TWI718481B - 防止部件腐蝕的保護 - Google Patents

防止部件腐蝕的保護 Download PDF

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TWI718481B
TWI718481B TW108106406A TW108106406A TWI718481B TW I718481 B TWI718481 B TW I718481B TW 108106406 A TW108106406 A TW 108106406A TW 108106406 A TW108106406 A TW 108106406A TW I718481 B TWI718481 B TW I718481B
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Taiwan
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layer
engine
microns
tbc
coating
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TW108106406A
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TW201945589A (zh
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大衛 布里茨
普萊文Ｋ 那瓦卡
大衛 湯普森
尤瑞 美林克
蘇克提 查特吉
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美商應用材料股份有限公司
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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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
    • 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
    • F01D5/186—Film 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
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    • 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
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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24612—Composite web or sheet
    • Y10T428/2462—Composite web or sheet with partial filling of valleys on outer surface

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

在此論述使用系統與方法，經由在引擎環境中的CMAS截斷抑制CMAS腐蝕及/或藉由在熱引擎區段部件上的金屬氧化物保護塗佈之形成避免或降低CMAS腐蝕。當引擎操作於飛行環境中或者測試或品質控制環境中，可發生CMAS截斷。金屬氧化物保護塗佈可施加在其他塗佈上方，包括Gd-鋯酸鹽(GZO)或氧化釔穩定化氧化鋯(YSZ)。金屬氧化物保護塗佈在原始設備製造商(OEM)處施加，且也可在飛行中的引擎使用期間或者在維護或品質測試期間，使用氣體注射系統原位地施加。金屬氧化物保護塗佈含有稀土元素、鋁、鋯、鉻、或前述物的組合，且厚度從1 nm至3微米。

Description

防止部件腐蝕的保護
本發明的具體例大體上關於用於渦輪葉片及暴露於腐蝕環境的其他部件之保護塗佈。
航太部件是由不鏽鋼、超合金、及鋁所製成。腐蝕可發生在各種模式中，高溫熱腐蝕(HTHC)、低溫熱腐蝕(LTHC)、及氧化。腐蝕可發生在葉片面上與葉片柄上、渦輪盤緣上、及暴露於腐蝕環境的其他部件上。
包括渦輪翼與葉片的航太部件由鎳與鈷系超合金所製造。在引擎操作期間的超合金保護利用黏附於部件的表面或多個表面的複數層，複數層包括緻密的穩定氧化皮(oxide scale)，且超合金保護在高達約1900 ºC的高溫是穩定的。各種阻障塗佈(包括熱阻障塗佈(TBC))可用於抑制航太部件的氧化與腐蝕。各種材料被用於形成此類抵抗腐蝕塗佈，諸如用於熱腐蝕保護的包括Cr2 O3 的原生氧化物及用於抵抗氧化的Al2 O3 。可使用電子束PVD或熱噴塗以沉積TBC及其他阻障塗佈。沉積的TBC包括氧化釔穩定化氧化鋯、釓鋯酸鹽、鉭-釔鋯氧化物、及其他混合的鋯酸鹽、鉿酸鹽、矽酸鹽、及鋁酸鹽化合物。然而，例如鈣-鎂-鋁-矽氧化物系統(CMAS)的環境汙染物會造成TBC的腐蝕。
因此，本領域中存有對於具有增進的抵抗腐蝕 (包括增進的抵抗CMAS腐蝕)的塗佈的需求。
本文論述的是保護超合金結構免於腐蝕的具體例。在一實例中，多層塗佈結構包括形成在超合金結構上的熱阻障塗佈(TBC)層；及經由原子層沉積(ALD)形成在TBC層上的金屬氧化物層。金屬氧化物層包括稀土金屬、鋁、鋯、鉻、或前述物的組合的至少一者。金屬氧化物層可為從1 nm至3微米厚且可具有+/-50%的厚度變動。
在一抑制腐蝕的實例方法中，此方法包括：執行包含溶解或懸浮的金屬之材料的受控釋放進入在引擎操作期間的引擎環境，金屬為鑭系元素、鋁、或鐵的一或多者。複數個夾雜物(foreign matter)存在於以下至少一者中：在氣相中或如氣態膠體(aerosol)之引擎環境、或一或多個引擎表面。此方法進一步包括作為在執行受控釋放期間所釋放之材料接觸複數個夾雜物的反應，複數個夾雜物轉換成包含釋放的材料之固相。
在一實例中，多層塗佈結構包括：由超合金形成的結構，其中由超合金形成的結構藉由包含複數個孔隙的外部表面所界定，其中複數個內部氣體通道形成通過超合金結構以連接至少一些孔隙；及熱阻障塗佈(TBC)層，形成在由超合金形成的結構之外部表面上方。多層塗佈結構進一步包括經由ALD形成在TBC層上且在複數個內部氣體通道之內的金屬氧化物層，並包含稀土金屬、鋁、鋯、鉻、或前述物的組合。
在此論述的系統與方法提供對於鈣-鎂-鋁-矽氧化物系統(CMAS)腐蝕的改善抵抗。CMAS以各種形式存在於包括航太引擎之引擎的自然環境中，包括火山灰、砂顆粒、灰塵、及燃料中。CMAS是高度反應性組成物，其透過腐蝕、化學反應、及滲透而化學地與機械地攻擊表面。在此統稱為「夾雜物(foreign matter)」的CMAS及其他微粒與汙染物也可進入引擎環境。用語「引擎環境」在此可用於指稱引擎在其中操作的空間，包括引擎所在的區域及在此論述的熱空氣及冷空氣路徑中的引擎部件之中與之間的空間。用語「引擎環境」在此可用於指稱引擎在其中操作的空間，包括引擎所在的區域及在此論述的熱空氣及冷空氣路徑中的引擎部件之中與之間的空間。用語「引擎環境」因而在此用於描述一個區域或複數個區域，其不在當塗佈失效時會發生CMAS的引擎部件的表面上。並未或在某些情況中尚未以熔融態或固態沉降在引擎部件上的夾雜物可存在於引擎環境中。CMAS可腐蝕由YSZ、GZO、及其他氧化物製成的引擎塗層與由超合金製成的引擎部件。例如，當引擎操作致使夾雜物將被拉引通過多孔塗層(意於保護下方的引擎部件)朝向引擎部件。當CMAS同時以熔融相或固相沉降在部件上時會發生腐蝕。氣相的CMAS可包括熔融材料或微粒材料。
在一實例中，在此論述的CMAS保護可為施加在原始設備製造商(OEM)處之新鑄造或加工的航太引擎部件上的保護塗層之形式。在另一實例中，CMAS保護可為在整修期間形成及/或修復或取代的保護塗層之形式。在整修期間，航太部件可被組裝或分解，且在某些實例中，在某些或部分的整修處理期間，包括當保護塗層形成時，可操作引擎。當諸如CMAS的夾雜物在引擎環境中及/或在一或多個引擎部件的表面上時，免於CMAS腐蝕的保護可進一步為在引擎操作期間之夾雜物截斷的形式。
在形成保護塗層的實例中，金屬氧化物保護塗層在此可稱為保護塗層且也可在OEM處形成在新製造的部件上及當引擎在使用時之已組裝的引擎部件上，帶有或沒有分解引擎及/或移除先前塗層。在此使用系統與方法，保護引擎部件免於CMAS腐蝕係藉由形成及/或整修保護塗層(「塗佈」)，及/或藉由截斷當以氣態或固態存在於引擎環境中的CMAS汙染物。藉由CMAS截斷、及/或保護性OEM塗層，及藉由修復/再施加保護塗層的整修處理提供改善的腐蝕抵抗。對於CMAS腐蝕的截斷及/或保護維持並改善超合金部件的黏附、安定性、及塗佈結構。
在此的某些實例中，在OEM塗佈或整修期間，使用原子層沉積(ALD)或化學氣相沉積(CVD)製造在此使用的保護塗層。在一實例中，利用ALD使用一或多個在此論述的沉積循環以形成3微米或更小厚度的層狀薄金屬氧化物保護塗層。在某些具體例中，形成金屬氧化物保護塗層係使用一或多種稀土元素，諸如鈰(Ce)、鏑(Dy)、鉺(Er)、銪(Eu)、釓(Gd)、鈥(Ho)、鑭(La)、鎦(Lu)、釹(Nd)、鐠(Pr)、鉕(Pm)、釤(Sm)、鈧(Sc)、鋱(Tb)、銩(Tm)、鐿(Yb)、或釔(Y)。在某些具體例中，使用鋁(Al)、矽(Si)、鉿(Hf)、鋯(Zr)、鉭(Ta)、鐵(Fe)、或鈦(Ti)的一或多者形成金屬氧化物保護塗層。在一實例中，金屬氧化物保護塗層指稱當塗層施加於並未被事先塗佈、組裝、及/或使用在引擎中新製造的部件時的原始設備製造商(OEM)塗層。在其他實例中，金屬氧化物保護塗層是整修塗層，形成在先前塗佈有相同或不同金屬氧化物保護塗層且已使用在組裝引擎中的部件上。在某些實例中，在塗佈部件的使用之後，形成在OEM處的金屬氧化物保護塗層可被移除與取代以維護並延長塗佈部件的操作壽命。在其他實例中，新金屬氧化物保護塗層形成在現存的塗層(例如，在此論述的熱阻障塗佈)上方，而不移除先前的下方塗層。保護塗層可形成在各種層上方，包括氧化物、Gd-鋯酸鹽(Gd2 Zr2 O7 「GZO」)、及經由電子束物理氣相沉積(EB-PVD)沉積的氧化釔穩定化氧化鋯(YSZ)，YSZ可具有柱狀晶粒結構。
在引擎操作期間CMAS被截斷的實例中，當CMAS或其他夾雜材料存在於引擎環境中及/或在經由材料的釋放進入引擎的預定時程上，可發生截斷。在引擎的氣氛(例如，引擎環境)中之CMAS的截斷可防止CMAS降落在引擎部件上。CMAS可以可包含熔融材料或微粒材料的氣相或氣態膠體相存在於引擎環境中。藉由截斷氣相或氣態膠體相中的CMAS，CMAS被防止提供引擎腐蝕，由於其藉由與在操作期間釋放在引擎中的材料的反應而抵銷。在此實例中，諸如前驅物的材料可包括在碳氫化合物燃料，且燃料可被釋放以截斷引擎環境中的CMAS及會以熔融或固態形式在部件上的CMAS。在某些具體例中，前驅物包括一或多種稀土元素，諸如鈰(Ce)、鏑(Dy)、鉺(Er)、銪(Eu)、釓(Gd)、鈥(Ho)、鑭(La)、鎦(Lu)、釹(Nd)、鐠(Pr)、鉕(Pm)、釤(Sm)、鈧(Sc)、鋱(Tb)、銩(Tm)、鐿(Yb)、或釔(Y)。在某些具體例中，前驅物可包括一或多者的鋁(Al)、矽(Si)、鉿(Hf)、鋯(Zr)、鉭(Ta)、鐵(Fe)、或鈦(Ti)，單獨或結合，或與一或多種稀土元件結合。可溶解在溶液中或懸浮為金屬微粒的包括前驅物的碳氫化合物燃料與各種態的CMAS反應以抵銷其腐蝕效果。
圖1A為根據本發明具體例之熱引擎區段部件100A的剖面。圖1B為用於圖1A中部件的實例製造方法100B的方法流程。圖1A與1B在下方一同被論述。圖1A是實例熱引擎區域部件100A的部分圖解剖面。熱引擎區域部件100A以部分視圖顯示，其包括內部通道120，在引擎使用期間冷卻空氣在內部通道120流動。熱引擎區段部件100A藉由外部表面122而進一步界定，其中在引擎使用期間可從1200 ºC至2000 ºC的氣體混合物140在外部表面122流動。在此論述的金屬氧化物保護塗層為共形塗層，其在外表面上方及管道與通道的內部延伸。金屬氧化物保護塗層形成在其上的各種表面在此統稱為「基板」。在此論述的金屬氧化物保護塗層可具有厚度均勻度的變動為+/-50%。在一具體例中，在此論述的基板104為三維熱區段引擎部件100A的一部分。基板104在第一側上以內部腐蝕保護層102所塗佈。儘管在圖1A中繪示為平坦部分，基板104可為具有邊緣、角落、曲線、及轉換面的熱引擎區段部件。基板104可進一步包括通到內部通道(統一表示為內部通道120)的複數個孔隙，與會暴露於CMAS腐蝕的其他特徵。在一具體例中，基板104可進一步具有形成在相對於內部腐蝕保護層102之基板的一側上的接合塗佈層106。接合塗層106可形成為從約10微米至約100微米的厚度並由MCrAlX所製造，其中M是鈷(Co)、鎳(Ni)、或前述物的組合，而X是鉑(Pt)、Y、Hf、Si、Ti、或前述物的組合。在另一具體例中，接合塗層106由鉑和鋁所製造。轉到圖1B的製造方法100B，在操作124藉由ALD或CVD可形成內部腐蝕保護層102。操作124可發生在真空下於約小於900℃，及在某些實例中，小於約500℃，的溫度之ALD或CVD腔室中。在操作126藉由陰極電弧沉積或藉由CVD可形成接合塗佈層106。
進一步在熱引擎區段部件100A中，第一氧化物層108形成在接合塗層106上，及紅外線(IR)反射層 110形成在第一氧化物層108上方。在操作128經由熱氧化或CVD形成從1微米至10微米厚度的第一氧化物層108。IR反射層110可為在操作130藉由電子束或物理氣相沉積(PVD)所形成的陶瓷層。IR反射層110可形成為總厚度從約13微米至約1000微米的一或多個層。在操作132，例如藉由電子束PVD在IR反射層110上方形成損害感測層112。再者，在操作134，藉由電子束PVD在損害感測層112上方形成約5微米與50微米之間厚度的韌性增進層114。損害感測層112可形成為厚度從約1微米至約120微米，且可由釔鋁石榴石(YAG)或氧化釔穩定化氧化鋯所製造。在某些實例中，損害感測層112進一步也可包括諸如銪(Eu)、鋱(Tb)、或鏑(Dy)的一或多種稀土金屬摻雜物的任一者。
在一具體例中，韌性增進層114包括氧化釔穩定化氧化鋯。熱阻障塗佈(TBC)層116在操作136形成在韌性增進層114上方。TBC層116可為多孔層，而包括CMAS的汙染物可被拉引進入TBC層116的孔洞，危及(compromising)包括超合金的一或多個下方層的完整性。TBC層116包括氧化物，諸如釓(Gd)-摻雜鋯酸鹽(GZO)或氧化釔穩定化氧化鋯(YSZ)。在替換具體例中，TBC層116包括鉺-摻雜YSZ、YbGd-YSZ、NdZrO2、Yb4Zr3O12、或含有Ce、Nd、Sm、Dy、Yb、Sc、或Lu的氧化物、或其他氧化物或氧化物的組合。在TBC層116是YSZ的至少一實例中，在操作136藉由電子束 PVD沉積帶有柱狀晶粒結構的TBC層116。TBC層116具有從100微米至2mm的厚度，且在替換具體例中，具有從150微米至500微米的厚度。
在操作138，包括金屬氧化物的保護塗佈層形成在TBC層上方。在操作138形成的保護塗佈層顯示為如圖1A中保護塗佈層118。使用保護塗佈層118以抑制TBC層116上的CMAS腐蝕且保護塗佈層118形成為TBC層116上方的一或多個共形層，並可形成在TBC層116的孔洞中。在一實例中，保護塗佈層118的厚度均勻性可變動至多+/-50%。保護塗佈層118可形成熱引擎區段部件100A的結構的外部表面122且因此接觸熱氣體路徑。在各種具體例中，經由ALD或CVD形成厚度從1nm至3微米的保護塗佈層118。保護塗佈層118包括一或多個金屬氧化物，諸如Al2O3、Cr2O3、ZrO2、La2O3、HfO2、或Gd2O3。在替換具體例中，其他稀土元素或金屬氧化物的組合可被用於形成保護塗佈層118。保護塗佈層118可為共形塗層，其進一步形成在內部通道中與包括內部通道120的表面及在此論述的引擎部件的外部表面。
圖2是根據本發明具體例之在諸如熱區段引擎部件的基板上形成抗腐蝕保護塗層的方法200。在方法200的操作202中，基板經由ALD處理或CVD處理而暴露於複數個前驅物。在操作202的基板在暴露於前驅物之前可加熱至從約900℃至約1300℃的溫度。在替換具體例中，經由化學氣相沉積(CVD)發生操作202。在此 實例中，與ALD操作的逐層沉積相對比，金屬前驅物與氧化劑兩者同時被引導。基板可為在熱區段引擎部件上的塗層，諸如GZO塗層或YSZ塗層。在操作202的為逐層處理之ALD的一實例中，在操作202的第一部分202A期間，金屬-有機前驅物被引導至基板。前驅物包括金屬，其可為稀土金屬、或可包括Al、Si、Hf、Zr、Ta、Ti、或前述物的合金或組合。在操作202的第二部分202B中，其可與第一部分202A同時發生或在從4秒至約60秒的預定延遲之後發生，氧化劑被引導至基板以形成在操作202的從1nm至3微米厚的保護塗層。在使用ALD系統執行操作202的實例中，實行複數個202A-202B的循環以形成在操作204的層。經由泵循環可縮短第一部分202A與第二部分202B之間的時間以降低在處理腔室中的壓力，接著藉由淨化將反應化合物取代為惰性氣體。形成在操作204的保護塗層是共形保護塗層，形成在基板的所有暴露表面上，包括內部通道與表面及外部表面。因此，當複數個循環202A-202B(其可為2個循環至100個循環)完成時，而完成操作204。202A-202B的每一個循環形成在基板上的金屬氧化物保護塗層的單一層，每一個循環沉積每個循環從約0.5Å至約1.2Å到達形成在操作204的小於3微米的總厚度。形成在操作204的保護塗層可包括化學計量化學式，諸如Al2O3、Cr2O3、ZrO2、La2O3、HfO2、或Gd2O3。保護塗層是帶有具有小於+/-25%之變動的平均厚度之共形塗層。在一具體例中，形成在操作204的保護塗層增加1%或小於1%的基板質量(例如，熱區段引擎部件的質量)。
在一實例中，操作202可重覆超過一次以形成塗佈的分離層。在此實例中，藉由複數個202A-202B循環形成包括第一組成和第一厚度的第一層。隨後，藉由第二複數個202A-202B循環形成包括第二組成和第二厚度的第二層。在使用已組裝塗佈的部件期間，或在組裝之前隨後的退火操作期間，源自使用的熱致使第一層與第二層的移位以在TBC層的頂部上形成塗佈層。此塗佈層可具有漸變組成，取決於組成與第一層和第二層的相對厚度。當使用超過一層用以塗佈時，形成在操作204的層之總厚度為至多3微米。
在一具體例中，金屬前驅物可包括稀土金屬、鋁、鋯、鉻、鐵、或前述物的組合。金屬氧化物保護塗層也與CMAS反應以降低及/或防止CMAS滲透進入熱阻障塗層，提供CMAS抗性予會具有對於CMAS較低抗性的基板(例如，下方TBC塗層)。在操作204形成的保護塗層被形成為在基板上方(包括在此論述的通道與管部內部)的共形塗層。保護塗層的厚度可變動+/-50%，且可形成在多孔TBC塗層的某些或所有的孔洞中，其進一步改善引擎部件的腐蝕抗性。在操作206，在與基板相關的部件(例如，當基板是來自引擎的葉片時)之使用之後，可移除形成在操作204的保護塗層。在操作208可分解引擎與可從部件移除保護塗層。保護塗層可隨後再形成在操作202-204。在另一實例中，操作206是可選的，而引擎部件可被使用、分解、及在操作202-204被再塗佈，而沒有在操作206之保護塗層的移除。
在一具體例中，在操作202的基板是使用在引擎的熱區段中的新部件，諸如葉片或翼，其在方法200之前從未為組裝的引擎或其他裝置的部分。在替換具體例中，在操作202的基板為經由方法200而被事先塗佈的熱引擎區域部件。在此實例中，方法200，在操作208，在操作202之暴露於前驅物之前，可進一步包括在操作202之暴露於前驅物之前分解一或多個熱引擎區段部件。在操作208的分解之後，其可包括複數個操作與裝備，熱引擎區段部件(例如，基板)可經歷在操作202-204的金屬氧化物保護塗層形成。在某些實例中，分解的部件可具有在操作202-204之保護塗層形成之前在操作206移除的塗層。執行在操作206的移除可使用例如氟及/或氯離子以選擇性蝕刻先前施加的塗層，而不損害下方TBC層或保護超合金的其他層。亦即，取決於具體例，在整修期間之保護塗佈層的形成之前，先前形成的金屬氧化物保護塗層可被或可不被完全地或部分地移除。
圖3是在引擎在操作時塗佈複數個熱區段引擎部件的系統300的示意繪圖。系統300顯示實例引擎302及氣體注射系統304。氣體注射系統304流體地耦接至引擎302，且包括閥門與包括噴頭與其他氣體注射器(未在此示出)的氣體分配系統以分配儲存在容器306中的前驅物。容器306可為安瓿或能夠儲存形成圖1中保護塗佈層118的金屬前驅物的其他存儲容器。氣體注射系統304耦接至控制器312並可耦接至電源314。在一具體例中，時鐘318可耦接至氣體注射系統304並可設置以在預定間隔寄送訊號至控制器312以執行指令而從容器306釋放前驅物。在替換具體例中，從耦接至引擎302的一或多個感測器310接收至控制器312的訊號。這些感測器310可包括紅外線感測器、粒徑感測器、雷射光散射設備、質譜儀、內視鏡設備、或感測器與相關設備的組合。控制器312進一步設置以調整在容器306釋放前驅物的壓力及氣體注射系統304的溫度。在一實例中，藉由氣體注射系統304的溫度修改來自容器306的前驅物溫度。氣體注射系統304可耦接至流體導管(未示出)，使得前驅物與複數個燃料一同供給進入引擎。在另一實例中，容器306具有分離的控制器316，以調節前驅物的溫度及/或壓力。在一實例中，氣體注射系統304可具有主動溫度控制以維持氣體線路溫度高於金屬氧化物的凝結溫度但低於分解溫度。氣體線路溫度是當氣體從容器306流動至氣體注射系統304或從氣體注射系統304流動至引擎302的氣體溫度。在下方於圖4中論述系統300的操作。
圖4是在引擎的使用期間原位整修複數個引擎部件的方法400之流程圖。當在商業用途(例如在飛行中)中或當在維護及/或品質控制操作期間的使用中，在此論述關於修復與整修的引擎使用可被塗佈。因此，引擎操作於被通常使用在的飛行器外部或引擎操作於在維護測試且不在飛行器飛行中的期間，並在此使用期間被塗佈。在一實例中，在圖2的方法200中操作204之後開始方法400，使得複數個引擎部件被塗佈具有小於3微米厚度的金屬氧化物保護塗層。在其他實例中，方法400可執行在先前並未被在此論述的金屬氧化物保護塗層所塗佈的引擎部件上。在方法400的操作402，包括複數個經塗佈引擎部件的引擎操作於商業或測試環境中。進一步在操作402，耦接於氣體注射系統(類似於圖3中氣體注射系統304)的時鐘或耦接至引擎的至少一感測器判定已超過預定的閾值。感測器310可包括紅外線感測器、粒徑感測器、雷射光散射設備、質譜儀、內視鏡設備、或感測器與相關設備的組合。在某些實例中，感測器310可設置以判定保護塗層的厚度是低於關於材料性質的預定閾值。因此，預定閾值可包括一或多種材料性質，諸如光折射或粒徑，或時間週期。在一具體例中，當到達預定閾值或超過預定閾值時(取決於此具體例)，一或多個感測器310設置以傳遞訊號至諸如來自圖3的控制器312的控制器。
在操作404，在操作402判定至少一預定閾值已經被超過且相應地接收訊號之後，控制器致使金屬前驅物將從耦接至氣體注射系統的氣體存儲容器被釋放進入引擎。氣體注射系統可類似於圖3中氣體注射系統304，且耦接至引擎，例如耦接至燃料線路，使得在注射期間前驅物與燃料混合。在操作404之前驅物釋放的期間可藉由在操作402接放到的訊號類型而判定。氣體存儲容器可類似於圖3中容器306。在操作406，作為在操作404之多個成分釋放的反應，金屬氧化物保護塗層形成在引擎的暴露表面上。保護塗層形成為在引擎部件的外部表面與引擎部件的內部管道與通道兩者上的共形塗層。保護塗層可進一步形成在多孔塗層(諸如在此論述的TBC層)的內部孔洞中並覆蓋在基板上。金屬氧化物保護塗層可形成高達一微米厚度並形成在引擎部件的內部通道與外部表面上。方法400中保護塗層的此原位修復節省修復成本與時間，因為其不涉及引擎的分解與再組裝及移除現存的保護塗層。在一具體例中，在操作408，可儲存關於感測器偵測與相關訊號的效能資料與修復資料及關於前驅物釋放的類型與期間的資訊。儲存的資料可在週期基礎上分析，以動態地更新並儲存在此論述的預定閾值。
在一實例中，在操作404，基於來自已經超過預定時間週期的時鐘(諸如圖3中時鐘318)的訊號，釋放前驅物以回應操作402的判定。此預定時間週期可包括引擎操作的持續期間、自從金屬氧化物保護塗層形成以來的時間、或其他時間週期或關於引擎製造與使用的時間週期之組合。
圖5是保護引擎部件免於CMAS腐蝕的方法500。相較於圖4所顯示及上方論述的方法400，方法500可截斷引擎部件上熔融或固體形式的CMAS，且也可截斷引擎環境中氣態或氣態膠體形式的CMAS。在方法500中，在操作502，引擎操作於飛行期間或其他使用期間，諸如在品質控制或維護操作期間。引擎的至少某些部件由鎳超合金所形成並且在其上方具有一或多個塗層，其可包括在此論述的保護塗層，如OEM或整修塗層。在替換具體例中，某些或所有的引擎部件不包括保護塗層。
在操作504，在引擎的操作期間，從諸如燃料槽的隔室或設置以儲存包含含金屬材料之材料的其他隔室釋放材料進入引擎。含金屬材料(在此稱為前驅物)包括一或多個稀土金屬且可進一步包括鑭系元素、鋁、鋯、鉻、鐵、釓、或前述物的組合之一或多者。在一具體例中，在操作504的材料釋放可包括材料的受控釋放。材料的受控釋放可包括在操作504的材料釋放，使用預定流率持續預定期間週期，取決於複數個因素，包括引擎尺寸、類型、製造、型號、或在此論述之在操作508接收的一或多個訊號。在一實例中，在操作504之前驅物的釋放可回應在此論述的預定排程。藉由在操作508從諸如時鐘或其他計時裝置的感測器接收的訊號，前驅物的釋放可因此在操作504被觸發。在一具體例中，相較於預定排程時間，當時鐘的時間關聯於一或更多次的引擎的操作天或持續期間，訊號在操作508於預定排程上傳遞。
在另一實例中，在操作504之材料釋放發生以回應在引擎操作期間回應夾雜物偵測的在操作508接收的訊號。在此實例中，在操作508接收的訊號可指示諸如CMAS或其他損害微粒物質的夾雜物以在預定閾值外的一濃度或持續一時間週期而存在於引擎中。含金屬材料可完全地或部分地溶解在諸如燃料的溶劑中，例如適用於使用在渦輪引擎的碳氫化合物燃料。溶液中含金屬材料的濃度可從約0.1%至約25%質量濃度。在其他實例中，含金屬材料可存在為懸浮物的部分，且可存在濃度為從約0.1%至約5%質量濃度。在操作504的釋放可發生持續預定時間週期及/或直到已經釋放預定容積的材料。在一實例中，預定時間週期可基於引擎操作的週期，使得操作504發生持續X%的引擎操作時間，或在操作的預定週期之後。可根據在此論述的一或多個基於時間的材料釋放觸發而設定上述的時鐘感測器。
在操作506，在引擎中CMAS和在操作504釋放的材料之間的反應將CMAS(其為可包括熔融材料或微粒材料的氣態或氣態膠體相)轉化成包括含金屬材料的固體相。在操作504的反應位移(提升)CMAS的共晶點，使得其具有高到足以承受高達2000 ºC的引擎操作溫度之熔點。形成在操作506的CMAS的固體相不被拉引進引擎部件的多孔表面，並含有含金屬材料。在引擎部件上的CMAS的腐蝕效果因而被減緩。
在各種具體例中，感測器可包括(除了或取代上述的時鐘)紅外線感測器、粒徑偵測器、或前述物的組合。在此實例中，回應在操作504的材料釋放，在操作510，於引擎的操作期間，引擎環境中的CMAS或其他夾雜物與前驅物反應。在操作510的反應固化在引擎部件的熔融相表面中的CMAS及/或在操作510與固體相的CMAS反應。在某些實例中，由於與此材料反應之CMAS的固化可被稱為形成在操作510的保護塗層，藉由固化熔融CMAS或藉由與固體相CMAS反應以抵銷腐蝕效果。保護塗層可形成從1 nm至3微米厚。
透過在引擎環境中或引擎部件上CMAS的截斷，或藉由形成與整修金屬氧化物塗層，或前述的組合，可因而發生在此論述的CMAS腐蝕抑制。在此論述的保護金屬氧化物塗層提供富含金屬界面(諸如與CMAS反應的Gd或La系塗層)以降低或停止CMAS滲透至包括TBC層的多層。金屬氧化物塗層進一步提供CMAS抗性予低抗性材料，諸如YSZ，因而提升其功效。在一實例中，含Gd前驅物由氣態/液體金屬有機前驅物沉積在GZO或YSZ之已加熱基板上，帶有同時地暴露於氧化劑或在暴露於處理腔室中的Gd前驅物之後的有限時間間隔處暴露於氧化劑。已加熱基板可在OEM處或可為事先地已塗佈組裝或分解部件。在原位沉積的實例中，複數個熱區段引擎部件被塗佈(或再塗佈)帶有在引擎的金屬氧化物保護塗層。引擎可為在飛行期間使用或在品質控制或維護操作期間使用。此原位修復創造商業價值保護塗層修復方法，降低成本與停機時間，同時改善引擎效能。
儘管已在此顯示並敘述併入本發明教示的各種具體例，本領域的熟習技藝者可輕易地構想到許多仍併入這些教示的其他變化具體例。
100A‧‧‧熱引擎區域部件 100B‧‧‧製造方法 102‧‧‧內部腐蝕保護層 104‧‧‧基板 106‧‧‧接合塗層 108‧‧‧第一氧化物層 110‧‧‧IR層 112‧‧‧損害感測層 114‧‧‧韌性增進層 116‧‧‧TBC層 118‧‧‧保護塗佈層 120‧‧‧內部通道 122‧‧‧外部表面 124、126、128、130、132、134、136、138‧‧‧操作 140‧‧‧氣體混合物 200‧‧‧方法 202A‧‧‧第一部分 202B‧‧‧第二部分 202、204、206、208‧‧‧操作 300‧‧‧系統 302‧‧‧引擎 304‧‧‧氣體注射系統 306‧‧‧容器 310‧‧‧感測器 312‧‧‧控制器 314‧‧‧電源 316‧‧‧控制器 318‧‧‧時鐘 400‧‧‧方法 402、404、406、408‧‧‧操作 500‧‧‧方法 502、504、506、508、510‧‧‧操作
為了可詳細地理解本發明的上述特徵，可藉由參照具體例，某些具體例繪示在隨附圖式中，而獲得簡短總結於上之本發明更明確的說明。然而將注意到隨附圖式僅繪示示例具體例，且因而不被認為限制本發明的範疇，且本發明可容許其他等效的實施例。
圖1A為根據本發明具體例之熱引擎區段部件的剖面。
圖1B為根據本發明具體例之用於圖1A中的部件之實例製造方法的方法流程圖。
圖2為根據本發明具體例之在基板上形成抗腐蝕保護塗佈的方法。
圖3為根據本發明具體例之當引擎在操作時，塗佈複數個熱區段引擎部件或其他部件的系統之示意繪圖。
圖4為根據本發明具體例之在基板上的抗腐蝕保護塗佈之原位形成的方法。
圖5為根據本發明具體例之保護引擎部件免於CMAS腐蝕的方法。
為了易於理解，儘可能已使用相同的元件符號指示圖式中共通的相同元件。料想一具體例的元件與特徵可有利地併入其他具體例中而不需進一步闡明。
國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無
國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記) 無
100A‧‧‧熱引擎區域部件
102‧‧‧內部腐蝕保護層
104‧‧‧基板
106‧‧‧接合塗層
108‧‧‧第一氧化物層
110‧‧‧IR層
112‧‧‧損害感測層
114‧‧‧韌性增進層
116‧‧‧TBC層
118‧‧‧保護塗佈層
120‧‧‧內部通道
122‧‧‧外部表面
140‧‧‧氣體混合物

Claims (20)

  1. 一種多層塗佈結構，包含：一熱阻障塗佈(TBC)層，形成在一超合金結構上；以及一金屬氧化物層，經由原子層沉積(ALD)形成在該TBC層上且包含一稀土金屬、鋁、鋯、鉻、或前述物的組合之至少一者，其中該金屬氧化物層為從1nm至小於3微米厚且具有厚度之一變動為+/-50%。
  2. 如請求項1所述之多層塗佈結構，其中該TBC層包含Gd-鋯酸鹽(GZO)或氧化釔穩定化氧化鋯(YSZ)。
  3. 如請求項1所述之多層塗佈結構，其中該TBC層為從100微米至500微米厚。
  4. 如請求項1所述之多層塗佈結構，其中藉由包含複數個孔隙的一外部表面界定該超合金結構，其中複數個內部氣體通道形成通過該超合金結構以連接該複數個孔隙的至少一些孔隙。
  5. 如請求項4所述之多層塗佈結構，其中該TBC層是一多孔層且該金屬氧化物層進一步形成在該TBC層的複數個孔洞之內。
  6. 如請求項5所述之多層塗佈結構，進一步包含： 一韌性增進層，接觸該TBC層且為從約5微米至約50微米厚，該韌性增進層由摻雜的氧化釔穩定化氧化鋯(YSZ)所形成；一損害感測層，形成接觸該韌性增進層，該韌性增進層為從1微米至120微米厚且由摻雜的釔鋁石榴石(YAG)或摻雜的YSZ所形成；以及一紅外線(IR)反射層，形成接觸該損害感測層，其中該IR反射層包含一陶瓷且為從約13微米至約1000微米厚。
  7. 如請求項6所述之多層塗佈結構，進一步包含：一氧化物層，形成接觸該IR反射層且為從約1微米至約10微米厚；以及一接合塗佈層，形成接觸該氧化物層與該超合金結構，該接合塗佈層包含MCrAlX或一Pt-Al合金且為從10微米至100微米厚，其中M是鈷或鎳，而X是鉑、釔、鉿、鈦或矽。
  8. 一種抑制腐蝕的方法，包含以下步驟：執行一材料的一受控釋放進入在引擎操作期間的一引擎環境中，該材料包含一溶解或懸浮的金屬，該金屬為鑭系元素、鋁、或鐵的一或多者，其中複數個夾雜物(foreign matter)存在於以下至少一者中： 在一氣相中或如一氣態膠體(aerosol)之該引擎環境、或一或多個引擎表面；及作為在執行該受控釋放期間所釋放之該材料接觸該複數個夾雜物的反應，該複數個夾雜物轉換成包含該釋放的材料之一固相。
  9. 如請求項8所述之方法，其中該材料進一步包含一碳氫化合物燃料。
  10. 如請求項9所述之方法，其中該碳氫化合物燃料在一預定的引擎操作期間持續地被釋放，並塗佈在該一或多個引擎表面上的一多孔塗層之複數個孔洞。
  11. 如請求項8所述之方法，進一步包含以下步驟：在該引擎操作期間，藉由耦接至該引擎的一感測器接收指示存在著該複數個夾雜物之一訊號，其中作為接收該訊號的反應，執行該材料的受控釋放，該材料進入該引擎；及在該引擎操作期間，作為轉換該複數個夾雜物的反應，在該引擎的複數個表面上形成從1nm至小於3微米厚的一金屬氧化物塗層。
  12. 如請求項11所述之方法，其中該感測器包 含一時鐘、一紅外線感測器、一粒徑偵測器、或前述物的組合。
  13. 如請求項12所述之方法，其中當該時鐘關於一或更多次的該引擎的操作天或期間，該訊號以預定的時程傳遞。
  14. 如請求項11所述之方法，其中該材料進一步包含鋯、鉻、釓、或前述物的組合。
  15. 如請求項11所述之方法，其中該金屬氧化物塗層形成在包含一氧化物的一熱阻障塗佈(TBC)層上方。
  16. 一種多層塗佈結構，包含：一包含一超合金的結構，其中該結構藉由一包含複數個孔隙的外部表面所界定，其中複數個內部氣體通道形成通過由該超合金形成的該結構以連接至少一些該等孔隙；一熱阻障塗佈(TBC)層，形成在由該超合金形成的該結構的一外部表面上方；以及一金屬氧化物層，經由ALD形成在該TBC層上且在該複數個內部氣體通道之內，並包含一稀土金屬、鋁、鋯、鉻、或前述物的組合，其中該金屬氧化物層為從1nm至小於3微米厚。
  17. 如請求項16所述之多層塗佈結構，其中該 TBC層為自100微米至500微米厚且包含Gd-鋯酸鹽(GZO)或氧化釔穩定化氧化鋯(YSZ)。
  18. 如請求項16所述之多層塗佈結構，進一步包含：一韌性增進層，接觸該TBC層，其中該韌性增進層為從約5微米至約50微米厚且由摻雜的氧化釔穩定化氧化鋯(YSZ)所形成；一損害感測層，形成接觸該韌性增進層，其中該損害感測層為從1微米至120微米厚且由摻雜的釔鋁石榴石(YAG)或摻雜的YSZ所形成；以及一紅外線(IR)反射層，形成接觸該損害感測層，其中該IR反射層為從約13微米至約1000微米厚且由一陶瓷所形成。
  19. 如請求項18所述之多層塗佈結構，進一步包含：一氧化物層，形成接觸該IR反射層，該氧化物層為從約1微米至約10微米厚；以及一接合塗佈層，形成接觸該氧化物層與由該超合金形成的該結構，該接合塗佈層由MCrAlX或一Pt-Al合金所形成且為從10微米至100微米厚，其中M是鈷或鎳，而X是鉑、釔、鉿、鈦或矽。
  20. 如請求項16所述之多層塗佈結構，其中該 超合金包含鎳或鈷。
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