JP2009150387A - 内部通路に対する耐環境保護を有するタービンエンジン構成部品 - Google Patents
内部通路に対する耐環境保護を有するタービンエンジン構成部品 Download PDFInfo
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- 230000007613 environmental effect Effects 0.000 title abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 170
- 239000011248 coating agent Substances 0.000 claims abstract description 159
- 241000501667 Etroplus Species 0.000 claims abstract description 108
- 229910000951 Aluminide Inorganic materials 0.000 claims abstract description 47
- 239000010953 base metal Substances 0.000 claims abstract description 47
- 238000001816 cooling Methods 0.000 claims abstract description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 59
- 239000011241 protective layer Substances 0.000 claims description 31
- 229910052697 platinum Inorganic materials 0.000 claims description 29
- 239000011651 chromium Substances 0.000 claims description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 27
- 229910052804 chromium Inorganic materials 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 238000009792 diffusion process Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910000943 NiAl Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- 239000010410 layer Substances 0.000 description 21
- 239000000919 ceramic Substances 0.000 description 17
- 239000000567 combustion gas Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 238000000151 deposition Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 229910000601 superalloy Inorganic materials 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012720 thermal barrier coating Substances 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- -1 chromium halide Chemical class 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000446 fuel Substances 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
- 239000011253 protective coating Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000907 nickel aluminide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
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- 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
- F01D5/14—Form or construction
- F01D5/18—Hollow blades, i.e. blades with cooling or heating channels or cavities; Heating, heat-insulating or cooling means on blades
- F01D5/187—Convection cooling
-
- 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
- F05D2230/30—Manufacture with deposition of material
-
- 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
- F05D2230/30—Manufacture with deposition of material
- F05D2230/31—Layer deposition
-
- 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
-
- 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
- F05D2230/90—Coating; Surface 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
【解決手段】ガスタービンブレードは、ベース金属、プラットフォーム14、プラットフォームから上向きに延びる翼形部12、及びプラットフォームから下向きに延びるシャンク18を含む。シャンクは、外壁71及び内部通路84を有し、翼形部12は、その内部に冷却流を流すための冷却流路34を有する。ブレードは、シャンク18の内表面の少なくとも一部分のベース金属に接触し且つこれと相互拡散される第1のクロマイドコーティングを有し、この場合、第1のクロマイドコーティングは、その上にアルミナイドコーティングが堆積されない。ブレードは、翼形部12の内表面の少なくとも一部分のベース金属に接触し且つこれと相互拡散される第2のクロマイドコーティングを有する。
【選択図】図2
Description
14 ブレードプラットフォーム
16 ブレードダブテール
18 ブレードシャンク
20 加圧空気冷媒
22 正圧側壁
24 負圧側壁
34 内部冷却回路
36 内部隔壁又はブリッジ
38、40 冷却孔
82 ダブテール内部通路
84 シャンク18の内部通路
71 シャンク外壁
72 ダブテール外壁
73 シャンク内壁
74 ダブテール内壁
Claims (13)
- ベース金属と、
プラットフォーム(14)と、
前記プラットフォームから上向きに延び、冷却流を流すための冷却流路(34)が内部に配置された翼形部(12)と、
前記プラットフォームから下向きに延び、外壁と、冷却流を流すため内部に配置された内部通路(84)とを有するシャンク(18)と、
前記シャンクの外壁の内表面(113)、(114)の少なくとも一部分のベース金属に接触し、且つこれと相互拡散され、その上にアルミナイドコーティングが堆積されていない第1のクロマイドコーティング(102)と、
前記翼形部の内表面の少なくとも一部分のベース金属に接触し、且つこれと相互拡散される第2のクロマイドコーティング(144)と、
を含むガスタービンブレード(10)。 - 前記第1のクロマイドコーティング(102)が、平均で20−50重量%のクロムを含む、
請求項1に記載のガスタービンブレード。 - 前記第1のクロマイドコーティング(102)が、0.0005−0.002インチの厚さを有する、
請求項1又は2に記載のガスタービンブレード。 - 前記第2のクロマイドコーティング(144)が、平均で20−50重量%のクロムを含む、
請求項1乃至3のいずれか1項に記載のガスタービンブレード。 - 前記第2のクロマイドコーティング(144)が、0.0005−0.002インチの厚さを有する、
請求項1乃至4のいずれか1項に記載のガスタービンブレード。 - 前記翼形部(12)の外表面の少なくとも一部分のベース金属に接触し、且つこれと相互拡散された第3のクロマイドコーティング(48)を更に含む、
請求項1乃至5のいずれか1項に記載のガスタービンブレード。 - 前記シャンク(18)の外表面111の少なくとも一部分のベース金属と接し、且つこれと相互拡散された第4のクロマイドコーティング(101)を更に含む、
請求項1乃至6のいずれか1項に記載のガスタービンブレード。 - 拡散コーティング及びオーバーレイコーティングからなる群から選択された保護層(50)を有する多層コーティングシステム(44)を更に含む、
請求項6又は7に記載のガスタービンブレード。 - 前記ベース金属が、重量比で、4−20%のコバルト、1−10%のクロム、5−7%のアルミニウム、0−2%のモリブデン、3−8%のタングステン、4−12%のタンタル、0−2%のチタニウム、0−8%のレニウム、0−6%のルテニウム、0−1%のニオビウム、0−0.1%の炭素、0−0.01%のホウ素、0−0.1%のイットリウム、0−1.5%のハフニウム、及び残部のニッケル並びに不可避的不純物からなる組成を有する、
請求項1乃至8のいずれか1項に記載のガスタービンブレード。 - 前記保護層(50)が、拡散アルミナイド及び拡散プラチナアルミナイドからなる群から選択された拡散コーティングを含む、
請求項8に記載のガスタービンブレード。 - 前記保護層(50)が、MCrAlXオーバーレイコーティングを含む、
請求項8に記載のガスタービンブレード。 - 前記保護層(50)が、NiAl金属間化合物オーバーレイコーティングを含む、
請求項8に記載のガスタービンブレード。 - ベース金属を含むガスタービンブレードを作製するための方法であって、
プラットフォーム、該プラットフォームから上向きに延びる翼形部、及び前記プラットフォームから下向きに延びるシャンクを備え、前記翼形部がその内部に配置された冷却流路を有し、前記シャンクがその内部に配置された内部通路と外壁とを有するガスタービンブレードを提供するステップ(170)と、
前記シャンクの外壁の内表面の少なくとも一部分のベース金属を覆い且つこれと相互拡散された第1のクロマイドコーティングを施工するステップ(171)と、
前記翼形部内部の冷却流路の少なくとも一部分のベース金属を覆い且つこれと相互拡散された第2のクロマイドコーティングを施工するステップ(172)と、
前記翼形部の外表面の少なくとも一部分のベース金属を覆い且つこれと相互拡散された第3のクロマイドコーティングを任意選択的に施工するステップ(173)と、
前記シャンクの外表面の少なくとも一部分のベース金属に接触し且つこれと相互拡散された第4のクロマイドコーティングを任意選択的に施工するステップ(174)と、
前記内部通路の内部に更なるコーティング堆積を防止し、これによって前記タービンブレード上への後続のコーティング施工中に前記冷却流路の内部への有意なコーティング堆積を防止するために、前記シャンク内部に配置された内部通路を遮蔽するステップ(180)と、
拡散コーティング及びオーバーレイコーティングからなる群から選択された保護層を有する多層コーティングシステムを、前記翼形部上の第3のクロマイドコーティングの少なくとも一部分に接触させて施工するステップ(182、184)と、
を含む方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/959,595 | 2007-12-19 | ||
US11/959,595 US8545185B2 (en) | 2007-12-19 | 2007-12-19 | Turbine engine components with environmental protection for interior passages |
Publications (2)
Publication Number | Publication Date |
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JP2009150387A true JP2009150387A (ja) | 2009-07-09 |
JP5466397B2 JP5466397B2 (ja) | 2014-04-09 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2008319543A Active JP5466397B2 (ja) | 2007-12-19 | 2008-12-16 | 内部通路に対する耐環境保護を有するタービンエンジン構成部品 |
Country Status (5)
Country | Link |
---|---|
US (1) | US8545185B2 (ja) |
EP (1) | EP2072759B1 (ja) |
JP (1) | JP5466397B2 (ja) |
CA (1) | CA2645780C (ja) |
TW (1) | TWI447295B (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014231780A (ja) * | 2013-05-29 | 2014-12-11 | 三菱日立パワーシステムズ株式会社 | Alコーティング方法とガスタービン翼 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US9297089B2 (en) | 2011-07-08 | 2016-03-29 | Barson Composites Corporation | Coatings for gas turbine components |
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US20090162209A1 (en) | 2009-06-25 |
TW200940810A (en) | 2009-10-01 |
EP2072759B1 (en) | 2019-04-10 |
TWI447295B (zh) | 2014-08-01 |
EP2072759A3 (en) | 2012-12-26 |
US8545185B2 (en) | 2013-10-01 |
EP2072759A2 (en) | 2009-06-24 |
CA2645780A1 (en) | 2009-06-19 |
CA2645780C (en) | 2016-04-05 |
JP5466397B2 (ja) | 2014-04-09 |
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