CN104562006B - 以耐腐蚀层保护的元件及制造该元件的方法 - Google Patents

以耐腐蚀层保护的元件及制造该元件的方法 Download PDF

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Publication number
CN104562006B
CN104562006B CN201310513463.3A CN201310513463A CN104562006B CN 104562006 B CN104562006 B CN 104562006B CN 201310513463 A CN201310513463 A CN 201310513463A CN 104562006 B CN104562006 B CN 104562006B
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matrix
corrosion layer
thermal barrier
bonding coat
barrier coating
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CN104562006A (zh
Inventor
王丽敏
钟大龙
周宏�
劳伦斯·B·库尔
张利明
克里斯多夫·E·汤普森
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General Electric Co PLC
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General Electric Co
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Priority to CN201310513463.3A priority Critical patent/CN104562006B/zh
Priority to DE201410115032 priority patent/DE102014115032A1/de
Priority to CH01606/14A priority patent/CH708791B1/de
Priority to JP2014214106A priority patent/JP6635651B2/ja
Priority to US14/521,008 priority patent/US20150118485A1/en
Publication of CN104562006A publication Critical patent/CN104562006A/zh
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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
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288—Protective coatings for blades
    • 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
    • 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
    • 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
    • C23C14/082—Oxides of alkaline earth metals
    • 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
    • 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
    • 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
    • C23C16/40—Oxides
    • 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
    • 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
    • C23C16/40—Oxides
    • C23C16/404—Oxides of alkaline earth metals
    • 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
    • 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
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • 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
    • 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
    • C23C28/04—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 only coatings of inorganic non-metallic material
    • C23C28/042—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 only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • 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
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    • 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
    • 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
    • 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
    • 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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    • C23C28/345—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
    • 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
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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
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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
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    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
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    • 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
    • F05D2300/00—Materials; Properties thereof
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
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Abstract

本发明涉及以耐腐蚀层保护的元件及制造该元件的方法，其中的一种燃气轮机发动机元件，包括用耐高温材料制成的基体和耐腐蚀层。所述耐腐蚀层包含分子式为MxVyOz的难熔金属钒酸盐，其中M选自碱土金属、IV族和V族过渡金属、稀土金属、以及它们的组合，其中z=x+2.5y，z=1.5x+2.5y，z=2x+2.5y或z=2.5x+2.5y。

Description

以耐腐蚀层保护的元件及制造该元件的方法
技术领域
本发明涉及一种以耐腐蚀层保护的发动机元件以及制造该元件的方法。
背景技术
为了提高燃气涡轮发动机的效率，需不断追求更高的操作温度。耐高温的材料被广泛用来制造各行业，包括飞机和发电行业的燃气涡轮发动机的元件。由于操作温度的升高，发动机元件的耐高温性能也应相应增强。基于这个原因，燃气涡轮发动机元部件，如燃烧室、高压涡轮机的叶片上常使用热障涂层（thermal barrier coatings，TBC），以其隔热性能来让发动机元件能耐受更高的操作温度下，从而提高元件的寿命，并提高发动机的可靠性。
燃气涡轮发动机环境内的燃烧室的高温可导致燃料内的熔融杂质不仅会腐蚀这些用对所述熔融杂质敏感的材料，如超合金和硅基非氧化物陶瓷（silicon-based non-oxide ceramics）制成的元件，还会腐蚀和破坏用来保护这些元件的热障涂层。这种现象称为热腐蚀，是一种由于杂质的存在，如在元件或其保护层表面形成熔融盐沉积的Na2SO4,NaVO3 and V2O5等的存在，导致的加速腐蚀。所述热腐蚀可导致元件的结构材料或涂层的性能迅速地发生退化，使得元件在几十到几千小时的时间内发生严重的损坏。
尽管上述问题和不确定性的存在，业界仍希望在燃气涡轮发动机中使用价格更加低廉的低品级燃料，这些低品级燃料中所含的盐杂质密度更高，会加剧热腐蚀的问题。因此，如何减轻发动机元件的热腐蚀的问题变得越来越具有挑战性。
发明内容
本发明的一方面涉及一种发动机元件，其包括用耐高温材料制成的基体和耐腐蚀层。所述耐腐蚀层包含分子式为MxVyOz的难熔金属钒酸盐，其中M选自：碱土金属、IV族和V族过渡金属、稀土金属、以及它们的组合，其中z=x+2.5y，z=1.5x+2.5y，z=2x+2.5y或z=2.5x+2.5y。
在一些实施例中，所述发动机元件进一步包括热障涂层系统，位于所述基体和至少一部分所述耐腐蚀层之间，该至少一部分耐腐蚀层是直接附着在所述热障涂层系统上的。
在一些实施例中，所述热障涂层系统包括厚度在100微米到1150微米之间的氧化钇稳定氧化锆层、以及位于所述氧化钇稳定氧化锆层和所述基体之间的第一黏合层。
在一些实施例中，所述第一黏合层包括分子式为RCrAlE的物质，其中R为铁、钴和/或镍，E为钇、稀土金属和/或其他活性金属。
在一些实施例中，所述热障涂层系统进一步包括位于所述第一黏合层和所述氧化钇稳定氧化锆层之间的热生长氧化物层。
在一些实施例中，所述热生长氧化物层包括Al2O3。
在一些实施例中，所述发动机元件进一步包括第二黏合层，其位于所述基体和至少一部分所述耐腐蚀层之间，该至少一部分耐腐蚀层附着在所述第二黏合层上，所述第二黏合层在所述基体和所述至少一部分耐腐蚀层之间提供粘接力。
在一些实施例中，所述第二黏合层包括铝化物。
在一些实施例中，所述耐腐蚀层至少有一部分是直接附着在所述基体上的。
在一些实施例中，M选自：Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Ca、Mg、Ti、Zr、Hf、Nb、Ta、以及它们的组合。特别地，在一些具体的实施例中，M选自：Ce、La、Y、Gd、以及它们的组合。另外，在一些具体的实施例中，M为镧系金属。
在一些实施例中，所述耐腐蚀层的厚度在50微米到200微米的范围之间。
在一些实施例中，所述基体是用超合金制成的。
本发明的另一方面涉及一种制造发动机元件的方法，在该方法中，用耐高温材料制成基体，在该基体上形成耐腐蚀层。所述耐腐蚀层包含分子式为MxVyOz的难熔金属钒酸盐，其中M选自：碱土金属、IV族和V族过渡金属、稀土金属、以及它们的组合，其中z=x+2.5y，z=1.5x+2.5y，z=2x+2.5y或z=2.5x+2.5y。
在一些实施例中，所述在基体上形成耐腐蚀层的步骤包括：在所述基体的至少一部分上提供热障涂层，以及直接在所述热障涂层上涂覆所述耐腐蚀层的至少一部分。
在一些实施例中，所述在基体的至少一部分上提供热障涂层的步骤包括：在基体的至少一部分上提供第一黏合层，以及在所述第一黏合层上形成一层厚度约在100微米到1150微米之间的氧化钇稳定氧化锆层。
在一些实施例中，所述第一黏合层包括分子式为RCrAlE的物质，其中R为铁、钴和/或镍，E为钇、稀土金属和/或其他活性金属。
在一些实施例中，所述在基体的至少一部分上提供热障涂层的步骤还包括：在所述第一黏合层和氧化钇稳定氧化锆层之间提供热生长氧化物层。
在一些实施例中，所述热生长氧化物层包括Al2O3。
在一些实施例中，所述在基体上形成耐腐蚀层的步骤包括：在所述基体的至少一部分上提供第二黏合层，以及在所述第二黏合层上直接形成至少一部分的所述耐腐蚀层。
在一些实施例中，所述第二黏合层包括铝化物。
在一些实施例中，所述在基体上形成耐腐蚀层的步骤包括：在所述基体的至少一部分直接形成至少一部分的所述耐腐蚀层。
在一些实施例中，M选自：Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Ca、Mg、Ti、Zr、Hf、Nb、Ta、以及它们的组合。特别地，在一些具体的实施例中，M选自：Ce、La、Y、Gd、以及它们的组合。另外，在一些具体的实施例中，M为镧系金属。
在一些实施例中，所述耐腐蚀层可能通过选自以下方法中的一种进行涂覆：热喷涂、冷喷涂、溶胶凝胶、物理气相沉积、化学气相沉积、涂浆法、溅射法、以及它们的组合。
附图说明
通过结合附图对于本发明的实施例进行描述，可以更好地理解本发明，在附图中：
图1为一种发动机元件的示意图，该发动机元件在覆盖其基体的热障涂层上直接涂覆有耐腐蚀层。
图2为一种发动机元件的示意图，该发动机元件的基体上直接涂覆有耐腐蚀层。
图3为一种发动机元件的示意图，该发动机元件的基体上隔着一个黏合层涂覆有耐腐蚀层，该黏合层用来在基体和耐腐蚀层之间提供更好的黏附性。
具体实施方式
除有定义外，本文中所用的技术和科学术语具有与本发明所属领域技术人员普遍理解的相同含义。本文所用的术语“第一”、“第二”等并不表示任何顺序、数量或重要性，而只是用于区别一种元件和另一种元件。并且，“一”或“一个”不表示数量的限定，而是表示存在一个的相关项目。
本文中所使用的近似性的语言可用于定量表述，表明在不改变基本功能的情况下可允许数量有一定的变动。因此，用“大约”、“左右”等语言所修正的数值不限于该准确数值本身。在一些实施例中，“大约”表示允许其修正的数值在正负百分之十（10%）的范围内变化，比如，“大约100”表示的可以是90到110之间的任何数值。此外，在“大约第一数值到第二数值”的表述中，大约同时修正第一和第二数值两个数值。在某些情况下，近似性语言可能与测量仪器的精度有关。
本发明的实施例提供了一种涂覆有耐腐蚀层的发动机元件（尤其是燃气轮机的发动机元件），该耐腐蚀层对于所述发动机元件所处理的燃料中所含的熔融盐杂质是惰性的。所述耐腐蚀层包括分子式为MxVyOz的难熔金属钒酸盐，其中M选自：碱土金属、IV族和V族过渡金属、稀土金属、以及它们的组合，且z=x+2.5y或z=1.5x+2.5y或z=2x+2.5y或z=2.5x+2.5y。所述耐腐蚀层是发动机元件在用于处理含熔融盐杂质的燃料之前涂覆在其上作为保护表面的，其可以保护所述发动机元件、以及发动机元件上的具有对熔融盐杂质引发的热腐蚀敏感的成分的热和/或环境防护涂层体系（thermal and/or environmental barriercoating systems），避免发生热腐蚀。
在一些实施例中，所述包括分子式为MxVyOz的难熔金属钒酸盐的耐腐蚀层也对三氧化硫（SO3）是惰性的，其可以保护所述发动机元件及其热和/或环境防护涂层体系，既可防止熔融盐杂质引发的热腐蚀，也可防止包括SO3等气相腐蚀剂引发的腐蚀。
在一些实施例中，所述分子式为MxVyOz的难熔金属钒酸盐中的M选：自钪（Sc）、钇（Y）、镧（La）、铈（Ce）、镨（Pr）、钕（Nd）、钷（Pm）、钐（Sm）、铕（Eu）、钆（Gd）、铽（Tb）、镝（Dy）、钬（Ho）、铒（Er）、铥（Tm）、镱（Yb）、镥（Lu）、钙（Ca）、镁（Mg）、钛（Ti）、锆（Zr）、铪（Hf）、铌（Nb）、钽（Ta）以及它们的组合。在一些具体的实施例中，M选自：Ce、La、Y、Gd以及它们的组合。
在一些实施例中，所述分子式为MxVyOz的难熔金属钒酸盐选自：CeVO4、LaVO4、YVO4、GdVO4以及它们的组合。
所述发动机元件的基体通常是以耐高温材料，如超合金材料和含硅材料等制成的。超合金材料的例子包括镍基、钴基和铁基合金，含硅材料的例子包括这些在一个金属或非金属基质中具有分散的碳化硅、碳化硅、金属硅化物、和/或硅强化材料的，以及这些具有碳化硅、碳化硅和/或含硅基质的材料，尤其是以碳化硅、碳化硅、金属硅化物（例如，铌硅化合物和钼硅化物）和/或硅为基质和增强体的成分材料（例如，陶瓷基复合材料）。尽管本申请是结合燃气涡轮发动机元件对本发明的优势进行描述的，但本发明的构思和内容普遍适用于基体和/或涂层系统易受熔融盐腐蚀的任何元件。
在一些实施例中，对于用于高温环境，比如高于1000℃的环境中的发动机元件，其基体上通常有热障涂层来增强其耐高温性能，对于这类发动机元件，所述耐腐蚀层可直接涂覆在所述热障涂层上。典型地，所述热障涂层包括隔热材料，其沉积在环境防护黏合层（environmentally-protective bond coating）上形成以一个涂层系统，称为热障涂层系统，其中所述环境防护黏合层是用来在所述隔热材料和发动机元件的基体之间获得更好的黏合效果的。所述耐腐蚀层可直接涂覆于所述热障涂层系统之上，也即，直接涂覆于所述隔热材料层之上。一种广泛使用的隔热材料是氧化钇稳定氧化锆（yttria-stabilizedzirconia，YSZ）。一种广泛使用的黏合层材料包括分子式为RCrAlE的物质，其中R为铁、钴和/或镍，E为钇、稀土金属和/或其他活性金属。
在一个具体的实施例中，如图1所示，一种燃气涡轮发动机元件100包括基体102、热障涂层系统104、以及一种如上所述的包括分子式为MxVyOz的难熔金属钒酸盐的耐腐蚀层106。所述热障涂层系统104包括形成于所述基体102上的黏合层108、在该黏合层108上的热生长氧化物（thermally grown oxide，TGO）层110、以及沉积于所述TGO层110上作为热障涂层的YSZ层112。在一个具体的实施例中，所述热生长氧化物层包括Al2O3。有了所述黏合层108，所述YSZ层112和TGO层110可以牢牢附着于发动机元件的基体102上。所述YSZ层112的厚度可在约100微米到1150微米的范围内。所述耐腐蚀层106是直接涂覆于热障涂层系统104上，即直接涂覆于YSZ层112上的。该耐腐蚀层106可保护其下的热障涂层系统和基体，防止它们被熔融盐杂质热腐蚀。
在一些实施例中，对于用于温度相对较低，如在800℃到1000℃，的环境中时，在发动机元件的基体上可能不需要热防护层系统，因而所述耐腐蚀层可直接涂覆于所述基体上。特别地，在一些实施例中，可在耐腐蚀层和发动机元件的基体之间增加一个黏合层来增加粘接性能，这样，所述耐腐蚀层是隔着所述黏合层涂覆在所述基体上。在一个具体的实施例中，所述耐腐蚀层和所述基体之间的黏合层包括铝化物。
比如，在一个具体的实施例中，如图2所示，一种发动机元件200包括基体202和一种如前所述的耐腐蚀层206，其直接附着于所述基体202上。在另一个具体的实施例中，如图3所示，一种发动机元件300包括基体302和一种如前所述的耐腐蚀层306，其隔着黏合层304附着于所述基体202上，所述黏合层304可增强所述耐腐蚀层306和基体302之间的粘接力。
在一些实施例中，在使用过程中发动机元件的不同部位可能面对不同的处理环境或条件，在这样的情况下，可在发动机元件的不同部位选择覆盖或不覆盖热障涂层系统，这取决于其所面对的环境。在元件的不同部位，耐腐蚀层可分别与热障涂层系统和基体（或其它中间层）接触。比如，在一个具体的实施例中，一种发动机元件包括一个具有第一部分和第二部分的基体，其中第一部分上有热障涂层系统，第二部分上没有热障涂层系统。所述元件的耐腐蚀层的第一部分直接涂覆于所述覆盖在基体第一部分的热障涂层系统上，第二部分隔着黏合层涂覆于基体的第二部分上，其中该黏合层有助于将所述耐腐蚀层更好地附着于所述基体的第二部分。此外，所述耐腐蚀层可进一步包括第三部分，其直接涂覆于元件基体上，而不在该部分和基体之间设置热障涂层系统或其它中间层。
在如前所述的实施例中，所述耐腐蚀层可能通过选自以下方法中的一种进行涂覆：热喷涂、冷喷涂、溶胶凝胶、物理气相沉积、化学气相沉积、涂浆法、溅射法、以及它们的组合。所述耐腐蚀层的厚度可在约1微米到约300微米的范围，或更进一步地，在约50微米到约200微米的范围。
实例
在本实例中，首先，制备用来形成所述耐腐蚀层的涂层材料，然后，将其用于耐腐蚀试验，在该试验中，将所述制备好的材料与不同的盐或如NaVO3、Na2SO4和V2O5等氧化物进行混合来测试其耐腐蚀性能。
合成:
所述涂层材料是将金属氧化物和NH4VO3（或氧化钒）按照所需比例混合后合成的，所述混合后的材料经过研磨后在1000-1300℃的温度下加热约5-24小时，以形成晶体粉末。然后用X射线衍射的方法对所述粉末进行分析，以确定物相。
耐腐蚀测试：
将前述粉末与盐或NaVO3,Na2SO4,V2O5等氧化物按照从6:1到2:1的重量比混合，然后在800-920℃加热约1-3小时。然后将所述粉末用去离子水清洗，再将其干燥，进行X射线衍射检测分析。结果显示，在x射线衍射检测的样品中无新相生成，表明所述粉末是耐混合物中的盐或氧化物的腐蚀的。
虽然结合特定的实施方式对本发明进行了说明，但本领域的技术人员可以理解，对本发明可以作出许多修改和变型。因此，要认识到，权利要求书的意图在于覆盖在本发明真正构思和范围内的所有这些修改和变型。

Claims (9)

1.一种发动机元件，包括：
用耐高温材料制成的基体；以及
包含分子式为MxVyOz的难熔金属钒酸盐的耐腐蚀层，其中M选自：Ti、Hf、Nb、Ta以及它们的组合，其中z＝x+2.5y，z＝1.5x+2.5y，z＝2x+2.5y或z＝2.5x+2.5y。
2.一种如权利要求1所述的发动机元件，其进一步包括热障涂层系统，位于所述基体和至少一部分所述耐腐蚀层之间，该至少一部分耐腐蚀层是直接附着在所述热障涂层系统上的，其中，所述热障涂层系统包括形成于所述基体上的第一黏合层、在该第一黏合层上的热生长氧化物层以及沉积于该热生长氧化物层上的热障涂层。
3.一种如权利要求2所述的发动机元件，其中，所述热障涂层为厚度在100微米到1150微米之间的氧化钇稳定氧化锆层。
4.一种如权利要求1或2所述的发动机元件，其进一步包括第二黏合层，其位于所述基体和至少一部分所述耐腐蚀层之间，该至少一部分耐腐蚀层附着在所述第二黏合层上，所述第二黏合层在所述基体和所述至少一部分耐腐蚀层之间提供粘接力。
5.如权利要求1或2所述的发动机元件，其中，所述耐腐蚀层至少有一部分是直接附着在所述基体上的。
6.一种制造发动机元件的方法，其包括：
用耐高温材料制成一个基体；以及
在该基体上形成耐腐蚀层，该耐腐蚀层包含分子式为MxVyOz的难熔金属钒酸盐，其中M选自：Ti、Zr、Hf、Nb、Ta以及它们的组合，其中z＝x+2.5y，z＝1.5x+2.5y，z＝2x+2.5y或z＝2.5x+2.5y。
7.一种如权利要求6所述的方法，其中，所述在基体上形成耐腐蚀层的步骤包括：
在所述基体的至少一部分上提供热障涂层系统；以及
直接在所述热障涂层系统上涂覆所述耐腐蚀层的至少一部分，
其中，所述提供热障涂层系统的步骤进一步包括：
在所述基体上形成第一黏合层；
在所述第一黏合层上形成热生长氧化物层；以及
在所述热生长氧化物层上沉积热障涂层。
8.一种如权利要求7所述的方法，其中，所述在基体上形成耐腐蚀层的步骤包括：
在所述基体的至少一部分上提供第二黏合层；以及
在所述第二黏合层上直接形成至少一部分的所述耐腐蚀层。
9.一种如权利要求7所述的方法，其中，所述在基体上形成耐腐蚀层的步骤包括：
在所述基体的至少一部分上直接形成至少一部分的所述耐腐蚀层。
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