US20070138019A1 - Platinum modified NiCoCrAlY bondcoat for thermal barrier coating - Google Patents
Platinum modified NiCoCrAlY bondcoat for thermal barrier coating Download PDFInfo
- Publication number
- US20070138019A1 US20070138019A1 US11/315,535 US31553505A US2007138019A1 US 20070138019 A1 US20070138019 A1 US 20070138019A1 US 31553505 A US31553505 A US 31553505A US 2007138019 A1 US2007138019 A1 US 2007138019A1
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- United States
- Prior art keywords
- bondcoat
- step comprises
- platinum
- substrate
- nicocraly
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
- C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/325—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with layers graded in composition or in physical properties
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
Definitions
- the present invention relates to a platinum modified NiCoCrAlY bondcoat for a thermal barrier coating and a method for forming same.
- Turbine engine components are subjected to elevated temperatures as a result of their exposure to high temperature gas. Such exposure can lead to the creation of unwanted defects in the components.
- bondcoats and/or ceramic topcoats are applied to the surfaces of the turbine engine components.
- the present invention is directed to an improved coating system for a turbine engine component and methods for forming same.
- a method for forming a coating on a substrate broadly comprises the steps of providing a substrate, depositing a layer of platinum onto a surface of the substrate, depositing a NiCoCrAlY layer onto the platinum layer, and heat treating the substrate with the deposited layers to form a platinum modified NiCoCrAlY bondcoat.
- an alternative method for forming a coating on a substrate broadly comprises the steps of providing a substrate, depositing a NiCoCrAlY layer onto a surface of the substrate, depositing a layer of platinum over the NiCoCrAlY layer, and heat treating the substrate with the deposited layers to form a platinum modified NiCoCrAlY bondcoat.
- a turbine engine component broadly comprising a substrate formed from a nickel based superalloy and a platinum modified NiCoCrAlY bondcoat applied to a surface of the substrate.
- FIG. 1 is a schematic representation of a first coating system in accordance with the present invention.
- FIG. 2 is a schematic representation of a second coating system in accordance with the present invention.
- the present invention is directed to an improved coating system that can be applied to turbine engine components, such as vanes, blades, and seals, that are exposed to high temperature gases.
- the coating system includes a thin bondcoat that offers oxidation protection to the nickel based superalloy forming the turbine engine component.
- the bondcoat is a platinum modified NiCoCrAlY coating. The addition of the platinum to the bondcoat improves the adherence of the aluminum oxide scale that forms during use of the turbine engine component.
- FIG. 1 illustrates a first sequence for forming a coating system in accordance with the present invention.
- a nickel based alloy substrate 10 has a surface 12 .
- a layer 14 of platinum is deposited onto the surface 12 , preferably using an electroplating technique.
- a useful electroplating bath may contain platinum quantities in the range of 17 to 26 grams/liter.
- the current density may range from 20 to 30 amps per square foot.
- the time for electroplating will be determined by the required thickness.
- the electroplating bath temperature can go up to 200 degrees F.
- the layer of electroplated platinum may have a thickness in the range of from about 0.01 to 1.0 mil. These electroplating parameters are offered merely for purposes of illustration as other platinum electroplating parameters can be employed.
- the platinum layer also can be deposited by techniques other than electroplating, such as including, but not limited to sputtering, and other deposition techniques.
- a layer 16 of NiCoCrAlY material is deposited onto the platinum layer.
- the NiCoCrAlY material is deposited using a cathodic arc deposition process.
- cathodic arc plasma vapor deposition techniques for applying the coatings of the present invention by cathodic arc plasma vapor deposition are discussed in U.S. Pat. Nos. 5,972,185; 5,932,078; 6,036,828; 5,792,267; and 6,224,726, all of which are incorporated by reference herein.
- Alternate methods of deposition including, but not limited to, other plasma vapor deposition techniques such as magnetron sputtering and electron beam plasma vapor deposition may be used.
- the NiCoCrAlY material which is deposited may have a composition comprising from about 4.0 to 25 wt %, preferably from about 4.0 to 18 wt %, chromium, from about 2.0 to 28 wt %, preferably from about 2.0 to 24 wt %, cobalt, from about 5.5 to 15 wt %, preferably from about 5.5 to 13.5 wt %, aluminum, from about 0.1 to 1.6 wt %, preferably from about 0.1 to 0.8 wt %, yttrium, up to about 2.0 wt %, preferably from about 0.001 to 0.4 wt %, hafnium, up to about 2.0 wt %, preferably from about 0.001 to 0.7 wt %, silicon, from about 3.0 to 12 wt %, preferably from about 3.0 to 10
- the coating may also comprise up to 2.0 wt % of other elements as impurities.
- the yttrium in the coating improves the adherence of the aluminum oxide scale layer 18 which is formed during use. Sulfur would usually migrate to the aluminum oxide scale layer 18 ; however, the presence of yttrium prevents this from occurring.
- the substrate 10 with the deposited layers 14 and 16 is subjected to a diffusion heat treatment.
- the diffusion heat treatment is carried out at a temperature in the range of from about 1200 to about 2100 degrees Fahrenheit for a time period in the range of from about 2.0 to 15 hours.
- the diffusion treatment is preferably carried out in an inert gas atmosphere such as an argon atmosphere.
- the fully heat treated platinum modified NiCoCrAlY bondcoat may have a platinum content in the range of from 5.0 to 0.70 wt %, preferably from 10 to 60 wt %, and a thickness in the range of from about 1.0 to 5.0 mils.
- the bondcoat typically forms a dense three-dimensional interconnected two-phase microstructure with grains sizes ranging from 0.5 to 30 microns. Platinum may be substituted by palladium, rhodium, iridium, and mixtures thereof.
- a ceramic topcoat 20 may be applied using any suitable ceramic composition known in the art.
- a preferred composition for the ceramic topcoat 20 is yttria stabilized zirconia such as 7.0 wt % yttria stabilized zirconia.
- Other favored compositions include zirconia based pyrochlores, 5.0 to 60 mol % gadolinia stabilized zirconia, and zirconia stabilized with various lanthanide sesquioxides and mixtures thereof described in U.S. Pat. No. 6,730,422, which is incorporated by reference herein.
- the ceramic topcoat layer 20 may have a thickness in the range of from about 1.0 to 50 mils, preferably from about 3.0 to 15 mils.
- the ceramic topcoat 20 may be applied using any suitable electron beam-physical vapor deposition (EB-PVD) technique known in the art.
- a preferred deposition technique is electron beam physical vapor deposition (EB-PVD).
- Ceramic coatings are preferably applied to bondcoated substrates at substrate temperature ranging from about 1700 to 2200 degrees Fahrenheit, and chamber pressures from about 0.1 to 1.0 millitorr.
- Deposition time ranges from 20 to 120 minutes using feedstock federates of from about 0.2 to 1.5 inches per hour.
- Other suitable deposition techniques include thermal spraying, chemical vapor deposition, and other physical vapor deposition techniques including, but not limited to, cathodic arc deposition, sputtering, and thermal evaporation. Either an inert or reactive atmosphere can optionally be used in all of these deposition techniques, as known to be appropriate to one skilled in the art.
- the ceramic topcoat layer 20 is characterized by a columnar grained microstructure with the columnar grains or columns being oriented substantially perpendicular to the surface 12 .
- the columnar grains or columns extend outwardly from the bondcoat or from an aluminum oxide scale layer, 18 that is intentionally formed on the bondcoat before or during deposition of the ceramic layer 20 .
- vapor deposition techniques that utilize means to increase the mobility of vapor species on the substrate surface, such as substrate bias or high-energy ion impingement, result in dense equiaxed ceramic coatings.
- thermally sprayed coatings that form by depositing liquid droplets on the substrate have a porous microstructure consisting of randomly piled frozen splats of liquid. These splats are typically microcracked and typically trap pores between them, resulting in a strain-tolerant microstructure.
- the bondcoat is formed by depositing the NiCoCrAlY layer 16 onto the surface 12 of the substrate and then depositing the platinum layer 14 over the NiCoCrAlY layer 16 .
- the NiCoCrAlY layer may have the same composition as described above and may be deposited using the technique described above.
- the platinum layer 14 may have the same compositional range as described above and may be deposited using the electroplating technique described above.
- the diffusion heat treatment step is performed after the platinum depositing step using the same parameters as described above.
- the preferred bondcoat thickness is the same as that discussed in the prior method.
- the ceramic topcoat layer 20 may be deposited as discussed above.
- Specimens coated in accordance with the present invention have survived greater than 1000 hours of cyclic oxidation in a burner rig at temperatures in excess of 2000 degrees Fahrenheit.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Ceramic Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Physical Vapour Deposition (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/315,535 US20070138019A1 (en) | 2005-12-21 | 2005-12-21 | Platinum modified NiCoCrAlY bondcoat for thermal barrier coating |
TW095139166A TW200724717A (en) | 2005-12-21 | 2006-10-24 | Platinum modified NiCoCrAlY bondcoat for thermal barrier coating |
IL178956A IL178956A0 (en) | 2005-12-21 | 2006-10-31 | METHOD FOR FORMING A COATING ON A SUBSTRATE AND A PLATINUM MODIFIED NiCoCrAIY COATING |
KR1020060114856A KR20070067602A (ko) | 2005-12-21 | 2006-11-21 | 기판상에 피막을 형성하는 방법 및 터빈 엔진 부품 |
SG200608680-5A SG133525A1 (en) | 2005-12-21 | 2006-12-12 | Platinum modified nicocraly bondcoat for thermal barrier coating |
MXPA06014620A MXPA06014620A (es) | 2005-12-21 | 2006-12-14 | Capa de union nicocraiy modificada con platino para revestimiento termico de barrera. |
EP06256430A EP1801263B1 (en) | 2005-12-21 | 2006-12-19 | Platinum modified NiCoCrAly bondcoat for thermal barrier coating |
CNA2006101690955A CN1986889A (zh) | 2005-12-21 | 2006-12-20 | 用于隔热涂层的经铂改性的NiCoCrAlY结合涂层 |
JP2006343990A JP2007169788A (ja) | 2005-12-21 | 2006-12-21 | 断熱被膜用の白金改質NiCoCrAlYボンドコート |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/315,535 US20070138019A1 (en) | 2005-12-21 | 2005-12-21 | Platinum modified NiCoCrAlY bondcoat for thermal barrier coating |
Publications (1)
Publication Number | Publication Date |
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US20070138019A1 true US20070138019A1 (en) | 2007-06-21 |
Family
ID=38016616
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/315,535 Abandoned US20070138019A1 (en) | 2005-12-21 | 2005-12-21 | Platinum modified NiCoCrAlY bondcoat for thermal barrier coating |
Country Status (9)
Country | Link |
---|---|
US (1) | US20070138019A1 (es) |
EP (1) | EP1801263B1 (es) |
JP (1) | JP2007169788A (es) |
KR (1) | KR20070067602A (es) |
CN (1) | CN1986889A (es) |
IL (1) | IL178956A0 (es) |
MX (1) | MXPA06014620A (es) |
SG (1) | SG133525A1 (es) |
TW (1) | TW200724717A (es) |
Cited By (11)
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US20080261073A1 (en) * | 2006-03-24 | 2008-10-23 | United Technologies Corporation | Coating suitable for use as a bondcoat in a thermal barrier coating system |
US20090004503A1 (en) * | 2007-06-27 | 2009-01-01 | Melvin Freling | Metallic alloy composition and protective coating |
US20090035485A1 (en) * | 2007-08-02 | 2009-02-05 | United Technologies Corporation | Method for forming active-element aluminide diffusion coatings |
US20090134035A1 (en) * | 2007-08-02 | 2009-05-28 | United Technologies Corporation | Method for forming platinum aluminide diffusion coatings |
US20090136664A1 (en) * | 2007-08-02 | 2009-05-28 | United Technologies Corporation | Method for forming aluminide diffusion coatings |
US20090191422A1 (en) * | 2008-01-30 | 2009-07-30 | United Technologies Corporation | Cathodic ARC deposition coatings for turbine engine components |
US20090258165A1 (en) * | 2008-04-14 | 2009-10-15 | United Technologies Corporation | Platinum-modified cathodic arc coating |
US20100143745A1 (en) * | 2006-11-24 | 2010-06-10 | Werner Stamm | NiCoCrl layer for forming dense and solid oxide layers and metallic layer system |
US20110143164A1 (en) * | 2009-12-14 | 2011-06-16 | United Technologies Corporation | Low sulfur nickel base substrate alloy and overlay coating system |
US8147982B2 (en) | 2007-12-19 | 2012-04-03 | United Technologies Corporation | Porous protective coating for turbine engine components |
US10183311B2 (en) | 2010-06-18 | 2019-01-22 | Safran Aircraft Engines | Method for aluminizing a surface by means of the advance deposition of a platinum and nickel layer |
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US8343591B2 (en) * | 2008-10-24 | 2013-01-01 | United Technologies Corporation | Method for use with a coating process |
FR2941967B1 (fr) * | 2009-02-11 | 2011-05-13 | Snecma | Methode de fabrication d'une barriere thermique recouvrant une piece realisee dans un substrat metallique en superalliage et piece thermomecanique resultant de cette methode de traitement |
CN101791893B (zh) * | 2010-01-22 | 2012-12-19 | 北京航空航天大学 | 一种双层结构MCrAlY粘结层及其制备方法 |
US8708659B2 (en) | 2010-09-24 | 2014-04-29 | United Technologies Corporation | Turbine engine component having protective coating |
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- 2006-10-31 IL IL178956A patent/IL178956A0/en unknown
- 2006-11-21 KR KR1020060114856A patent/KR20070067602A/ko not_active Application Discontinuation
- 2006-12-12 SG SG200608680-5A patent/SG133525A1/en unknown
- 2006-12-14 MX MXPA06014620A patent/MXPA06014620A/es unknown
- 2006-12-19 EP EP06256430A patent/EP1801263B1/en not_active Not-in-force
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Also Published As
Publication number | Publication date |
---|---|
CN1986889A (zh) | 2007-06-27 |
SG133525A1 (en) | 2007-07-30 |
IL178956A0 (en) | 2007-03-08 |
EP1801263B1 (en) | 2013-03-27 |
JP2007169788A (ja) | 2007-07-05 |
EP1801263A1 (en) | 2007-06-27 |
MXPA06014620A (es) | 2008-10-24 |
KR20070067602A (ko) | 2007-06-28 |
TW200724717A (en) | 2007-07-01 |
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