JP2011080148A - 噴霧スプレーを用いた金属皮膜の堆積方法 - Google Patents
噴霧スプレーを用いた金属皮膜の堆積方法 Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 239000007921 spray Substances 0.000 title claims abstract description 26
- 230000008021 deposition Effects 0.000 title abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000601 superalloy Inorganic materials 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002844 melting Methods 0.000 claims description 78
- 230000008018 melting Effects 0.000 claims description 78
- 239000000843 powder Substances 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 13
- 238000005219 brazing Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims 1
- 239000008199 coating composition Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000011253 protective coating Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 230000008439 repair process Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000951 Aluminide Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012720 thermal barrier coating Substances 0.000 description 3
- 235000002566 Capsicum Nutrition 0.000 description 2
- 239000006002 Pepper Substances 0.000 description 2
- 241000722363 Piper Species 0.000 description 2
- 235000016761 Piper aduncum Nutrition 0.000 description 2
- 235000017804 Piper guineense Nutrition 0.000 description 2
- 235000008184 Piper nigrum Nutrition 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910020706 Co—Re Inorganic materials 0.000 description 1
- 229910019819 Cr—Si Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010218 electron microscopic analysis Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0018—Brazing of turbine parts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/008—Soldering within a furnace
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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
- 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
- C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
-
- 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
- C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
- C23C10/32—Chromising
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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
- 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
- C23C10/38—Chromising
-
- 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
- C23C10/44—Siliconising
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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
- 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
- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/001—Turbines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/34—Coated articles, e.g. plated or painted; Surface treated articles
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- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
【解決手段】高温動作環境下で金属基材(17)の耐酸化性及び耐食性を高めるため、ガスタービンエンジンの第2段及び第3段における部品などの金属基材(17)のコーティング方法であって、本方法は、高融点超合金又はMCrAlY(式中、MはFe、Ni及び/又はCoを含む)成分(14)と、約2〜5重量%のケイ素、ホウ素又はハフニウムを含有する低融点成分(15)とからなる粉体混合物を形成する段階と、噴霧スプレーを用いて室温で金属基材(17)の表面に粉体混合物を施工し、均一な表面皮膜を形成する段階と、真空条件下の被覆した基材表面を約1900°F〜2275°Fの範囲の温度まで加熱して、下層の基材に耐酸化性をもたらす均一な皮膜組成物(19)を得る段階と、を含む。
【選択図】 図1
Description
15 低融点成分
16 バインダー材料
17 金属基材
18 バインダー材料
19 皮膜
Claims (14)
- 基材(17)のコーティング方法であって、
高融点超合金成分(14)及び低融点ろう付けバインダー成分(15)の粉体混合物を形成する段階と、
噴霧スプレーを用いて室温で前記基材(17)の表面に前記粉体混合物を施工し、前記基材表面上に実質的に均一な厚みの皮膜(19)を形成する段階と、
前記皮膜に強度及び耐酸化性/耐食性を与えるのに十分な温度まで前記基材(17)を加熱する段階と
を含む方法。 - 前記基材が金属を含む、請求項1記載の方法。
- 金属基材(17)を被覆して高温での前記基材(17)の耐酸化性を向上させる方法であって、
高融点超合金成分(14)又はMCrAlY(式中、MはFe、Ni及び/又はCoを含む)と、ケイ素、ホウ素、ハフニウム又は金を含む低融点成分(15)とからなる粉体混合物を形成する段階と、
噴霧スプレーを用いて室温で前記金属基材(17)の表面に前記粉体混合物を施工し、前記基材表面上に実質的に均一な厚みの皮膜(19)を形成する段階と、
真空条件下の前記被覆した基材表面を1900°F〜2275°Fの範囲の温度まで加熱して液相を生じさせ、高融点粉体を懸濁せしめ、液相焼結によって金属結合を成長させる段階と、
を含む方法。 - 前記被覆した基材表面を加熱する段階が、約840°Fの温度から約2225°Fまで上昇した後、約1975°Fまで低下するように段階的に行われる、請求項3記載の方法。
- 前記低融点成分(15)が2〜12重量%の量のケイ素を含む、請求項3記載の方法。
- 前記被覆した基材表面を段階的に加熱する段階が4〜6時間にわたって行われる、請求項4記載の方法。
- 前記被覆した基材表面を段階的に加熱する段階が5×10-4torrの真空条件下で行われる、請求項4記載の方法。
- 前記高融点成分(14)の量が前記皮膜の10重量%〜60重量%の範囲である、請求項3記載の方法。
- 前記低融点成分(15)の量が90重量%〜40重量%の範囲である、請求項3記載の方法。
- 前記加熱段階の次に、前記金属基材(17)上の前記皮膜(19)を機械的に仕上げる段階を更に含む、請求項3記載の方法。
- 前記皮膜(19)の表面温度を1975°F〜2050°Fまで高める段階を更に含む、請求項3記載の方法。
- 真空条件下で前記被覆した基材表面を加熱する段階が、最終の熱処理され且つコーティングされた表面の気孔率のレベルが20%未満を達成する、請求項4記載の方法。
- 前記粉体混合物を施工する段階が前記金属基材(17)の一部だけを覆う、請求項3記載の方法。
- ガスタービンエンジン部品の金属表面を補修する方法であって、
高融点超合金成分(14)又はMCrAlY(式中、MはFe、Ni及び/又はCoを含む群から選択される)と、ケイ素を含有する低融点成分(15)とからなる粉体混合物を形成する段階と、
バインダー(16)を用いて室温で前記タービンエンジン部品の表面に前記粉体混合物を施工し、実質的に均一な厚みの皮膜(19)を形成する段階と、
真空条件下の前記皮膜を1900°F〜2275°Fの範囲の温度まで加熱して、低融点成分を液化し、液相焼結による前記高融点成分の結合を開始する段階と
を含む方法。
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US12/574,809 | 2009-10-07 | ||
US12/574,809 US9023423B2 (en) | 2009-10-07 | 2009-10-07 | Method of deposition of metallic coatings using atomized spray |
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JP2011080148A true JP2011080148A (ja) | 2011-04-21 |
JP5802372B2 JP5802372B2 (ja) | 2015-10-28 |
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EP (1) | EP2309019B1 (ja) |
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CN (1) | CN102031477B (ja) |
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ES2391321B1 (es) * | 2011-04-29 | 2013-10-21 | Universitat Jaume I De Castellón | Método para recubrir materiales mediante proyección térmica de composiciones. |
US8591986B1 (en) | 2012-08-17 | 2013-11-26 | General Electric Company | Cold spray deposition method |
CN102995002B (zh) * | 2012-11-30 | 2015-02-25 | 杭州杭氧透平机械有限公司 | 一种离心式空压机气体流道的喷涂防腐方法 |
US10279438B2 (en) * | 2013-03-15 | 2019-05-07 | Siemens Energy, Inc. | Presintered preform for repair of superalloy component |
CN104372338B (zh) * | 2014-11-04 | 2017-02-15 | 西安热工研究院有限公司 | 一种锅炉过/再热器用奥氏体不锈钢管表面合金化方法 |
CN104561881B (zh) * | 2014-12-25 | 2016-10-05 | 中国航空工业集团公司北京航空制造工程研究所 | 一种高温可磨耗封严涂层的制备方法 |
US10052724B2 (en) * | 2016-03-02 | 2018-08-21 | General Electric Company | Braze composition, brazing process, and brazed article |
FR3062324B1 (fr) * | 2017-01-30 | 2019-03-22 | Safran Aircraft Engines | Procede de fabrication de pieces realisees en metallurgie des poudres comportant l’application d'un revetement |
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EP2309019B1 (en) | 2018-06-27 |
US9023423B2 (en) | 2015-05-05 |
JP5802372B2 (ja) | 2015-10-28 |
EP2309019A3 (en) | 2012-03-21 |
US20110081480A1 (en) | 2011-04-07 |
CN102031477B (zh) | 2016-05-18 |
CN102031477A (zh) | 2011-04-27 |
EP2309019A2 (en) | 2011-04-13 |
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