EP1428982B1 - A method of depositing a local MCrAIY-coating - Google Patents
A method of depositing a local MCrAIY-coating Download PDFInfo
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- EP1428982B1 EP1428982B1 EP02406066A EP02406066A EP1428982B1 EP 1428982 B1 EP1428982 B1 EP 1428982B1 EP 02406066 A EP02406066 A EP 02406066A EP 02406066 A EP02406066 A EP 02406066A EP 1428982 B1 EP1428982 B1 EP 1428982B1
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- Prior art keywords
- coating
- coatings
- mcraiy
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- 238000000576 coating method Methods 0.000 title claims description 101
- 239000011248 coating agent Substances 0.000 title claims description 55
- 238000000034 method Methods 0.000 title claims description 41
- 238000000151 deposition Methods 0.000 title claims description 8
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 230000007797 corrosion Effects 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 11
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 description 19
- 239000000758 substrate Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000601 superalloy Inorganic materials 0.000 description 3
- 239000012720 thermal barrier coating Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2230/00—Manufacture
- F05D2230/80—Repairing, retrofitting or upgrading methods
Definitions
- This invention relates according to claim 1 to a method of depositing a MCrAlY-coating.
- MCrAlY overlay coatings are used for protection of turbine blades and vanes.
- MCrAlY protective overlay coatings are widely known in the prior art. They are a family of high temperature coatings, wherein M is selected from one or a combination of iron, nickel and cobalt.
- US-A-3,528,861 or US-A-4,585,481 are disclosing such kind of oxidation resistant coatings.
- US-A-4, 152,223 as well discloses such method of coating and the coating itself.
- ⁇ / ⁇ -MCrAlY-coating there is another class of overlay MCrAlY coatings which are based on a ⁇ / ⁇ '-gamma/gamma prime-structure, which is for example disclosed in US-A-4,546,052 or US-A-4,973,445 .
- the advantages of ⁇ / ⁇ '-coatings is that they have a negligible thermal expansion mismatch with alloy of the underlying turbine article and are likely to have a better thermal mechanical properties.
- US-A-4,313,760 discloses a superalloy coating composition with good oxidation, corrosion and fatigue resistance. Additional examples MCrAlY coatings are known from US-B1-6,280,857 , US-B1-6,221,181 , US-A-5,455,119 , US-A-5,154,885 , US-A-5, 035,958 or US-B1-6,207,297 . They all deal primarily with improving the oxidation resistance of MCrAlY coatings.
- Thermal barrier coatings are used to provide thermal insulation of the components in various types of engines e.g. in turbine engines.
- Thermal Barrier Coatings are known from different patents.
- US-A-4,055,705 , US-A-4,248,940 , US-A-4,321,311 or US-A-4,676,994 disclose a TBC-coating for the use in the turbine blades and vanes.
- the ceramics used are yttria stabilized zirconia and applied by plasma spray ( US-A-4, 055,705 , US-A-4, 248,940 ) or by electron beam process ( US-A-4, 321,311 , US-A-4, 676,994 ) on top of the MCrAlY bond coat.
- the coatings on turbine blades or vanes can fail by one or more of the following degradation modes. These are oxidation, corrosion, TMF (Thermal Mechanical Fatigue) and a combination of TMF and oxidation. Coatings failure in a turbine engine solely by oxidation is not a typical scenario. Further, in advanced turbine engines, incidences of corrosion are not common due to higher engine operating temperature and use of cleaner fuels. What is commonly observed is that the MCrAlY coatings are cracked by TMF. Subsequently the cracks allow oxygen diffusion into the substrate. Since the substrate is not oxidation resistant the advancing oxygen (through the cracks) causes the oxidation of the underlying substrate and triggers the failure of the components. It is therefore important that the coatings be resistant to fatigue as well as oxidation since fatigue cracking appears to be one of the primary triggering mechanisms of the failure of the coatings.
- TMF Thermal Mechanical Fatigue
- One approach of improving the fatigue resistance of coatings is by modification of the composition of the coatings and secondly by the use of a thin coating or possibly a combination of both.
- US-A-4,346,137 and US-A-4,758,480 described a method of improving the fatigue resistance of overlay coatings by a modification of composition.
- the platinum was added to MCrAlY coatings, which reduces the thermal expansion mismatch between the coatings and the substrate, hence also reduces the propensity of the coatings to cracking. This results in a significant improvement of the TMF life of the coatings.
- the US-A-4,758,480 discloses a class of protected coatings for superalloys in which the coating compositions are based on the composition of the underlying substrate. By tailoring the coatings to the substrate composition, diffusional stability results and other mechanical properties of the coating such as coefficient of thermal expansion and modulas, are brought closer to the substrate. The coatings thus obtained showed both increased oxidation and TMF resistance.
- the increase of coating thickness decreases TMF life of coatings; the problem is then to find a method that allows a deposition of thin protective coatings on complex turbine airfoils.
- a literature search shows that the MCrAlY overlay coatings are generally deposited by plasma spray process (i.e. APS, VPS, LPPS or HVOF) or electron beam physical vapor deposition (EB-PVD) and sputtering.
- plasma spray process i.e. APS, VPS, LPPS or HVOF
- EB-PVD electron beam physical vapor deposition
- a line of sight limitation Since airfoils contain many complex contoured surface i.e. airfoil to platform transition area, leading edge etc., the line of sight limitation present a difficulty in getting a good uniform coverage of coatings with thickness uniformity.
- US-A-5,558,758 , US-A-5,824,205 and US-A-5,833,829 described the deposition of MCrAlY coatings by electroplated process.
- the process involves a deposition of the coating precursor, CrAlM2 powder in a M1 bath where M2 is one or more of Si, Ti, Hf, Ga, Nb, Mn, Pt and rare earth elements and M1 consists of Ni, Co, Fe alone or in combination.
- the as-deposited coating is heat-treated to obtain the final coating structure.
- the stress strain distribution and thermal-mechanical loading are different area to area.
- some local area i.e. zone in an airfoil may be sensitive to oxidation or corrosion or thermal mechanical fatigue, or possibly a combination of one or more of degradation mode.
- a local coating with appropriate set of properties could be potentially beneficial in increasing the lifetime of airfoils.
- the plasma spray process generally used for manufacturing of coating is not ideal for local coating - it has a line of sight limitation and cannot coat effectively many 'difficult to coat area' such as platform to airfoil transition area with good thickness control.
- EP-B1-0 139 396 disclosed a process of local coating of turbine blade by plasma spraying of MCrAlY coatings.
- US-B1-6,435,830 and US-B1-6,270,318 wherein the underside of the platform is coated locally with a corrosion resistant coating.
- local coatings for repair or refurbish of components degraded by oxidation or corrosion For example, US-B1-6,203,847 provided a method of repairing by first plating the affected areas with Pt or noble metals then aluminising the surfaces.
- US-B1-6,274,193 restored a protective coating in a local areas with a replacement aluminide coating.
- the aim of the present invention is to find a MCrAlY-bond or overlay coating with good oxidation and fatigue resistance according to the requirements on local areas of a gas turbine component. Another aim is to find a method of depositing a MCrAlY-coating on a turbine component with uniformity. Yet another aim of the invention is to deposit a thin MCrAlY-coating on a large industrial gas turbine blade or vane with a good thickness control of the deposited layer.
- the process of the invention has a thickness control of ⁇ 20 ⁇ m of the thickness of the deposited layer, where as conventional plasma spray coating processes have thickness scatters of ⁇ 75 ⁇ m or even more.
- a coating with a layer thickness in a range of 25-400 ⁇ m can be applied.
- a thinner coating increase the TMF life of the coating.
- the used electroplated process has no line of sight limitation and can coat complex contour surfaces without any difficulty.
- the coating/masking step is repeated at different local areas on the surface of the article.
- the different areas are coated with different MCrAIY-coatings.
- the MCrAlY-coatings are selected according to the required properties in said areas in respect to one or a combination of oxidation, corrosion, thermal mechanical fatigue (TMF).
- TMF thermal mechanical fatigue
- Examples of electroplated ⁇ / ⁇ ' and that of ⁇ / ⁇ -MCrAlY local coatings are Ni-24Cr-5Al-1Ta-1.2Si-0.3Y and Ni-23C0-18Cr-10Al.0.5Y, respectively, or known from the European patent application EP-A1-1 411 210 , which has the same applicant as the present application.
- the present invention is generally applicable to components that operate within environments characterised by relatively high temperature, and are therefore subjected to severe thermal stresses and thermal cycling.
- Notable examples of such components include the high and low pressure nozzles and blades, shrouds, combustor liners and augmentor hardware of gas turbine engines.
- Fig. 1 shows as an example such an article 1 as blades or vanes comprising a blade 2 against which hot combustion gases are directed during operation of the gas turbine engine, a cavity, not visible in Figure 1, and cooling holes 4, which are on the external surface 5 of the component 1 as well as on the platform 3 of the component. Through the cooling holes 4 cooling air is ducted during operation of the engine to cool the external surface 5.
- the external surface 5 is subjected to severe attack by oxidation, corrosion and erosion due to the hot combustion gases and more importantly TMF cracking due to thermal mechanical loading.
- the article 1 consists of a nickel or cobalt base super alloy such as disclosed, by way of an example, in US-A-5,759,301 .
- the article 1 is a single crystal (SX) or directionally solidified (DS). While the advantages of this invention is described with reference to a turbine blade or vane as shown in Fig. 1, the invention is generally applicable to any component on which a coating system may be used to protect the component from its environment.
- the present invention individualized local or zone-coating 6 by using an electroplated method.
- the TMF life of the electroplated coating 6 was at least 2 times higher than the life of the plasma sprayed coatings. It is noted that the cost of the application of a coating 6 by an electroplated process is with advantage a third of a conventional plasma spray coating.
- the process of the invention has a thickness control of ⁇ 20 ⁇ m of the thickness of the deposited layer, where as conventional plasma spray coating processes have thickness scatters of ⁇ 75 ⁇ m or even more. Thus, a coating with a layer thickness in a range of 25-400 ⁇ m can be applied. A thinner coating 6 increase the TMF life of the coating 6.
- the used electroplated process has no line of sight limitation and can coat complex contour surfaces without any difficulty.
- the target coatings 6 shall be selected from the MCrAlX family of coatings tailored for oxidation/corrosion or fatigue resistance according the requirements at the local zone.
- the coatings 6 shall be applied in steps. Initially the areas not be coated are masked and the target area is coated by the electroplated method.
- Another previously masked area is coated, whereas the other areas is previously masked.
- To be able to coat the mask from the target area is removed and at the same time mask the previously coated area.
- the process of masking and coating of target areas are repeated as often as necessary.
- the surface will appear as if decorated with a series of 'patch coatings' each distinct from the other.
- the different areas are coated with different MCrAlY-coatings 6.
- the MCrAlY-coatings are selected according to the required properties in said areas in respect to one or a combination of oxidation, corrosion, thermal mechanical fatigue (TMF).
- TMF thermal mechanical fatigue
- One example of localized coating could be the TMF resistant coating on the platform/airfoil transition area of gas turbine blades and vanes and a highly oxidation resistant coating provided on the upper airfoil - the tip section.
- the masks used are wax and organic polymers. These masks can be applied and removed easily and do not leave any residue or chemical impurity behind on the surface.
- the method can be used as a repair process for a used MCrAlY-coating 6.
- Examples of electroplated ⁇ / ⁇ ' and that of ⁇ / ⁇ -MCrAlY local coatings are Ni-24Cr-5Al-1Ta-1.2Si-0.3Y and Ni-23C0-18Cr-10Al.0.5Y, respectively, or known from the European patent application EP-A1-1 411 210 , which has the same applicant as the present application.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Coating By Spraying Or Casting (AREA)
- Electroplating Methods And Accessories (AREA)
Description
- This invention relates according to
claim 1 to a method of depositing a MCrAlY-coating. - The turbine blades and vanes designed for use at high temperature are usually coated with environmentally resistant coatings. For example, MCrAlY overlay coatings are used for protection of turbine blades and vanes. MCrAlY protective overlay coatings are widely known in the prior art. They are a family of high temperature coatings, wherein M is selected from one or a combination of iron, nickel and cobalt. As an example
US-A-3,528,861 orUS-A-4,585,481 are disclosing such kind of oxidation resistant coatings.US-A-4, 152,223 as well discloses such method of coating and the coating itself. Besides the γ/β-MCrAlY-coating, there is another class of overlay MCrAlY coatings which are based on a γ/γ'-gamma/gamma prime-structure, which is for example disclosed inUS-A-4,546,052 orUS-A-4,973,445 . The advantages of γ/γ'-coatings is that they have a negligible thermal expansion mismatch with alloy of the underlying turbine article and are likely to have a better thermal mechanical properties. - Among γ/γ'- and γ/β-coatings, the field of γ/β-coatings have been an active area of research and a series of patents has been issued. E.g. a NiCrAlY coating is described in
US-A-3,754,903 and a CoCrAlY coating inUS-A-3,676,085 .US-A-4,346,137 discloses an improved high temperature fatigue resistance NiCoCrAlY coating.US-A-4,419,416 ,US-A-4,585,481 ,RE-32,121 and US-A-A-4, 743,514 describe MCrAlY coatings containing Si and Hf.US-A-4,313,760 discloses a superalloy coating composition with good oxidation, corrosion and fatigue resistance. Additional examples MCrAlY coatings are known fromUS-B1-6,280,857 ,US-B1-6,221,181 ,US-A-5,455,119 ,US-A-5,154,885 ,US-A-5, 035,958 orUS-B1-6,207,297 . They all deal primarily with improving the oxidation resistance of MCrAlY coatings. - Thermal barrier coatings are used to provide thermal insulation of the components in various types of engines e.g. in turbine engines. Furthermore, in the state of the art Thermal Barrier Coatings (TBC) are known from different patents.
US-A-4,055,705 ,US-A-4,248,940 ,US-A-4,321,311 orUS-A-4,676,994 disclose a TBC-coating for the use in the turbine blades and vanes. The ceramics used are yttria stabilized zirconia and applied by plasma spray (US-A-4, 055,705 ,US-A-4, 248,940 ) or by electron beam process (US-A-4, 321,311 ,US-A-4, 676,994 ) on top of the MCrAlY bond coat. - It is generally known in the industry that the coatings on turbine blades or vanes can fail by one or more of the following degradation modes. These are oxidation, corrosion, TMF (Thermal Mechanical Fatigue) and a combination of TMF and oxidation. Coatings failure in a turbine engine solely by oxidation is not a typical scenario. Further, in advanced turbine engines, incidences of corrosion are not common due to higher engine operating temperature and use of cleaner fuels. What is commonly observed is that the MCrAlY coatings are cracked by TMF. Subsequently the cracks allow oxygen diffusion into the substrate. Since the substrate is not oxidation resistant the advancing oxygen (through the cracks) causes the oxidation of the underlying substrate and triggers the failure of the components. It is therefore important that the coatings be resistant to fatigue as well as oxidation since fatigue cracking appears to be one of the primary triggering mechanisms of the failure of the coatings.
- One approach of improving the fatigue resistance of coatings is by modification of the composition of the coatings and secondly by the use of a thin coating or possibly a combination of both.
-
US-A-4,346,137 andUS-A-4,758,480 described a method of improving the fatigue resistance of overlay coatings by a modification of composition. InUS-A-4, 346,137 , the platinum was added to MCrAlY coatings, which reduces the thermal expansion mismatch between the coatings and the substrate, hence also reduces the propensity of the coatings to cracking. This results in a significant improvement of the TMF life of the coatings. On the other hand, theUS-A-4,758,480 discloses a class of protected coatings for superalloys in which the coating compositions are based on the composition of the underlying substrate. By tailoring the coatings to the substrate composition, diffusional stability results and other mechanical properties of the coating such as coefficient of thermal expansion and modulas, are brought closer to the substrate. The coatings thus obtained showed both increased oxidation and TMF resistance. - The increase of coating thickness decreases TMF life of coatings; the problem is then to find a method that allows a deposition of thin protective coatings on complex turbine airfoils. A literature search shows that the MCrAlY overlay coatings are generally deposited by plasma spray process (i.e. APS, VPS, LPPS or HVOF) or electron beam physical vapor deposition (EB-PVD) and sputtering. However, there are limitations of these processes; a) difficult or unable to deposit a thin coating, b) poor thickness control and c) a line of sight limitation. Since airfoils contain many complex contoured surface i.e. airfoil to platform transition area, leading edge etc., the line of sight limitation present a difficulty in getting a good uniform coverage of coatings with thickness uniformity.
- Interestingly, in a series of
patents, US-A-5,558,758 ,US-A-5,824,205 andUS-A-5,833,829 described the deposition of MCrAlY coatings by electroplated process. The process involves a deposition of the coating precursor, CrAlM2 powder in a M1 bath where M2 is one or more of Si, Ti, Hf, Ga, Nb, Mn, Pt and rare earth elements and M1 consists of Ni, Co, Fe alone or in combination. The as-deposited coating is heat-treated to obtain the final coating structure. The process provides a much better uniformity of coating distribution and coating of transition surfaces such as platforms to air foil can be performed with better thickness=uniformity and consistency. - In a given airfoil the stress strain distribution and thermal-mechanical loading are different area to area. For example, some local area i.e. zone in an airfoil may be sensitive to oxidation or corrosion or thermal mechanical fatigue, or possibly a combination of one or more of degradation mode. Thus a local coating with appropriate set of properties could be potentially beneficial in increasing the lifetime of airfoils. Unfortunately, the plasma spray process generally used for manufacturing of coating is not ideal for local coating - it has a line of sight limitation and cannot coat effectively many 'difficult to coat area' such as platform to airfoil transition area with good thickness control.
- This inherent difficulty of line of sight limitation of plasma spray process is not shown by electroplated process.
- There are references of local coating of turbine components or combustion components in the literature. For example,
EP-B1-0 139 396 disclosed a process of local coating of turbine blade by plasma spraying of MCrAlY coatings.US-B1-6,435,830 andUS-B1-6,270,318 wherein the underside of the platform is coated locally with a corrosion resistant coating. There are also examples of local coatings for repair or refurbish of components degraded by oxidation or corrosion. For example,US-B1-6,203,847 provided a method of repairing by first plating the affected areas with Pt or noble metals then aluminising the surfaces. SimilarlyUS-B1-6,274,193 restored a protective coating in a local areas with a replacement aluminide coating. - The aim of the present invention is to find a MCrAlY-bond or overlay coating with good oxidation and fatigue resistance according to the requirements on local areas of a gas turbine component. Another aim is to find a method of depositing a MCrAlY-coating on a turbine component with uniformity. Yet another aim of the invention is to deposit a thin MCrAlY-coating on a large industrial gas turbine blade or vane with a good thickness control of the deposited layer.
- According to the invention a method of deposition a MCrAlY-coating was found described in the features of the
claim 1. - According to the present invention individualized local or zone-coating by using an electroplated method. It is noted that the cost of the application of a coating by a galvanic process is with advantage a third of a conventional plasma spray coating. In addition, the process of the invention has a thickness control of ±20 µm of the thickness of the deposited layer, where as conventional plasma spray coating processes have thickness scatters of ±75 µm or even more. Thus, a coating with a layer thickness in a range of 25-400 µm can be applied. A thinner coating increase the TMF life of the coating. The used electroplated process has no line of sight limitation and can coat complex contour surfaces without any difficulty.
- The coating/masking step is repeated at different local areas on the surface of the article. The different areas are coated with different MCrAIY-coatings. The MCrAlY-coatings are selected according to the required properties in said areas in respect to one or a combination of oxidation, corrosion, thermal mechanical fatigue (TMF). As mask material wax and organic polymers are suitable.
- Examples of electroplated γ/γ' and that of γ/β-MCrAlY local coatings are Ni-24Cr-5Al-1Ta-1.2Si-0.3Y and Ni-23C0-18Cr-10Al.0.5Y, respectively, or known from the
European patent application EP-A1-1 411 210 , which has the same applicant as the present application. - Preferred embodiments of the invention are illustrated in the accompanying drawings, in which the enclosed Figure shows a gas turbine blade as an example. The drawing shows only parts important for the invention.
- The present invention is generally applicable to components that operate within environments characterised by relatively high temperature, and are therefore subjected to severe thermal stresses and thermal cycling. Notable examples of such components include the high and low pressure nozzles and blades, shrouds, combustor liners and augmentor hardware of gas turbine engines. Fig. 1 shows as an example such an
article 1 as blades or vanes comprising ablade 2 against which hot combustion gases are directed during operation of the gas turbine engine, a cavity, not visible in Figure 1, andcooling holes 4, which are on theexternal surface 5 of thecomponent 1 as well as on the platform 3 of the component. Through the cooling holes 4 cooling air is ducted during operation of the engine to cool theexternal surface 5. Theexternal surface 5 is subjected to severe attack by oxidation, corrosion and erosion due to the hot combustion gases and more importantly TMF cracking due to thermal mechanical loading. In many cases thearticle 1 consists of a nickel or cobalt base super alloy such as disclosed, by way of an example, inUS-A-5,759,301 . Thearticle 1 is a single crystal (SX) or directionally solidified (DS). While the advantages of this invention is described with reference to a turbine blade or vane as shown in Fig. 1, the invention is generally applicable to any component on which a coating system may be used to protect the component from its environment. - According to the present invention individualized local or zone-
coating 6 by using an electroplated method. With advantages, the TMF life of the electroplatedcoating 6 was at least 2 times higher than the life of the plasma sprayed coatings. It is noted that the cost of the application of acoating 6 by an electroplated process is with advantage a third of a conventional plasma spray coating. In addition, the process of the invention has a thickness control of ±20 µm of the thickness of the deposited layer, where as conventional plasma spray coating processes have thickness scatters of ±75 µm or even more. Thus, a coating with a layer thickness in a range of 25-400 µm can be applied. Athinner coating 6 increase the TMF life of thecoating 6. The used electroplated process has no line of sight limitation and can coat complex contour surfaces without any difficulty. Thetarget coatings 6 shall be selected from the MCrAlX family of coatings tailored for oxidation/corrosion or fatigue resistance according the requirements at the local zone. Thecoatings 6 shall be applied in steps. Initially the areas not be coated are masked and the target area is coated by the electroplated method. - Another previously masked area is coated, whereas the other areas is previously masked. To be able to coat the mask from the target area is removed and at the same time mask the previously coated area. The process of masking and coating of target areas are repeated as often as necessary. At completion, the surface will appear as if decorated with a series of 'patch coatings' each distinct from the other.
- The different areas are coated with different MCrAlY-
coatings 6. The MCrAlY-coatings are selected according to the required properties in said areas in respect to one or a combination of oxidation, corrosion, thermal mechanical fatigue (TMF). One example of localized coating could be the TMF resistant coating on the platform/airfoil transition area of gas turbine blades and vanes and a highly oxidation resistant coating provided on the upper airfoil - the tip section. - The masks used are wax and organic polymers. These masks can be applied and removed easily and do not leave any residue or chemical impurity behind on the surface.
- The method can be used as a repair process for a used MCrAlY-
coating 6. - Examples of electroplated γ/γ' and that of γ/β-MCrAlY local coatings are Ni-24Cr-5Al-1Ta-1.2Si-0.3Y and Ni-23C0-18Cr-10Al.0.5Y, respectively, or known from the
European patent application EP-A1-1 411 210 , which has the same applicant as the present application. - While our invention has been described by an example, it is apparent that other forms could be adopted by one skilled in the art. Accordingly, the scope of our invention is to be limited only by the attached claims.
-
- 1
- Article
- 2
- Blade
- 3
- Platform
- 4
- Cooling holes
- 5
- External surface of
article 1 - 6
- Layer of MCrAlY
Claims (5)
- A method of depositing a MCrAIY-coating (6) on the surface (5) of a single crystal (SX) or directionally solidified (DS) article (1), the method comprising the step of coating the article (1) only at a local area with the a γ/γ' or with a γ/β MCrAIY-coating (6) by an electroplated method, wherein the step of coating the article (1) only at a local area with the MCrAIY-coating (6) by an electroplated method is repeated at different local areas on the surface (5) of the article (1), and wherein different areas are coated with different MCrAIY-coatings, the MCrAIY-coatings are selected according to the required properties in said areas in respect to one or a combination of oxidation, corrosion, thermal mechanical fatigue (TMF).
- The method according to claim 1, wherein during the step of coating the article (1) only at a local area with the MCrAIY-coating (6) by an electroplated method the areas not to be coated are masked with a masked material.
- The method according to claim 2, wherein the areas not to be coated are masked with wax or organic polymers.
- The method according to any of the claims 1 to 3, wherein the method is used as a repair process for a used MCrAIY-coating (6).
- The method according to any of the claims 1 to 4, wherein a gas turbine article (1) such as blades or vanes is coated.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60231084T DE60231084D1 (en) | 2002-12-06 | 2002-12-06 | Method for the selective deposition of an MCrAlY coating |
EP02406066A EP1428982B1 (en) | 2002-12-06 | 2002-12-06 | A method of depositing a local MCrAIY-coating |
US10/726,593 US20040159552A1 (en) | 2002-12-06 | 2003-12-04 | Method of depositing a local MCrAIY-coating |
JP2003407617A JP2004190140A (en) | 2002-12-06 | 2003-12-05 | METHOD OF DEPOSITING LOCAL MCrAlY COATING |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02406066A EP1428982B1 (en) | 2002-12-06 | 2002-12-06 | A method of depositing a local MCrAIY-coating |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1428982A1 EP1428982A1 (en) | 2004-06-16 |
EP1428982B1 true EP1428982B1 (en) | 2009-02-04 |
Family
ID=32319725
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02406066A Expired - Lifetime EP1428982B1 (en) | 2002-12-06 | 2002-12-06 | A method of depositing a local MCrAIY-coating |
Country Status (4)
Country | Link |
---|---|
US (1) | US20040159552A1 (en) |
EP (1) | EP1428982B1 (en) |
JP (1) | JP2004190140A (en) |
DE (1) | DE60231084D1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1411210A1 (en) * | 2002-10-15 | 2004-04-21 | ALSTOM Technology Ltd | Method of depositing an oxidation and fatigue resistant MCrAIY-coating |
DE102006051813A1 (en) | 2006-11-03 | 2008-05-08 | Mtu Aero Engines Gmbh | Blade for a compressor or turbine of an aircraft engine, aircraft engine with such a blade and method for coating a blade of an aircraft engine |
EP2157209B1 (en) | 2008-07-31 | 2014-10-22 | Rohm and Haas Electronic Materials LLC | Inhibiting Background Plating |
JP6126852B2 (en) * | 2012-02-21 | 2017-05-10 | ハウメット コーポレイションHowmet Corporation | Gas turbine component coating and coating method |
US8728951B2 (en) | 2012-07-31 | 2014-05-20 | Varian Semiconductor Equipment Associates, Inc. | Method and system for ion-assisted processing |
WO2014159212A1 (en) * | 2013-03-14 | 2014-10-02 | United Technologies Corporation | Gas turbine engine stator vane platform cooling |
CN104141157A (en) * | 2013-05-07 | 2014-11-12 | 景祥凯工业股份有限公司 | Method for manufacturing hand tool |
US11261742B2 (en) | 2013-11-19 | 2022-03-01 | Raytheon Technologies Corporation | Article having variable composition coating |
US9957629B2 (en) * | 2014-08-27 | 2018-05-01 | Praxair S.T. Technology, Inc. | Electroplated coatings |
CN105348198B (en) * | 2015-09-29 | 2018-10-26 | 中能科泰(北京)科技有限公司 | Metal organic framework film and preparation method thereof |
WO2020180325A1 (en) * | 2019-03-07 | 2020-09-10 | Oerlikon Metco (Us) Inc. | Advanced bond coat materials for tbc with improved thermal cyclic fatigue and sulfidation resistance |
Family Cites Families (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3528861A (en) * | 1968-05-23 | 1970-09-15 | United Aircraft Corp | Method for coating the superalloys |
US3754903A (en) * | 1970-09-15 | 1973-08-28 | United Aircraft Corp | High temperature oxidation resistant coating alloy |
US3676085A (en) * | 1971-02-18 | 1972-07-11 | United Aircraft Corp | Cobalt base coating for the superalloys |
US4248940A (en) * | 1977-06-30 | 1981-02-03 | United Technologies Corporation | Thermal barrier coating for nickel and cobalt base super alloys |
US4055705A (en) * | 1976-05-14 | 1977-10-25 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Thermal barrier coating system |
US4152223A (en) * | 1977-07-13 | 1979-05-01 | United Technologies Corporation | Plasma sprayed MCrAlY coating and coating method |
US4313760A (en) * | 1979-05-29 | 1982-02-02 | Howmet Turbine Components Corporation | Superalloy coating composition |
US4346137A (en) * | 1979-12-19 | 1982-08-24 | United Technologies Corporation | High temperature fatigue oxidation resistant coating on superalloy substrate |
US4321311A (en) * | 1980-01-07 | 1982-03-23 | United Technologies Corporation | Columnar grain ceramic thermal barrier coatings |
USRE32121E (en) * | 1981-08-05 | 1986-04-22 | United Technologies Corporation | Overlay coatings for superalloys |
US4585481A (en) * | 1981-08-05 | 1986-04-29 | United Technologies Corporation | Overlays coating for superalloys |
US4419416A (en) * | 1981-08-05 | 1983-12-06 | United Technologies Corporation | Overlay coatings for superalloys |
US4676994A (en) * | 1983-06-15 | 1987-06-30 | The Boc Group, Inc. | Adherent ceramic coatings |
US4743514A (en) * | 1983-06-29 | 1988-05-10 | Allied-Signal Inc. | Oxidation resistant protective coating system for gas turbine components, and process for preparation of coated components |
DE3372501D1 (en) * | 1983-07-22 | 1987-08-20 | Bbc Brown Boveri & Cie | High-temperature protective coating |
US5035958A (en) * | 1983-12-27 | 1991-07-30 | General Electric Company | Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superaloys |
GB2167446B (en) * | 1984-10-05 | 1988-05-05 | Baj Ltd | Electrode deposited composite coating |
FR2571386B1 (en) * | 1984-10-05 | 1990-01-12 | Baj Ltd | PROTECTIVE METAL COATINGS |
GB8706951D0 (en) * | 1987-03-24 | 1988-04-27 | Baj Ltd | Overlay coating |
DE3740478C1 (en) * | 1987-11-28 | 1989-01-19 | Asea Brown Boveri | High temperature protective layer |
US4758480A (en) * | 1987-12-22 | 1988-07-19 | United Technologies Corporation | Substrate tailored coatings |
DE3815976A1 (en) * | 1988-05-10 | 1989-11-23 | Mtu Muenchen Gmbh | METHOD FOR PRODUCING GALVANICALLY SEPARATED HOT GAS CORROSION LAYERS |
DE3926479A1 (en) * | 1989-08-10 | 1991-02-14 | Siemens Ag | RHENIUM-PROTECTIVE COATING, WITH GREAT CORROSION AND / OR OXIDATION RESISTANCE |
CA2048804A1 (en) * | 1990-11-01 | 1992-05-02 | Roger J. Perkins | Long life abrasive turbine blade tips |
GB9216706D0 (en) * | 1992-08-06 | 1992-09-23 | Baj Ltd | Electrodeposited composite coatings |
US5455119A (en) * | 1993-11-08 | 1995-10-03 | Praxair S.T. Technology, Inc. | Coating composition having good corrosion and oxidation resistance |
GB9326082D0 (en) * | 1993-12-21 | 1994-02-23 | Baj Coatings Ltd | Rotor blades |
GB9414858D0 (en) * | 1994-07-22 | 1994-09-14 | Baj Coatings Ltd | Protective coating |
GB9414859D0 (en) * | 1994-07-22 | 1994-09-14 | Baj Coatings Ltd | Protective coating |
DE19624056A1 (en) * | 1996-06-17 | 1997-12-18 | Abb Research Ltd | Nickel-based super alloy |
FR2757181B1 (en) * | 1996-12-12 | 1999-02-12 | Snecma | PROCESS FOR PRODUCING A HIGH EFFICIENCY PROTECTIVE COATING AGAINST HIGH TEMPERATURE CORROSION FOR SUPERALLOYS, PROTECTIVE COATING OBTAINED BY THIS PROCESS AND PARTS PROTECTED BY THIS COATING |
US5837385A (en) * | 1997-03-31 | 1998-11-17 | General Electric Company | Environmental coating for nickel aluminide components and a method therefor |
US5985122A (en) * | 1997-09-26 | 1999-11-16 | General Electric Company | Method for preventing plating of material in surface openings of turbine airfoils |
US5902471A (en) * | 1997-10-01 | 1999-05-11 | United Technologies Corporation | Process for selectively electroplating an airfoil |
WO1999023279A1 (en) * | 1997-10-30 | 1999-05-14 | Abb Research Ltd. | High temperature protective coating |
US5935407A (en) * | 1997-11-06 | 1999-08-10 | Chromalloy Gas Turbine Corporation | Method for producing abrasive tips for gas turbine blades |
EP1082216B1 (en) * | 1998-04-29 | 2001-11-21 | Siemens Aktiengesellschaft | Product with an anticorrosion protective layer and a method for producing an anticorrosion protective layer |
US6203847B1 (en) * | 1998-12-22 | 2001-03-20 | General Electric Company | Coating of a discrete selective surface of an article |
AU4505399A (en) * | 1999-06-02 | 2000-12-28 | Abb Research Ltd | Coating composition for high temperature protection |
US6296447B1 (en) * | 1999-08-11 | 2001-10-02 | General Electric Company | Gas turbine component having location-dependent protective coatings thereon |
US6207297B1 (en) * | 1999-09-29 | 2001-03-27 | Siemens Westinghouse Power Corporation | Barrier layer for a MCrAlY basecoat superalloy combination |
US6435830B1 (en) * | 1999-12-20 | 2002-08-20 | United Technologies Corporation | Article having corrosion resistant coating |
US6270318B1 (en) * | 1999-12-20 | 2001-08-07 | United Technologies Corporation | Article having corrosion resistant coating |
SG96589A1 (en) * | 1999-12-20 | 2003-06-16 | United Technologies Corp | Methods of providing article with corrosion resistant coating and coated article |
SG98436A1 (en) * | 1999-12-21 | 2003-09-19 | United Technologies Corp | Method of forming an active-element containing aluminide as stand alone coating and as bond coat and coated article |
US20020132132A1 (en) * | 2000-12-12 | 2002-09-19 | Sudhangshu Bose | Method of forming an active-element containing aluminide as stand alone coating and as bond coat and coated article |
JP2002371803A (en) * | 2001-06-13 | 2002-12-26 | Mitsubishi Heavy Ind Ltd | Forming method for wear resistance layer for moving blade, wear resistance layer and regenerating method thereof |
JP2003120935A (en) * | 2001-10-09 | 2003-04-23 | Hitachi Zosen Corp | Transition piece in gas turbine |
JP3708909B2 (en) * | 2002-06-28 | 2005-10-19 | 独立行政法人科学技術振興機構 | Method for producing a high-temperature oxidation-resistant heat-resistant alloy member formed by depositing a rhenium-containing alloy film |
-
2002
- 2002-12-06 EP EP02406066A patent/EP1428982B1/en not_active Expired - Lifetime
- 2002-12-06 DE DE60231084T patent/DE60231084D1/en not_active Expired - Lifetime
-
2003
- 2003-12-04 US US10/726,593 patent/US20040159552A1/en not_active Abandoned
- 2003-12-05 JP JP2003407617A patent/JP2004190140A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US20040159552A1 (en) | 2004-08-19 |
DE60231084D1 (en) | 2009-03-19 |
EP1428982A1 (en) | 2004-06-16 |
JP2004190140A (en) | 2004-07-08 |
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