1Y-based bond layer (12) is applied to the base metal (11), the bond layer (12) is coated by overaluminizing with an Al diffusion layer (14), the Al diffusion layer (14) is subjected to abrasion treatment so that an outer build-up layer (14.2) is removed from the Al diffusion layer (14), and a ceramic thermal barrier coating (13) of yttria partially stabilized zirconia is applied to the remaining Al diffusion layer (14), wherein the ceramic thermal barrier coating (13) is applied to the remaining Al diffusion layer (14) by air plasma spraying, characterized in that the applied bond layer (12) is subjected to a polishing treatment before being overaluminized such that a surface roughness of Ra < 2 p.m is produced at the bond layer (12), wherein M is Ni, Co or combinations thereof.
A further object of the invention is to provide a component part for use in a hot gas region of a gas turbine, which component part is coated with a protective layer that is resistant to high-temperature degradation by corrosion and erosion, and to provide a gas turbine having a component part of this type, wherein the protective layer can be produced on the component part in a simple manner and has a good resistance to thermal fatigue.
In another aspect of the present invention there is a gas turbine with a hot gas region and a component part herein described.
- 2a -Further developments of the invention are defined herein.
With regard to the bond layer ¨ preferably in stationary gas turbines ¨
thermally sprayed MCrAlY-based (M = Ni, Co) undercoats are used. MCrAlY layers contain the intermetallic 13 phase NiCoAl as aluminum reserve in a NiCoCr ("Y") matrix.
But this also has an embrittling effect so that the Al content that can be realized in the MCrAlY layer in practice is < 12 weight percent.
To further enhance resistance to oxidation, the MCrAlY coats are overaluminized with an Al diffusion layer. Owing to the risk of embrittlement, this is largely limited to low-aluminwn (Al < 8%) starting layers.
The structure of an overaluminized MCrAlY layer includes an inner, substantially
It is the object of the invention to further develop a method of applying a protective layer in such a way that a good resistance to thermal fatigue is achieved in the protective layer while still allowing the method to be carried out in a simple manner.
In accordance with one aspect of the present invention, there is provided a method for applying a protective layer which is resistant to high-temperature degradation by corrosion and erosion to a base metal (11), wherein a MCrA1Y-based bond layer (12) is applied to the base metal (11), the bond layer (12) is coated by overaluminizing with an Al diffusion layer (14), the Al diffusion layer (14) is subjected to abrasion treatment so that an outer build-up layer (14.2) is removed from the Al diffusion layer (14), and a ceramic thermal barrier coating (13) of yttria partially stabilized zirconia is applied to the remaining Al diffusion layer (14), wherein the ceramic thermal barrier coating (13) is applied to the remaining Al diffusion layer (14) by air plasma spraying, characterized in that the applied bond layer (12) is subjected to a polishing treatment before being overaluminized such that a surface roughness of Ra < 2 p.m is produced at the bond layer (12), wherein M is Ni, Co or combinations thereof.
A further object of the invention is to provide a component part for use in a hot gas region of a gas turbine, which component part is coated with a protective layer that is resistant to high-temperature degradation by corrosion and erosion, and to provide a gas turbine having a component part of this type, wherein the protective layer can be produced on the component part in a simple manner and has a good resistance to thermal fatigue.
In another aspect of the present invention there is a gas turbine with a hot gas region and a component part herein described.
- 2a -Further developments of the invention are defined herein.
With regard to the bond layer ¨ preferably in stationary gas turbines ¨
thermally sprayed MCrAlY-based (M = Ni, Co) undercoats are used. MCrAlY layers contain the intermetallic 13 phase NiCoAl as aluminum reserve in a NiCoCr ("Y") matrix.
But this also has an embrittling effect so that the Al content that can be realized in the MCrAlY layer in practice is < 12 weight percent.
To further enhance resistance to oxidation, the MCrAlY coats are overaluminized with an Al diffusion layer. Owing to the risk of embrittlement, this is largely limited to low-aluminwn (Al < 8%) starting layers.
The structure of an overaluminized MCrAlY layer includes an inner, substantially
-3 -20%, and an outer I3-NiA1 phase with an Al proportion of about 30%. This outer i3-NiA1 phase represents a certain weak point in the layer system as regards brittleness and sensitivity to cracking. Therefore, the overaluminized coat is subjected to an abrasion treatment so that the outer I3-NiA1 phase is removed down to the diffusion zone. This also has a favorable effect on the aluminum activity and thus benefits the capability of TGO
formation.
In this regard, a good bonding of the ceramic layer can be achieved without the need for a rough bond layer so that it is possible inter alia to apply the MCrAlY
layer by means of low pressure plasma spraying (LPPS) or thermal spraying, for example, high velocity flame spraying (HVOF) or vacuum plasma spraying. High velocity flame spraying is more economical and tends to generate smoother surfaces.
According to a first aspect of the invention, a method is provided for applying a protective layer that is resistant to high-temperature degradation by corrosion and erosion to a base metal, wherein a MCrAlY-based bond layer is applied to the base metal, the bond layer is coated by overaluminizing with an Al diffusion layer, the Al diffusion layer is subjected to abrasion treatment so that an outer build-up layer is removed from the Al diffusion layer, and a ceramic thermal barrier coating of yttria partially stabilized zirconia is applied to the remaining Al diffusion layer. The method according to the invention is characterized in that the ceramic thermal barrier coating is applied to the remaining Al diffusion layer by air plasma spraying.
According to an embodiment form of the method according to the invention, the applied bond layer is subjected to a polishing treatment before being overaluminized. A
surface roughness of Ra < 2 vtin is preferably produced at the bond layer by the polishing treatment.
According to yet another embodiment form of the method according to the invention, the bond layer is applied to the base metal by thermal spraying, for example, high velocity flame spraying (HVOF) or vacuum plasma spraying high velocity flame spraying or deposition from the vapor phase.
According to a further embodiment form of the method according to the invention, the Al diffusion layer is subjected to a polishing treatment after the abrasion treatment such that a surface roughness of Ra < 2 vim is produced at the remaining Al diffusion layer.
According to yet another embodiment form of the method according to the invention, a heat treatment is carried out after overaluminizing the bond layer and before the abrasion
formation.
In this regard, a good bonding of the ceramic layer can be achieved without the need for a rough bond layer so that it is possible inter alia to apply the MCrAlY
layer by means of low pressure plasma spraying (LPPS) or thermal spraying, for example, high velocity flame spraying (HVOF) or vacuum plasma spraying. High velocity flame spraying is more economical and tends to generate smoother surfaces.
According to a first aspect of the invention, a method is provided for applying a protective layer that is resistant to high-temperature degradation by corrosion and erosion to a base metal, wherein a MCrAlY-based bond layer is applied to the base metal, the bond layer is coated by overaluminizing with an Al diffusion layer, the Al diffusion layer is subjected to abrasion treatment so that an outer build-up layer is removed from the Al diffusion layer, and a ceramic thermal barrier coating of yttria partially stabilized zirconia is applied to the remaining Al diffusion layer. The method according to the invention is characterized in that the ceramic thermal barrier coating is applied to the remaining Al diffusion layer by air plasma spraying.
According to an embodiment form of the method according to the invention, the applied bond layer is subjected to a polishing treatment before being overaluminized. A
surface roughness of Ra < 2 vtin is preferably produced at the bond layer by the polishing treatment.
According to yet another embodiment form of the method according to the invention, the bond layer is applied to the base metal by thermal spraying, for example, high velocity flame spraying (HVOF) or vacuum plasma spraying high velocity flame spraying or deposition from the vapor phase.
According to a further embodiment form of the method according to the invention, the Al diffusion layer is subjected to a polishing treatment after the abrasion treatment such that a surface roughness of Ra < 2 vim is produced at the remaining Al diffusion layer.
According to yet another embodiment form of the method according to the invention, a heat treatment is carried out after overaluminizing the bond layer and before the abrasion
- 4 -treatment of the Al diffusion layer in order to influence the mechanical properties of the base metal.
According to yet another embodiment form of the method according to the invention, during overaluminizing an inner diffusion zone with an Al content of about 20 weight percent is produced in the Al diffusion layer and the outer build-up layer with an Al content of about 30 weight percent is produced on the diffusion zone, and the outer build-up layer of the Al diffusion layer is removed by abrasion treatment until the Al content in a surface of the remaining Al diffusion layer amounts to more than 18 weight percent and less than 30 weight percent.
According to a second aspect of the invention, a component part is provided for use in a hot gas region of a gas turbine, wherein the component part has a surface that is at least partially provided with a protective layer which is resistant to high-temperature degradation by corrosion and erosion and which is applied by a method according to one or more or all of the above-described embodiment forms of the invention in any conceivable combination.
According to a third aspect of the invention, there is provided a gas turbine with a hot gas region and with a component part according to the second aspect of the invention arranged therein.
Owing to the application of the method according to the invention for producing the protective layer on the component part, the protective layer has a good resistance to thermal fatigue and can nevertheless be produced in a simple manner.
Finally, the invention provides a thermal barrier coating concept which combines the favorable costs of the APS method with the advantages of chemical bonding between the bond layer and the ceramic layer. In this way, TCF behavior can be improved over that of conventional APS layers. Accordingly, thermal barrier coatings with improved resistance to thermal fatigue can be produced in a simpler manner and, therefore, at a lower cost than with EB-PVD methods.
The invention expressly extends to embodiment forms which are not given by combinations of features from explicit references of the claims so that the disclosed features of the invention can be combined with one another in any way insofar as technically meaningful.
According to yet another embodiment form of the method according to the invention, during overaluminizing an inner diffusion zone with an Al content of about 20 weight percent is produced in the Al diffusion layer and the outer build-up layer with an Al content of about 30 weight percent is produced on the diffusion zone, and the outer build-up layer of the Al diffusion layer is removed by abrasion treatment until the Al content in a surface of the remaining Al diffusion layer amounts to more than 18 weight percent and less than 30 weight percent.
According to a second aspect of the invention, a component part is provided for use in a hot gas region of a gas turbine, wherein the component part has a surface that is at least partially provided with a protective layer which is resistant to high-temperature degradation by corrosion and erosion and which is applied by a method according to one or more or all of the above-described embodiment forms of the invention in any conceivable combination.
According to a third aspect of the invention, there is provided a gas turbine with a hot gas region and with a component part according to the second aspect of the invention arranged therein.
Owing to the application of the method according to the invention for producing the protective layer on the component part, the protective layer has a good resistance to thermal fatigue and can nevertheless be produced in a simple manner.
Finally, the invention provides a thermal barrier coating concept which combines the favorable costs of the APS method with the advantages of chemical bonding between the bond layer and the ceramic layer. In this way, TCF behavior can be improved over that of conventional APS layers. Accordingly, thermal barrier coatings with improved resistance to thermal fatigue can be produced in a simpler manner and, therefore, at a lower cost than with EB-PVD methods.
The invention expressly extends to embodiment forms which are not given by combinations of features from explicit references of the claims so that the disclosed features of the invention can be combined with one another in any way insofar as technically meaningful.
-5 -In the following, the invention will be described with reference to a preferred embodiment form and with reference to the accompanying drawing.
Fig. 1 shows a sectional view of a region of a component part of a gas turbine according to an embodiment form of the invention, which component part is arranged in a hot gas region and is provided with a protective layer.
Fig. 1 is a sectional view showing a region of a component part 10 of a gas turbine 1 according to an embodiment form of the invention, which component part 10 is arranged in a hot gas region and is provided with a protective layer 12 - 14.
For protection against high-temperature degradation by corrosion and erosion, the component part 10, e.g., a turbine blade or other component part of the gas turbine 1 coming into contact with hot gas, has a base metal 11 (base material) with a surface which is provided in its entirety or partially with a ceramic thermal barrier coating that is resistant to high-temperature corrosion and erosion. The ceramic thermal barrier coating 13 is formed of zirconium oxide that is partially stabilized with approximately 7 weight percent of yttrium oxide (the international acronym for yttria partially stabilized zirconia is YPSZ).
To improve the adhesion of the thermal barrier coating 13 to the base metal 11, an undercoat or bond layer 12 is first applied to this base metal 11 (to the surface thereof). The bond layer 12 comprises a special alloy based on MCrAlY (e.g., LCO 22). Here the letter M
represents Ni or Co or a combination thereof. The bond layer 12 is applied by means of low pressure plasma spraying (LPPS) or, as is preferable in this case, by high velocity flame spraying (HVOF).
The applied bond layer 12 is subsequently subjected to a polishing treatment (e.g., fine finishing) by which a surface roughness of Ra < 2 p.m is generated on the bond layer 12.
To increase the Al content in the bond layer 12, this bond layer 12 is then coated by overaluminizing with an Al diffusion layer 14. The overaluminizing can be realized by means of a treatment in which a reactive Al-containing gas, possibly an Al halide (A1X2), causes an inward diffusion of Al combined with an outward diffusion of Ni, e.g., a chemical vapor deposition (CVD), at high temperatures.
The overaluminizing causes an inner diffusion zone 14.1 with an Al content of about 20 weight percent to be formed in the Al diffusion layer 14 on the largely unchanged bond layer 12 and thereon an outer build-up layer 4.2 comprising a brittle 0-NiA1 phase with an Al content of about 30 weight percent.
Fig. 1 shows a sectional view of a region of a component part of a gas turbine according to an embodiment form of the invention, which component part is arranged in a hot gas region and is provided with a protective layer.
Fig. 1 is a sectional view showing a region of a component part 10 of a gas turbine 1 according to an embodiment form of the invention, which component part 10 is arranged in a hot gas region and is provided with a protective layer 12 - 14.
For protection against high-temperature degradation by corrosion and erosion, the component part 10, e.g., a turbine blade or other component part of the gas turbine 1 coming into contact with hot gas, has a base metal 11 (base material) with a surface which is provided in its entirety or partially with a ceramic thermal barrier coating that is resistant to high-temperature corrosion and erosion. The ceramic thermal barrier coating 13 is formed of zirconium oxide that is partially stabilized with approximately 7 weight percent of yttrium oxide (the international acronym for yttria partially stabilized zirconia is YPSZ).
To improve the adhesion of the thermal barrier coating 13 to the base metal 11, an undercoat or bond layer 12 is first applied to this base metal 11 (to the surface thereof). The bond layer 12 comprises a special alloy based on MCrAlY (e.g., LCO 22). Here the letter M
represents Ni or Co or a combination thereof. The bond layer 12 is applied by means of low pressure plasma spraying (LPPS) or, as is preferable in this case, by high velocity flame spraying (HVOF).
The applied bond layer 12 is subsequently subjected to a polishing treatment (e.g., fine finishing) by which a surface roughness of Ra < 2 p.m is generated on the bond layer 12.
To increase the Al content in the bond layer 12, this bond layer 12 is then coated by overaluminizing with an Al diffusion layer 14. The overaluminizing can be realized by means of a treatment in which a reactive Al-containing gas, possibly an Al halide (A1X2), causes an inward diffusion of Al combined with an outward diffusion of Ni, e.g., a chemical vapor deposition (CVD), at high temperatures.
The overaluminizing causes an inner diffusion zone 14.1 with an Al content of about 20 weight percent to be formed in the Al diffusion layer 14 on the largely unchanged bond layer 12 and thereon an outer build-up layer 4.2 comprising a brittle 0-NiA1 phase with an Al content of about 30 weight percent.
- 6 -After overaluminizing the bond layer 12, heat treatment may be performed to influence or adjust the mechanical properties of the base metal 11.
Subsequently, the outer build-up layer 14.2 is removed down to the inner diffusion zone 14.1 of the Al diffusion layer 14 by abrasion treatment, e.g., blasting with hard particles (e.g., corundum, silicon carbide, cut metal wire, etc.) or treating with other known abrasive media or polishing media. The abrasion treatment is carried out until the surface of the remaining Al diffusion layer 14 (diffusion zone 14.1) has an Al content of greater than approximately 18 weight percent and less than approximately 30 weight percent.
After abrading, the Al diffusion layer 14 is subjected to a polishing treatment (e.g., fine finishing) such that a surface roughness of Ra < 2 p.m is produced at the remaining Al diffusion layer 14 (diffusion zone 14.1).
The ceramic thermal barrier coating (YPSZ ceramic layer) 13 is then applied by air plasma spraying (APS) to the surface of the remaining AL diffusion layer 14 which has been prepared as described above. The same parameters can be used for the APS
method as for conventional bond layers.
Subsequently, the outer build-up layer 14.2 is removed down to the inner diffusion zone 14.1 of the Al diffusion layer 14 by abrasion treatment, e.g., blasting with hard particles (e.g., corundum, silicon carbide, cut metal wire, etc.) or treating with other known abrasive media or polishing media. The abrasion treatment is carried out until the surface of the remaining Al diffusion layer 14 (diffusion zone 14.1) has an Al content of greater than approximately 18 weight percent and less than approximately 30 weight percent.
After abrading, the Al diffusion layer 14 is subjected to a polishing treatment (e.g., fine finishing) such that a surface roughness of Ra < 2 p.m is produced at the remaining Al diffusion layer 14 (diffusion zone 14.1).
The ceramic thermal barrier coating (YPSZ ceramic layer) 13 is then applied by air plasma spraying (APS) to the surface of the remaining AL diffusion layer 14 which has been prepared as described above. The same parameters can be used for the APS
method as for conventional bond layers.
- 7 -List of Reference Numerals 1 gas turbine component part 11 base metal 12 bond layer 13 thermal barrier coating 14 Al diffusion layer 14.1 inner diffusion zone 14.2 outer build-up layer
Claims (7)
1. Method for applying a protective layer which is resistant to high-temperature degradation by corrosion and erosion to a base metal (11), wherein a MCrAlY-based bond layer (12) is applied to the base metal (11), the bond layer (12) is coated by overaluminizing with an Al diffusion layer (14), the Al diffusion layer (14) is subjected to abrasion treatment so that an outer build-up layer (14.2) is removed from the Al diffusion layer (14), and a ceramic thermal barrier coating (13) of yttria partially stabilized zirconia is applied to the remaining Al diffusion layer (14), wherein the ceramic thermal barrier coating (13) is applied to the remaining Al diffusion layer (14) by air plasma spraying, characterized in that the applied bond layer (12) is subjected to a polishing treatment before being overaluminized such that a surface roughness of Ra <= 2 µm is produced at the bond layer (12), wherein M is Ni, Co or combinations thereof.
2. Method according to claim 1, characterized in that the bond layer (12) is applied to the base metal (11) by a thermal spraying method.
3. Method according to one of claims 1 to 2, characterized in that the Al diffusion layer (14) is subjected to a polishing treatment after the abrasion treatment such that a surface roughness of Ra <= 2 µm is produced at the remaining Al diffusion layer (14).
4. Method according to one of claims 1 to 3, characterized in that a heat treatment is carried out after overaluminizing the bond layer (12) and before abrading the Al diffusion layer (14) in order to influence the mechanical properties of the base metal (11).
5. Method according to one of claims 1 to 4, characterized in that during overaluminizing an inner diffusion zone (14.1) with an Al content of about 20 weight percent is produced in the Al diffusion layer (14) and the outer build-up layer (14.2) with an Al content of about 30 weight percent is produced on the diffusion zone (14.1), and in that the outer build-up layer (14.2) of the Al diffusion layer (14) is removed by abrasion treatment until the Al content in a surface of the remaining Al diffusion layer (14) amounts to more than 18 weight percent and less than 30 weight percent.
6. Component part (10) for use in a hot gas region of a gas turbine (1), wherein the component part (10) has a surface that is at least partially provided with a protective layer which is resistant to high-temperature degradation by corrosion and erosion and which is applied by a method according to one of claims 1 to 5.
7. Gas turbine (1) with a hot gas region and with a component part (10) according to claim 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011103731.8 | 2011-05-31 | ||
| DE102011103731A DE102011103731A1 (en) | 2011-05-31 | 2011-05-31 | Method for applying a protective layer, with a protective layer coated component and gas turbine with such a component |
| PCT/EP2012/060195 WO2012163991A1 (en) | 2011-05-31 | 2012-05-31 | Method for applying a protective layer, component coated with a protective layer, and gas turbine comprising such a component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2837415A1 CA2837415A1 (en) | 2012-12-06 |
| CA2837415C true CA2837415C (en) | 2016-11-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2837415A Expired - Fee Related CA2837415C (en) | 2011-05-31 | 2012-05-31 | Method for applying a protective layer, component coated with a protective layer, and gas turbine comprising such a component |
Country Status (6)
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| US (1) | US20140141276A1 (en) |
| EP (1) | EP2714957A1 (en) |
| JP (1) | JP5878629B2 (en) |
| CA (1) | CA2837415C (en) |
| DE (1) | DE102011103731A1 (en) |
| WO (1) | WO2012163991A1 (en) |
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| FR3002239B1 (en) * | 2013-02-15 | 2015-04-10 | Messier Bugatti Dowty | METHOD FOR MANUFACTURING AN AIRCRAFT PART COMPRISING A SUBSTRATE AND A COATING LAYER OF THE SUBSTRATE |
| US9518325B2 (en) * | 2013-03-19 | 2016-12-13 | General Electric Company | Treated coated article and process of treating a coated article |
| CN104404436B (en) * | 2014-11-25 | 2017-02-22 | 西安交通大学 | Method for preparing columnar ceramic coating layer by low-pressure plasma spraying based on liquid phase filtration |
| DE102016103664A1 (en) | 2016-03-01 | 2017-09-07 | Lufthansa Technik Ag | Flow element and method for coating a flow element |
| GB201903484D0 (en) * | 2019-03-14 | 2019-05-01 | Rolls Royce Plc | A method of removing a ceramic coating from a ceramic coated metallic article |
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| US5236745A (en) * | 1991-09-13 | 1993-08-17 | General Electric Company | Method for increasing the cyclic spallation life of a thermal barrier coating |
| JP3219594B2 (en) * | 1994-04-27 | 2001-10-15 | 三菱重工業株式会社 | Thermal barrier coating method for high temperature oxidation prevention |
| EP0826076B1 (en) * | 1995-04-27 | 1999-07-07 | Siemens Aktiengesellschaft | Metal component with a high-temperature protection coating system and a method of coating the component |
| ES2132927T3 (en) * | 1995-07-25 | 1999-08-16 | Siemens Ag | PRODUCT WITH A BASIC METAL BODY WITH REFRIGERATION CHANNELS AND ITS MANUFACTURE. |
| US6555179B1 (en) * | 1998-01-14 | 2003-04-29 | General Electric Company | Aluminizing process for plasma-sprayed bond coat of a thermal barrier coating system |
| DE19801424B4 (en) * | 1998-01-16 | 2004-08-05 | Forschungszentrum Jülich GmbH | Thermal insulation for high temperatures and its use |
| US6203685B1 (en) * | 1999-01-20 | 2001-03-20 | International Business Machines Corporation | Apparatus and method for selective electrolytic metallization/deposition utilizing a fluid head |
| US6472018B1 (en) * | 2000-02-23 | 2002-10-29 | Howmet Research Corporation | Thermal barrier coating method |
| US6576067B2 (en) * | 2001-08-31 | 2003-06-10 | General Electric Co. | Fabrication of an article having a protective coating with a polished, pre-oxidized protective-coating surface |
| DE102004045049A1 (en) | 2004-09-15 | 2006-03-16 | Man Turbo Ag | Protection layer application, involves applying undercoating with heat insulating layer, and subjecting diffusion layer to abrasive treatment, so that outer structure layer of diffusion layer is removed by abrasive treatment |
| DE102005053531A1 (en) * | 2005-11-08 | 2007-05-10 | Man Turbo Ag | Heat-insulating protective layer for a component within the hot gas region of a gas turbine |
| DE102005060243A1 (en) * | 2005-12-14 | 2007-06-21 | Man Turbo Ag | Process for coating hollow internally cooled gas turbine blades with adhesive-, zirconium oxide ceramic- and Cr diffusion layers useful in gas turbine engine technology has adhesive layer applied by plasma or high rate spraying method |
| WO2007112783A1 (en) * | 2006-04-06 | 2007-10-11 | Siemens Aktiengesellschaft | Layered thermal barrier coating with a high porosity, and a component |
| US20090162692A1 (en) * | 2007-12-24 | 2009-06-25 | Bangalore Aswatha Nagaraj | Coated Superalloy Articles |
| DE102008007870A1 (en) * | 2008-02-06 | 2009-08-13 | Forschungszentrum Jülich GmbH | Thermal barrier coating system and process for its preparation |
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- 2011-05-31 DE DE102011103731A patent/DE102011103731A1/en not_active Withdrawn
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- 2012-05-31 WO PCT/EP2012/060195 patent/WO2012163991A1/en active Application Filing
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- 2012-05-31 JP JP2014513181A patent/JP5878629B2/en not_active Expired - Fee Related
- 2012-05-31 EP EP12725000.9A patent/EP2714957A1/en not_active Withdrawn
- 2012-05-31 CA CA2837415A patent/CA2837415C/en not_active Expired - Fee Related
Also Published As
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| JP5878629B2 (en) | 2016-03-08 |
| JP2014520205A (en) | 2014-08-21 |
| US20140141276A1 (en) | 2014-05-22 |
| CA2837415A1 (en) | 2012-12-06 |
| DE102011103731A1 (en) | 2012-12-06 |
| WO2012163991A1 (en) | 2012-12-06 |
| EP2714957A1 (en) | 2014-04-09 |
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