CN109982838A - Composition and forming method thereof containing gallium and/or indium - Google Patents

Composition and forming method thereof containing gallium and/or indium Download PDF

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Publication number
CN109982838A
CN109982838A CN201780071063.8A CN201780071063A CN109982838A CN 109982838 A CN109982838 A CN 109982838A CN 201780071063 A CN201780071063 A CN 201780071063A CN 109982838 A CN109982838 A CN 109982838A
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mixture
compound containing
ceramic component
component according
silicon
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CN201780071063.8A
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CN109982838B (en
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G·H·柯比
J·万
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General Electric Co
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General Electric Co
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Priority claimed from US15/267,370 external-priority patent/US9944563B2/en
Priority claimed from US15/267,335 external-priority patent/US10138740B2/en
Priority claimed from US15/267,400 external-priority patent/US10214457B2/en
Application filed by General Electric Co filed Critical General Electric Co
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • 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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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • C04B2235/764—Garnet structure A3B2(CO4)3
    • 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
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/12—Light metals
    • F05D2300/123—Boron
    • 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
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/15—Rare earth metals, i.e. Sc, Y, lanthanides
    • 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
    • F05D2300/60—Properties or characteristics given to material by treatment or manufacturing
    • F05D2300/603—Composites; e.g. fibre-reinforced
    • F05D2300/6033—Ceramic matrix composites [CMC]
    • 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
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  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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  • General Engineering & Computer Science (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

Provide a kind of composition comprising material (for example, silicon metal and/or silicide) and about 0.001% is to about 85% compound containing Ga, compound containing In or their mixture.Silicon base layer can be the adhesive coatings directly in substrate surface.Alternatively, or in addition, silicon base layer can be the outer layer for limiting substrate surface, there is Environmental Barrier Coatings on Si-based Ceramics on the surface of the substrate.Additionally provide coating component and a kind of method of coated ceramic component.Additionally provide the gas-turbine unit including this ceramic component.

Description

Composition and forming method thereof containing gallium and/or indium
Priority information
This application claims the U.S. Patent Application No.s 15/267,335 that September in 2016 is submitted on the 16th；It mentions on September 16th, 2016 The U.S. Patent Application No. 15/267,370 of friendship；And the U.S. Patent Application No. 15/267,400 that September in 2016 is submitted on the 16th Priority.
Technical field
This patent disclosure relates generally to include gallium (Ga) and/or indium in silicon substrate coating (silicone based coating) (In) compound.Particularly, the silicon substrate coating (for example, silicone coupling coating) comprising Ga and/or In is generally provided for making pottery The Environmental Barrier Coatings on Si-based Ceramics of porcelain component.
Background technique
In order to improve the efficiency of gas-turbine unit, constantly seek higher gas-turbine unit operating temperature.So And with the increase of operating temperature, the high temperature durability of engine components is proportionally increased.By forming iron, nickel and cobalt Base superalloy has been realized in the marked improvement of high-temperature behavior.Nevertheless, since many hot gas path components are by superalloy structure At thermal barrier coating (TBC) can be used for that component is made to insulate, and can maintain apparent temperature between carrying alloy and coating surface Difference, therefore limit the heat exposure of structure member.
Although it have been found that superalloy is widely used in the component used in gas-turbine unit entirety, especially exist Component used in high-temperature part, but the lightweight base material of substitution, such as ceramic matrix composite (CMC) material has been proposed Material.CMC and layered ceramic component can coat Environmental Barrier Coatings on Si-based Ceramics (EBC), to protect them from the severe ring in high-temperature engine part The influence in border.EBC can provide the gas-tight seal to resist corrosive gas of densification in hot burning situation.
Silicon carbide and silicon nitride ceramics can aoxidize in dry hot environment.Upper generation is blunt on the surface of the material for this oxidation The silicon oxide skin (oxide scale) of change.In the moist hot environment containing vapor, for example, turbogenerator, due to It forms the silicon oxide skin being passivated and subsequent silica and occurs to aoxidize and be recessed to the conversion of gaseous state silicon hydroxide (recession).Recess in moist hot environment in order to prevent, by Environmental Barrier Coatings on Si-based Ceramics (EBC) be deposited on silicon carbide and On silicon nitride material.
Currently, EBC material is made of rare earth silicate compound.These materials prevent (seal out) vapor, prevent Vapor reaches the silicon oxide skin in silicon carbide or silicon nitride surface, to prevent from being recessed.However, this material cannot anti-block Infiltration, this leads to the oxidation of following substrate.The oxidation of substrate generates the silicon oxide skin of passivation, with oxycarbide or nitrogen oxidation The release of object gas.Oxycarbide (i.e. CO, CO2) or nitrogen oxides (i.e. NO, NO2Deng) gas cannot pass through fine and close EBC ease Out, it therefore blisters.It so far, is the solution of this bubble problem using silicone coupling coating.Silicone coupling coating provides (silicon oxide layer of passivation is formed below EBC) when oxidation and does not discharge the layer of gaseous by-product.
However, the presence of silicone coupling coating limits the upper limit of the operating temperature of EBC, because the fusing point of silicon metal is relatively It is low.In use, the thermal growth oxide of silica is formed on the top surface of the silicon metallic bond coat of multilayer EBC system (TGO) layer.The silicon oxide skin keeps amorphous state at 1200 DEG C of temperature below, sometimes even at 1315 DEG C of temperature below Amorphous state is kept, although the property additionally depends on the time of adhesive coatings exposure at such a temperature.At relatively high temperatures, or when few When measuring Steam soak EBC arrival adhesive coatings, silicon oxide skin crystallization (for example, becoming cristobalite) undergoes phase transformation, along with cold A large amount of volume changes when but.Volume change leads to EBC disbonding.
Therefore, it is intended that improving the property of silicone coupling coating in EBC, to realize the operating temperature limit of higher EBC.
Summary of the invention
Aspects and advantages of the present invention will illustrate partly in the following description, or can from description it is clear that or Person can be grasped by implementing the present invention.
Generally provide a kind of composition comprising material (for example, silicon metal and/or silicide) peace treaty 0.001% to about 85% compound containing Ga, compound containing In or their mixture.Directly exist for example, silicon base layer can be Adhesive coatings on substrate surface.Alternatively, or in addition, silicon base layer can be the outer layer for limiting substrate surface, in substrate surface It is upper that there is Environmental Barrier Coatings on Si-based Ceramics.
The component of coating is also generally provided, in one embodiment, the component includes ceramic component, the pottery Porcelain component includes multiple CMC layer and a restriction one surface and adhesive coatings directly on the surface of ceramic component, The adhesive coatings include such composition.
A kind of method of coated ceramic component is also generally provided.In one embodiment, adhesive coatings are direct On surface coated in ceramic component, the adhesive coatings packet siliceous metal, and compound containing Ga, compound containing In or they At least one of mixture.
Gas-turbine unit including this ceramic component is also generally provided.
With reference to the following description and the appended claims, be better understood with these and other features of the invention, aspect and Advantage.Comprising in the present specification and constitute it is part thereof of accompanying drawing shows embodiment of the present invention, and with specification one It rises for explaining the principle of the present invention.
Detailed description of the invention
In the description in conjunction with attached drawing to those of ordinary skill in the art just present invention including preferred forms Make abundant and enforceable disclosure, in which:
Fig. 1 be include silicon base layer exemplary ceramics component cross-sectional side view；
Fig. 2 is the cross-sectional side view of the exemplary ceramics component on silicon base layer including thermally grown oxide layer of Fig. 1；
Fig. 3 be include silicon base layer another exemplary ceramic component cross-sectional side view；
Fig. 4 is the cross-sectional side view of the exemplary ceramics component on silicon base layer including thermally grown oxide layer of Fig. 3； And
Fig. 5 is the schematic cross sectional views according to the exemplary gas turbogenerator of the various embodiments of this theme.
The reference character reused in the present description and drawings is intended to indicate that same or similar feature of the invention Or element.
Specific embodiment
Now with detailed reference to embodiments of the present invention, wherein one or more embodiments are shown in the accompanying drawings.It provides Each embodiment is rather than to limit the present invention to explain the present invention.In fact, to those skilled in the art show and It is clear to, without departing from the scope or spirit of the invention, can carry out various modifications and change in the present invention. For example, the feature that a part as an embodiment shows or describes can be used together with another embodiment, with Generate another embodiment.Therefore, the present invention is directed to cover this come within the scope of the appended claims and their A little modifications and variations.
As used herein, term " first ", " second " and " third " are used interchangeably with by a component and another group Part distinguishes, and is not intended to the position for indicating various components or importance.
Chemical element is discussed using their general chemical abbreviation in the disclosure, such as usually in the periodic table of elements The chemical abbreviations found.For example, hydrogen is indicated with its common chemical abbreviations H；Helium is indicated with its common chemical abbreviations He；Deng Deng.As used herein, " Ln " refers to the mixture of rare earth element or rare earth element.More specifically, " Ln " refers to rare earth element: scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) or their mixture.
In the disclosure, when one layer of "upper" or " top " for being described as be in another layer or substrate, it should be appreciated that unless there are Phase antirepresentation is specified, these layers can be in direct contact with one another or between layers with another layer or feature.Therefore, these terms Merely depict a layer the relative position of each other, do not necessarily mean that " ... on " because above or below relative position Direction depending on device relative to observer.
The silicon substrate coating comprising compound containing Ga, compound containing In or their mixture is generally provided, with environment Barrier coating is used for ceramic component and their forming method together.In specific embodiments, it is commonly provided for environment barrier The silicon substrate adhesive coatings of coating (EBC) are for refractory ceramics component and their formation and application method.Particularly, silicon substrate Adhesive coatings include the component containing Ga and/or In, for preventing the thermal growth oxide on the silicon substrate adhesive coatings in EBC (" TGO ") crystallization, this prevents the disbonding as caused by this crystallization of TGO in turn.That is, in silicon substrate adhesive coatings The middle Ga and/or In that is introduced into is maintained at TGO (i.e. SiO) in amorphous phase.It is thus possible to improve silicon substrate adhesive coatings (and therefore TGO and EBC coating) operating temperature.In addition, can inhibit and prevent the crystallization of TGO comprising Ga and/or In, without significantly Accelerate the growth rate of TGO.In addition, compound containing Ga and/or compound containing In or their mixture and silica react And/or the solubility in silica is limited, this will limit the rate of oxide scale growth.
Fig. 1-4 respectively illustrates the ceramic component 100 formed by substrate 102 and silicon base layer 104a (Fig. 1), 104b (Fig. 3) Illustrative embodiments.Each of silicon base layer 104a, 104b include that material and about 0.001% to about 85% contain Ga compound, compound containing In or their mixture, for example, about 1 weight % to about 60 weight % compound containing Ga, contain In Compound or their mixture are (for example, about 1 weight % to about 50 weight %, for example, about 1 weight % are to about 25 weight %).It is logical Often, the composition (for example, silicon metal) of compound containing Ga, compound containing In or their mixture and silicon base layer 104a is not anti- It answers.
In one embodiment, silicon base layer 104a can include in the continuous phase of (intertwined) interlaced with each other Compound containing Ga, compound containing In or their mixture and material (for example, silicon metal, silicide etc.).For example, containing Silicon materials and compound containing Ga, compound containing In or their mixture are staggered continuous phase, are contained by volume about 0.001% to about 85% compound containing Ga, compound containing In or their mixture, for example, by volume about 1% to about 60% (for example, by volume about 40% to about 60% compound containing Ga, compound containing In or their mixture).For example, Silicon base layer 104a may include by volume about 15% to about 85% compound containing Ga, compound containing In or their mixture, Surplus is silicon-containing compound.
In another embodiment, compound containing Ga, compound containing In or their mixture formation are dispersed in siliceous Multiple discrete phases in material (for example, in the continuous phase of material), such as discrete particle phase.In such embodiment party In case, silicon base layer 104a may include by volume about 0.001% to about 40% compound containing Ga, compound containing In or they Mixture, such as by volume about 1% to about 25% (for example, by volume the compound containing Ga of about 1% to about 10%, contain In compound or their mixture).
In a particular implementation, substrate 102 is by CMC material (for example, the non-oxide ceramics matrix based on silicon is multiple Close object) it is formed.As used herein, " CMC " refers to siliceous or oxide-oxide, matrix and reinforcing material.As used herein, " layered ceramic " refers to no fibre-reinforced material (for example, only having host material).Herein, CMC and layered ceramic are referred to as For " ceramics ".
The some examples that can be used for the CMC of this paper include but is not limited to the material with matrix and reinforcing fiber, including non- Silica based materials such as silicon carbide, silicon nitride, silicon oxide carbide, silicon oxynitride and their mixture.Example includes but not It is limited to the CMC with carborundum substrate and silicon carbide fibre；CMC with nitridation silicon matrix and silicon carbide fibre；And have Silicon carbide/silicon nitride substrate mixture and silicon carbide fibre CMC.In addition, CMC can have matrix and be made of oxide ceramics Reinforcing fiber.Specifically, oxide-oxide CMC can the reinforcing fiber by matrix and comprising oxide-based materials form, The oxide-based materials such as aluminium oxide (Al2O3), silica (SiO2), alumino-silicate and their mixture.Silicon Aluminate may include crystalline material, such as mullite (3Al2O3 2SiO2) and glassy alumino-silicate.
In the embodiment of figure 1, substrate 102 defines surface 103, and coating 106 is formed on surface 103.Coating 106 Including silicon base layer 104a and Environmental Barrier Coatings on Si-based Ceramics 108.In a particular implementation, silicon base layer 104a is adhesive coatings, wherein Material be silicon metal, silicide (for example, Rare-earth silicides, molybdenum silicide, silication rhenium or their mixture) or they Mixture.In one embodiment, it usually provides (for example, with above-mentioned relative amount (for example, by volume about 0.01 to about 85%)) the composition of packet siliceous metal and compound containing Ga, compound containing In or their mixture.Implement in a substitution In scheme, usually provide a kind of composition, (for example, with above-mentioned relative amount (for example, by volume about 0.01~about 85%)) comprising silicide (for example, Rare-earth silicides, molybdenum silicide, silication rhenium or their mixture) and compound containing Ga, contain In compound or their mixture.
In use, thermal growth oxide (" TGO ") layer is formed on the surface of adhesive coatings.For example, silicon metal and/ Or silicon oxide layer (sometimes referred to as " silicon oxide skin " or " titanium dioxide siliceous skin ") is formed on the adhesive coatings of silicide.Referring to fig. 2, hot Grown oxide layer 105 (for example, silica) can with its during component 100 is exposed to oxygen (for example, manufacture and/or In use process) it is formed and occurs directly in silicon base layer 104a (for example, containing material (silicon metal and/or silicide) Adhesive coatings) on.It is thermally grown due to there is compound containing Ga, compound containing In or their mixture in silicon base layer 104a Oxide skin(coating) 105 is kept substantially amorphous state under its operating temperature, wherein " operating temperature " refers to thermally grown oxide layer 105 temperature.For example, for silicon metallic bond coat, TGO layer can be at about 1415 DEG C or less (for example, about 1200 DEG C to about 1410 DEG C) operating temperature under keep amorphous state, being slightly below the fusing points of silicon substrate adhesive coatings, (fusing point of Si metal is about 1414 ℃).In another example, for silicide adhesive coatings, TGO layer can about 1485 DEG C or less (for example, about 1200 DEG C extremely About 1415 DEG C) operating temperature under keep amorphous state, be slightly below the maximum operation (service) temperature of CMC.It is not intended to by any specific reason The constraint of opinion, it is believed that, gallium and/or indium in silicon base layer 104a move in thermally grown oxide layer 105 and inhibit hot life The crystallization of long oxide skin(coating) (for example, silica), otherwise thermally grown oxide layer (for example, silica) is at these tem-peratures It will crystallize.It is not intended to be any particular theory, it is now recognized that Ga and/or In inhibits impurity (such as Na and/or K) The crystallization of caused amorphous material.
In embodiment shown in fig 1 and 2, silicon base layer 104a is directly on surface 103, therebetween without any layer. However, in other embodiments, can there is one layer or more between silicon base layer 104a and surface 103.
Fig. 3 shows the another embodiment of ceramic component 100, which has substrate 102, wherein base There is outer layer 104b, the outer layer 104b to limit the surface 103 of substrate 102 at bottom 102.That is, outer layer 104b and substrate 102 It constitutes whole.In this embodiment, outer layer 104b is silicon base layer, and coating 106 is on surface 105.Coating 106 may include Environmental Barrier Coatings on Si-based Ceramics 108 and/or other layers (for example, adhesive coatings etc.).In one embodiment, outer layer 104b can be siliceous Monolithic ceramic layer.For example, outer layer 104b may include silicon carbide.In one embodiment, substrate 102 may include being formed Outer layer 104b (for example, comprising silicon carbide as monolithic ceramic layer) on multiple CMC layers of the remainder of substrate.
Fig. 4 shows the heat directly on silicon base layer 104b (for example, the adhesive coatings for containing material (silicon metal)) Grown oxide layer 105 (for example, silica), (for example, in manufacture and/or validity period during component 100 is exposed to oxygen Between) formed.Due to there is compound containing Ga and/or compound containing In in silicon base layer 104b, thermally grown oxide layer 105 is in heat Amorphous state is kept substantially under the operating temperature of grown oxide layer 105.It is not intended to be any particular theory, according to recognizing For gallium and/or indium in silicon base layer 104b move in thermally grown oxide layer 105 and inhibit thermally grown oxide layer (example Such as, silica) crystallization, otherwise thermally grown oxide layer (for example, silica) will crystallize at these tem-peratures.
As described above, the specific location regardless of silicon base layer 104 in ceramic component 100, compound containing Ga, chemical combination containing In Object or their mixture are included in silicon base layer 104a, 104b.In specific embodiments, compound containing Ga, contain Inization It closes object or their mixture is the form of oxide or nitride.
For example, compound containing Ga can be gallium nitride (GaN), gallium oxide (Ga2O3) or their mixture.Containing Gaization Closing object includes in the embodiment of gallium oxide, and gallium oxide can be entrained in another oxide.For example, compound containing Ga can be with It is doped at most about 10 moles of %Ga2O3Zirconium oxide (ZrO2), hafnium oxide (HfO2) or their combination.
In one embodiment, compound containing Ga can be gallium-metal-oxide.For example, in an embodiment In, compound containing Ga can have the chemical formula of following formula:
Ga2-xMxO3
X is 0 to less than 2 when wherein M is In, when M is Al x be 0 to x when about 1.4, M is B be 0 to x when about 1.4, M is Fe be 0 to About 1.4 or their mixture.In one embodiment, x is greater than 0 to less than 2 when M is In, and x is greater than 0 when M is Al It is greater than 0 to x when about 1.4, M is B to x when about 1.4, M is Fe is greater than 0 to about 1.4 or their mixture, so that gallium-gold There are other at least one metals (In, Al, B and/or Fe) in category-oxide.
In one embodiment, compound containing Ga can be rare earth-gallium-oxide.For example, in an embodiment In, compound containing Ga can have the chemical formula of following formula:
Ln4-xDxGa2-yInyO9
Wherein Ln is La, Ce, Pr, Nd, Pm, Sm or their mixture；D be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or their mixture, D are different from Ln (i.e. D is the element or element combinations different from Ln)；And y is 0 to about 1 (for example, 0≤y≤1, such as 0≤y≤0.5).In a specific embodiment, y be greater than 0 to about 1 (for example, 0 < Y≤1, such as 0 < y≤0.5).If D is La, Ce, Pr, Nd, Pm, Sm or their mixture (that is, the atomic radius with Sm Or it is bigger), then x be 0 to less than 4 (for example, 0 < x < 4, such as 0 < x≤about 2).However, if D be Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or their mixture (that is, having the atomic radius less than Sm), then x is 0 to about 2 (for example, 0 < x < 2, such as 0 < x ≤ about 1).
In another embodiment, compound containing Ga can have the chemical formula of following formula:
Ln3Ga5-xMxO12
Wherein Ln is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or their mixture； And when M is In x be 0 to less than 5 (for example, 0≤x < 5, such as 0 < x≤2.5), when M is Al x be 0 to less than 5 (for example, 0≤x < 5, such as 0 < x≤2.5), x is 0 to less than 5 (for example, 0≤x < 5, such as 0 < x≤2.5) when M is Fe, and x is 0 to about 2.5 (example when M is B Such as, 0≤x≤2.5) or their combination.In a specific embodiment, M B, wherein x is greater than 0 to about 2.5 (examples Such as, 0 < x≤2.5), for example, about 0.1 to about 2 (for example, 0.1≤x≤2).In one embodiment, x be greater than 0 (for example, 0.1 to about 2), so that there is at least one M (for example, In, Al, Fe and/or B) in compound containing Ga.
In another embodiment, compound containing In can be indium nitride (InN), indium oxide (In2O3) or theirs is mixed Close object.In the embodiment that compound containing In includes indium oxide, indium oxide can be entrained in another oxide.For example, Compound containing In can be doped at most about 10 moles of %In2O3Zirconium oxide (ZrO2), hafnium oxide (HfO2) or their group It closes.
In one embodiment, compound containing In can be indium-metal-oxide.For example, in an embodiment In, compound containing In can have the chemical formula of following formula:
In2-xMxO3
X is 0 to less than 2 when wherein M is Ga, when M is Al x be 0 to x when about 1.4, M is B be 0 to x when about 1.4, M is Fe be 0 to About 1.4 or their mixture.In one embodiment, x is greater than 0 to less than 2 when M is Ga, and x is greater than 0 when M is Al It is greater than 0 to x when about 1.4, M is B to x when about 1.4, M is Fe is greater than 0 to about 1.4 or their mixture, so that indium-gold There are other at least one metals (Ga, Al, B and/or Fe) in category-oxide.
In one embodiment, compound containing In can have the chemical formula of following formula:
Ln3In5-xMxO12
Wherein Ln is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or their mixture； And when M is Ga x be 0 to less than 5 (for example, 0≤x < 5, such as 0 < x≤2.5), when M is Al x be 0 to less than 5 (for example, 0≤x < 5, such as 0 < x≤2.5), x is 0 to less than 5 (for example, 0≤x < 5, such as 0 < x≤2.5) when M is Fe, and x is 0 to about 2.5 (example when M is B Such as, 0≤x≤2.5) or their combination.In a specific embodiment, M B, wherein x is greater than 0 to about 2.5 (examples Such as, 0 < x≤2.5), for example, about 0.1 to about 2 (for example, 0.1≤x≤2).In one embodiment, x be greater than 0 (for example, 0.1 to about 2), so that there is at least one M (for example, Ga, Al, Fe and/or B) in compound containing In.
In one embodiment, compound containing Ga, compound containing In or their mixture can have the chemistry of following formula Formula:
Ln2-x-yGaxInySi2O7
Wherein Ln is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or their mixture；x It is 0 to about 1；Y is 0 to about 1；And the summation of x and y is greater than 0 (that is, (x+y) > 0).In one embodiment, x's and y is total With for greater than 0 to about 1 (that is, 0 < (x+y)≤about 1), such as approximately more than 0 to about 0.5 (that is, 0 < (x+y)≤about 0.5).
In one embodiment, compound containing Ga, compound containing In or their mixture can have the chemistry of following formula Formula:
Ln2-x-yGaxInySi2O5
Wherein Ln is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or their mixing Object；X is 0 to about 1；Y is 0 to about 1；And the summation of x and y is greater than 0 (that is, (x+y) > 0).In one embodiment, x and y Summation be greater than 0 to about 1 (that is, 0 < (x+y)≤about 1), such as approximately more than 0 to about 0.5 (that is, 0 < (x+y)≤about 0.5).
The Environmental Barrier Coatings on Si-based Ceramics 108 of Fig. 1-4 may include one formed by the material selected from typical case EBC or TBC layer chemical substance Any combination of layer or multilayer, typical EBC or TBC layer chemical substance include but is not limited to rare earth silicate (monosilicate and two Silicate), mullite, barium strontium aluminosilicate (BSAS), hafnium oxide, zirconium oxide, stable hafnium oxide, stabilizing zirconia, rare earth Hafnates, rare earth zirconate, rare earth gallate etc..
The ceramic component 100 of Fig. 1-4 is be especially suitable for the component that finds in the high temperature environment, such as is present in combustion gas whirlpool Component those of in turbine, such as combustor component, turbo blade (turbine blades), shield, nozzle, heat shield With blade (vanes).Particularly, turbine components can be the portion CMC in the hot gas flow path of combustion gas turbine Part, so that coating forms Environmental Barrier Coatings on Si-based Ceramics on component, to protect in combustion gas turbine when being exposed to hot gas flow path Component.
Fig. 5 is the schematic cross sectional views of gas-turbine unit according to an exemplary embodiment of the present disclosure.More specifically Ground, for the embodiment of Fig. 5, gas-turbine unit is high 10 (a high-bypass of duct turbofan jet engine Turbofan jet engine), hereon referred to as " fanjet 10 ".As shown in figure 5, fanjet 10 limits axial side To A (being parallel to as with reference to the extension of longitudinal centre line 12 provided) and radial direction R.In general, turbofan 10 includes fan section 14 With the core turbogenerator 16 in the downstream that fan section 14 is arranged in.Although being described below with reference to fanjet 10, But the disclosure is suitable for general turbine, including turbojet, turboprop and turbine wheel shaft combustion gas whirlpool Turbine, including industry and gas-turbine unit peculiar to vessel and auxiliary power unit.
Described exemplary core turbogenerator 16 generally includes substantially tubular shape shell 18, limits annular and enters Mouth 20.Shell 18 surrounds compressor section with continuous flow relation, which includes booster or low pressure (LP) compressor 22 and high pressure (HP) compressor 24；Combustion parts 26；Turbine portion, including high pressure (HP) turbine 28 and low pressure (LP) turbine 30； And jet exhaust nozzle segment 32.HP turbine 28 is drivingly connected to HP compressor 24 by high pressure (HP) axis or spool 34.It is low Press (LP) axis or spool 36 that LP turbine 30 is drivingly connected to LP compressor 22.
The embodiment for shown in, fan section 14 include variable pitch fan 38, and the variable pitch fan 38 has There are the multiple fan blade 40 for being connected to disk 42 in a spaced apart manner.As shown, fan blade 40 is generally radially square Extend outwardly to R from disk 42.Each fan blade 40 is operably connected to suitable actuating component by means of fan blade 40 44 and it is rotatable around pitch axis P relative to disk 42, the actuating component 44 is configured to consistently change fan blade 40 jointly Spacing.Fan blade 40, disk 42 and actuating component 44 together can by LP axis 36 on optional power gear box 46 around longitudinal direction Axis 12 rotates.Power gear box 46 includes multiple gears, for the rotation speed of LP axis 36 to be reduced to more effective fan Rotation speed.
Referring still to the illustrative embodiments of Fig. 5, disk 42 is covered by rotatable forward engine room 48, which has Aerodynamic profile is to promote the air-flow by multiple fan blade 40.In addition, exemplary fan part 14 includes annular Blower-casting or outer cabin 50, shell or outer cabin 50 circumferentially about fan 38 and/or core turbogenerator 16 at least A part.It should be understood that cabin 50 can be configured to through multiple circumferentially spaced export orientation blades 52 relative to core Turbogenerator 16 supports.In addition, the downstream part 54 of cabin 50 can extend on the outside of core turbogenerator 16, with Define therebetween bypass gas flow channel 56.
During fanjet 10 is run, the air 58 of certain volume passes through cabin 50 and/or the phase of fan section 14 It closes entrance 60 and enters turbofan 10.When the air 58 of the volume passes through fan blade 40, the first part of air 58 such as arrow 62 It is shown to be guided or be directed in bypass gas flow channel 56, and the second part of air 58 is guided or leads as shown in arrow 64 To into LP compressor 22.Ratio between first part's air 62 and second part air 64 is commonly referred to as bypass ratio (a bypass ratio).Then, the pressure of second part air 64 passes through high pressure (HP) compressor 24 at it and enters combustion parts Increase when 26, second part air 64 mixes combining combustion with fuel in combustion parts 26 to provide burning gases 66.
Burning gases 66 are directed through HP turbine 28, wherein a part of thermal energy from burning gases 66 and/or dynamic It can be extracted by the HP turbine stator vane 68 of order levels (sequential stage), the HP turbine stator vane 68 connects To shell 18 and HP turbine rotor blade 70, the HP turbine rotor blade 70 is connected to HP axis or spool (spool) 34, thus Rotate HP axis or spool 34, to support the operation of HP compressor 24.Burning gases 66 are then directed through LP turbine 30, wherein the second part thermal energy and kinetic energy of burning gases 66 are extracted by the LP turbine stator vane 72 of order levels, it is described LP turbine stator vane 72 is connected to shell 18 and LP turbine rotor blade 74, and the LP turbine rotor blade 74 is connected to LP axis Or spool 36, to make LP axis or spool 36 rotate, to support the operation of LP compressor 22 and/or the rotation of fan 38.
Then, burning gases 66 are directed through the jet exhaust nozzle segment 32 of core turbogenerator 16, to provide Propulsive thrust.Meanwhile in first part's air 62 before the discharge of the fan nozzle discharge portion 76 of turbofan 10, in first part When air 62 is directed through bypass gas flow channel 56, the pressure of first part's air 62 substantially increases, and also provides propulsion Thrust.HP turbine 28, LP turbine 30 and jet exhaust nozzle segment 32 are at least partially defined for guiding burning gases 66 Pass through the hot gas path 78 of core turbogenerator 16.
The method for being used for coated ceramic component is also generally provided.In one embodiment, this method includes that will glue It closes coating to be applied directly on the surface of ceramic component, wherein adhesive coatings include material (for example, silicon metal and/or silicon Compound), and at least one of compound containing Ga, compound containing In or their mixture.
This specification discloses the present invention, including its preferred forms using embodiment, and also aims to and make this field Technical staff can implement the present invention, including manufacture and use device or system, and implement method included in it.This hair Bright is defined by the claims by the range of patent protection, and may include other implementations that those skilled in the art will recognize that Example.If these other embodiments include the structural element being not different with the character express of claim, or comprising with power Equivalent structural element of the character express without essential difference that benefit requires, then these other embodiments are considered as in claim In the range of.

Claims (15)

1. a kind of ceramic component, comprising:
The substrate that surface is defined, wherein the substrate is formed by ceramic matrix composite (CMC) material；With
The silicon base layer of adhesive coatings is directly formed in the substrate surface, wherein the silicon base layer includes material peace treaty 0.001% to about 85% compound containing Ga, compound containing In or their mixture.
2. ceramic component according to claim 1, wherein in compound containing Ga, compound containing In or their mixture At least one reaction or be dissolved in the silicon oxide skin being formed on the adhesive coatings, with inhibit silicon oxide skin formed knot It is brilliant.
3. ceramic component according to claim 1, wherein the material is silicon metal.
4. ceramic component according to claim 3, wherein thermal growth oxide is on the adhesive coatings, also, heat is raw Long oxide skin(coating) keeps amorphous state at about 1415 DEG C of operating temperatures below.
5. ceramic component according to claim 1, wherein the material includes silicide.
6. ceramic component according to claim 5, wherein thermal growth oxide is on the adhesive coatings, also, heat is raw Long oxide skin(coating) keeps amorphous state at about 1485 DEG C of operating temperatures below.
7. ceramic component according to claim 5, wherein the silicide includes molybdenum silicide, silication rhenium or theirs is mixed Close object.
8. ceramic component according to claim 1, wherein the ceramic component further include:
Environmental Barrier Coatings on Si-based Ceramics on the silicon base layer.
9. ceramic component according to claim 1, wherein the compound containing Ga, compound containing In or their mixing At least one of object forms continuous crystal boundary in the material.
10. ceramic component according to claim 1, wherein the compound containing Ga, compound containing In or their mixing At least one of object forms discrete particle phase in the material.
11. ceramic component according to claim 1, wherein the compound containing Ga, compound containing In or their mixing At least one of object is not reacted with the material.
12. ceramic component according to any one of the preceding claims, wherein the silicon base layer includes material peace treaty The compound containing Ga of 0.001% to about 85%.
13. ceramic component according to claim 12, wherein the compound containing Ga is selected from:
GaN；
Ga2O3；
Ga2-xMxO3, wherein when M is In, x is 0 to about 2；When M is Al, x is 0 to about 1.4；When M is B, x is 0 to about 1.4；M is When Fe, x is 0 to about 1.4；Or their mixture；
Doped at most about 10 moles of %Ga2O3ZrO2、HfO2Or their combination；
Ln2-x-yGaxInySi2O7, wherein Ln is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu Or their mixture；X is greater than 0 to about 1；Y is 0 to about 1；
Ln2-x-yGaxInySi2O5, wherein Ln is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu Or their mixture；X is greater than 0 to about 1；Y is 0 to about 1；
Ln4-xDxGa2-yInyO9, wherein Ln is La, Ce, Pr, Nd, Pm, Sm or their mixture；D be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or their mixture, wherein D be different from Ln, if D be La, Ce, Pr, Nd, Pm, Sm or their mixture, then x is 0 to less than 4, if D is Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or theirs is mixed Object is closed, then x is 0 to about 2；And y is 0 to about 1；
Ln3Ga5-xMxO12, wherein Ln be Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or it Mixture；M be In when, 0≤x < 5, M be Al when, 0≤x < 5, M be Fe when, 0≤x < 5, M be B when, 0≤x≤2.5 or it Combination；And
Their mixture.
14. ceramic component described according to claim 1~any one of 11, wherein the silicon base layer include material and The compound containing In of about 0.001% to about 85%.
15. ceramic component according to claim 14, wherein the compound containing In is selected from:
InN；
In2O3；
In2-xMxO3, wherein when M is Ga, x be 0 to about 2, M when being Al, and x is 0 to about 1.4, M when being B, and x is for 0 to about 1.4, M When Fe, x is 0 to about 1.4 or their mixture；
Doped with about 0.1 mole of % to about 10 moles of %In2O3ZrO2、HfO2Or their combination；
Ln2-x-yGaxInySi2O7, wherein Ln is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu Or their mixture；X is 0 to about 1；Y is greater than 0 to about 1；
Ln2-x-yGaxInySi2O5, wherein Ln is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu Or their mixture；X is 0 to about 1；Y is greater than 0 to about 1；
Ln4-xDxIn2-yGayO9, wherein Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd or their mixture；D be Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or their mixture；X is 0 to about 2；Y is 0 to about 1； And
Their mixture.
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