Patent Grant
12196093
Articles that are subject to corrosion, such as gas turbine engine components, may include a coating to protect an underlying material from corrosion. Some articles have internal passages which are subject to corrosion and can be protected by such a coating.
Various techniques can be used to deposit a coating, such as “chromizing” or “aluminizing,” which result in, respectively, a chromium-rich or aluminum-rich coating. Chromizing or aluminizing are commonly applied by vapor deposition and diffusion processes.
A gas turbine engine component according to an example of the present disclosure includes a metal substrate and a coating system disposed on the metal substrate. The coating system contains at least one layer of aluminum-chromium oxide.
In a further embodiment of any of the foregoing embodiments, the aluminum-chromium oxide includes Al2O3 and Cr2O3.
In a further embodiment of any of the foregoing embodiments, aluminum-chromium oxide includes αAl2O3 and α-Cr2O3.
In a further embodiment of any of the foregoing embodiments, the aluminum-chromium oxide includes Al(2-x)CrxO3, wherein x is from 0.6 to 1.4.
In a further embodiment of any of the foregoing embodiments, x is from 1.0 to 1.2.
In a further embodiment of any of the foregoing embodiments, the layer of aluminum-chromium oxide has an average grain size of 100 nanometers or less.
In a further embodiment of any of the foregoing embodiments, the layer of aluminum-chromium oxide has a lamellar structure, and the lamellar structure has a thickness of less than 100 nanometers.
In a further embodiment of any of the foregoing embodiments, the layer of aluminum-chromium oxide is homogeneous.
In a further embodiment of any of the foregoing embodiments, the metal substrate has an internal passage and the layer of aluminum-chromium oxide is disposed on the internal passage.
A further embodiment of any of the foregoing embodiments include a bond coat or a diffusion coating disposed between the layer of aluminum-chromium oxide and the substrate.
A further embodiment of any of the foregoing embodiments include a ceramic thermal barrier topcoat disposed on the layer of aluminum-chromium oxide.
In a further embodiment of any of the foregoing embodiments, the one or more layers of aluminum-chromium oxide contain a dopant metal, and the dopant metal is present in an amount, relative to the total weight of all metals in the one or more layers of aluminum-chromium, of 0.1 wt % to 5 wt %.
A method of forming a coating on a gas turbine engine component according to an example of the present disclosure includes applying one or more films of polynuclear aluminum oxide hydroxide and polynuclear chromium hydroxide to a metal substrate, and thermally treating the metal substrate with the one or more films at a temperature of at least 250° C. The thermal treatment reduces the polynuclear aluminum oxide hydroxides and the polynuclear chromium hydroxides to at least one layer of aluminum-chromium oxide.
In a further embodiment of any of the foregoing embodiments, the polynuclear aluminum oxide hydroxide includes [AlO4Al12(OH)24(H2O)12]7+ and the polynuclear chromium hydroxide includes one or more of ([Cr2(OH)2]4+), ([Cr3(OH)4]5+), ([Cr4(OH)6]6+), and polynuclear chromium hydroxide carboxylates.
In a further embodiment of any of the foregoing embodiments, the one or more films contain a dopant metal, and the dopant metal is present in the one or more films in an amount, relative to the total weight of all metals in the one or more films, of 0.1 wt % to 5 wt %.
In a further embodiment of any of the foregoing embodiments, the dopant metal is selected from the group consisting of titanium, zirconium, hafnium, tantalum, manganese, tungsten, iron, copper, nickel, and combinations thereof.
In a further embodiment of any of the foregoing embodiments, the dopant metal is selected from the group consisting of cerium, dysprosium, erbium, gadolinium, lanthanum, lutetium, neodymium, praseodymium, scandium, thulium, ytterbium, yttrium, and combinations thereof.
In a further embodiment of any of the foregoing embodiments, the dopant metal includes a first dopant metal selected from the group consisting of titanium, zirconium, hafnium, tantalum, manganese, tungsten, iron, copper, nickel, and combinations thereof and a second dopant metal selected from the group consisting of cerium, dysprosium, erbium, gadolinium, lanthanum, lutetium, neodymium, praseodymium, scandium, thulium, ytterbium, yttrium, and combinations thereof.
In a further embodiment of any of the foregoing embodiments, the at least one layer of aluminum-chromium oxide includes α-Al2O3 and α-Cr2O3.
In a further embodiment of any of the foregoing embodiments, the at least one layer of aluminum-chromium oxide includes Al(2-x)CrxO3, wherein x is from 0.6 to 1.4.
The various features and advantages of the present disclosure will become apparent to those skilled in the art from the following detailed description. The drawings that accompany the detailed description can be briefly described as follows.
In use the article 10 may be exposed to a range of temperatures and substances from the surrounding environment. The conditions may cause corrosion (chemical attack by substances that deposit on the component, such as molten sulfates that cause hot corrosion at intermediate temperatures) and high temperature oxidation of the metal at elevated temperatures. Both of these phenomena may occur when components are cycled over a wide temperature range during operation. Chromide or aluminide diffusion coatings and overlay bond coats have been used to form oxide scales during thermal cycling to protect against corrosion.
Chromium oxide passivation layers formed from chromide coatings provide good protection against hot corrosion, especially from 600 to 950° C. Chromium oxides do not provide protection against high temperature oxidation, due to the high volatility of chromium, as Cr(VI) species, above 1000° C. Aluminum oxide passivation layers formed from aluminide coatings provide good protection against high temperature oxidation above 1000° C. Since sulfate contaminants are volatilized above 980° C., hot corrosion protection is not a significant issue at higher temperatures, where protection against high temperature oxidation is needed. In this regard, as will be described herein, the component 10 includes a coating system 14 that has one or more layers of aluminum-chromium oxide 16 to facilitate protection against both hot corrosion and high temperature oxidation. Unlike diffusion coatings that rely primarily on diffusion of deposited species into the substrate and chemical interaction of the species with elements of the substrate to form a coating, the one or more layers of aluminum-chromium oxide 16 is a stand-alone coating that does not rely primarily on diffusion and chemical interaction with the substrate for formation. Thus, the application of this aluminum-chromium oxide layer 16 decouples the need to design superalloy or bond coat compositions to balance (or compromise) both surface reaction functionality and mechanical properties. The following examples may refer to the layer of aluminum-chromium oxide 16, although it is to be understood that the examples can alternatively have additional layers of the aluminum-chromium oxide.
In the example of
The layer of aluminum-chromium oxide 16 can be implemented alone or in various configurations with other coating layers to enhance performance of the component 10.
In another example, the aluminum-chromium oxide 116 has a composition of Al(2-x)CrxO3, wherein x is from 0.6 to 1.4. In a further example, x is from 1.0 to 1.2 to provide a more balanced dual benefit of both aluminum oxide and chromium oxide.
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Synthesis of Polynuclear Al13
A solution or dispersion of polynuclear aluminum oxide hydroxide may be synthesized. The solution or dispersion may contain metastable polynuclear Al(III) [Al3+] oxide hydroxide precursors. These polynuclear clusters, also called “Al13 Keggin clusters” or “Al13 clusters,” have the formula [AlO4Al12(OH)24(H2O)12]7+, and are less than 1.5 nanometers in diameter. Synthesized solutions most typically will have concentrations from 0.007 to 0.07 moles [AlO4Al12(OH)24(H2O)12]7+/liter.
The Al13 cluster synthesis starts with an aqueous solution having an Al(III) concentration of about 0.02 to 2.0 moles/liter. The Al(III) solution is prepared by dissolving Al(III) salt precursors, including: Al(NO3)3 (Al nitrate), AlCl3 (Al chloride), Al(CH3CO2)3 (Al triacetate), or Al[OCH(CH3)C2H5]3 (Al tri-sec-butoxide), in water at room temperature.
These Al13 clusters are synthesized via controlled neutralization or hydrolysis of the Al(III) solution, by titrating with a base solution at elevated temperatures (e.g., 70° C.), to achieve a mole ratio (OH−/Al(III)) of 2.1-2.6, preferably in the range of 2.2-2.4, resulting in a pH of 4-7. The base solutions for titration can include: NaOH, KOH, ammonium hydroxide, NaHCO3 (sodium bicarbonate), or Na2CO3 (sodium carbonate).
Alternatively, the Al13 clusters can be synthesized by electrolytic neutralization or electroless reduction of an Al(III) solution.
In another alternative, the Al13 clusters can be prepared by aqueous electrolysis using sacrificial Al anodes in a mildly acidic or neutral solution, following a similar method to Al electro-coagulation technologies employed for water purification.
The as-synthesized Al13 solution contains Al13 clusters that are coordinated to multiple counter-anions originating from the Al salt precursor, in order to form a charge-neutralized “Al13 complex” or “Al13 Keggin complex.” For example, the Al13 Keggin complex formed from neutralization of Al(NO3)3 will have the formula {[AlO4Al12(OH)24(H2O)12]7+*7NO3−}. If other Al salts are used as precursors, the counter-ions in the Al13 Keggin complex will be formed from the salt anions, e.g., {[AlO4Al12(OH)24(H2O)12]7+*7Cl−} will be formed from AlCl3 neutralization, etc.
Synthesis of Polynuclear Cr(III) Clusters
Al13 and Fe13 clusters have similar structures, and such clusters have been shown to be precursors (“pre-polymers”) for forming their respective metal hydroxide and oxide solid-state phases. They can be considered to act as nuclei that are related in structure to intermediate hydroxide and oxide phases. Since Cr, Al, and Fe all form isomorphic, hexagonal sesquioxide phases (those having a M2O3 stoichiometry with M=metal, i.e., Cr2O3 eskolaite, Al2O3 corundum, and Fe2O3 hematite), Cr(III) ions may form a similar precursor clusters.
Cr(III) ions are known to form various polynuclear structures. For example, the hydrolysis of Cr(III) in a slightly acidic aqueous solution results in the formation of monomeric, dimeric ([Cr2(OH)2]4+), trimeric ([Cr3(OH)4]5+), and tetrameric ([Cr4(OH)6]6+) species. These clusters will complex with charge-neutralizing counter-ions, that originate as the anions in the Cr(III) salt that was used to prepare the polynuclear clusters. These species are formed in weak acids (up to pH=4). Condensation (olation or oxolation) reactions can occur between hydroxyl groups at higher pH values, resulting in the formation of Cr polymer chains connected by bridging hydroxyl or oxygen groups. Molecules with functional groups such as carboxylates, like acetates, may act as bridging ligands. In this manner, three-dimensional Cr(III) hydroxide acetate clusters can form, e.g., such as those incorporating 6, 8, and 12 Cr(III) ions. The cluster plus charges depend on the coordination and linkage with negatively-charged bridging ligands. These clusters are complexed with negative counter-ions in order to neutralize the cluster charge. Some examples of Cr clusters include chromium(III) hydroxide carboxylates and cyclic and cubane type hexachromium hydroxide acetates.
Polynuclear clusters containing Al(III) and Cr(III) can be prepared as separate solutions or mixed together, depending on the desired characteristics of the final coating, i.e., the chromia and alumina local degree of mixing (at the atomic, nano, or sub-micron scales) and compositional uniformity or gradation across the coating thickness. For example, the co-hydrolysis of Al(III) and Cr(III) salt precursors will form a mixture of their respective pure polynuclear clusters. A single liquid coating formulation containing both polynuclear clusters of Al(III) and Cr(III) will result in an intimately mixed aluminum-chromium oxide solid solution or nanocrystals, depending on the deposition and heat treatment conditions (e.g., a layer of aluminum-chromium oxide 116). Alternatively, the polynuclear clusters containing Al(III) and Cr(III) may be prepared separately, and mechanically mixed together, where high energy ball-milling may result in their partial transformation and nucleation of solid-state phase structures.
Liquid Coating Formulation
After synthesis, the polynuclear clusters can be collected by concentration (drying), precipitation, or coagulation. They can be purified by filtration, washing, ion exchange, or dialysis. They can be reconstituted or re-suspended in an acidic (pH>4) or basic (pH=8.5-9.5) aqueous solution, a high pH (>9) sol, or an organic or inorganic solvent dispersion. In addition to water, solvents and dispersion media can include methanol, ethanol, isopropanol, butanol, acetic acid, formic acid, dimethylformamide, ethyl acetate, and tetrahydrofuran. The polynuclear clusters are positively charged over a large pH range, where their complex charges may decrease with increasing pH due to hydrolysis reactions.
The polynuclear cluster counter-anions can be exchanged with anionic ligands, such as F− and carboxylate ions, which bind to the outer coordination sphere of the polynuclear complex. The complex outer coordination sphere waters can be also exchanged with alcohols or esters that can associate with the complex.
The polynuclear Al(III) and/or Cr(III) cluster solution or dispersion formulae can include additives such as surfactants or amphiphilic ligands, organic or polymer binders, buffer species, viscosity modifiers, co-coagulants, corrosion-inhibitors, or chelating agents. These additives serve to accelerate deposition and adhesion to the substrate surface layer.
Dopants, such as metals, can be combined with the polynuclear Al(III) or Cr(III) liquid precursor coating formulations, where the dopant concentration may range up to 5 wt % of the total metal content. For instance, the one or more layers of aluminum-chromium oxide contain a dopant metal in an amount, relative to the total weight of all metals in the one or more layers of aluminum-chromium, of 0.1 wt % to 5 wt %.
For example, the dopant metal includes at least one of titanium, zirconium, hafnium, tantalum, manganese, tungsten, iron, copper, nickel, and combinations thereof. In a further example, the dopant metal includes at least one of iron, manganese, copper, and combinations thereof. In one example, the dopant metal is or includes titanium. In an additional example, the dopant metal includes at least one of cerium, dysprosium, erbium, gadolinium, lanthanum, lutetium, neodymium, praseodymium, scandium, thulium, ytterbium, yttrium, and combinations thereof. In one further example, the dopant metal includes a first dopant metal of titanium, zirconium, hafnium, tantalum, manganese, tungsten, iron, copper, nickel, and combinations thereof and a second dopant metal of cerium, dysprosium, erbium, gadolinium, lanthanum, lutetium, neodymium, praseodymium, scandium, thulium, ytterbium, yttrium, and combinations thereof.
The dopants may modify the precipitate crystalline ordering, enhance phase transformation kinetics of the consolidating coating, and/or act as nucleation agents for crystallization. For example, intermediate size dopants, like iron, manganese, or copper may accelerate and reduce the temperature for oxide formation. Other dopants, such as titanium, may function as grain refiners and prevent particle growth. Maintaining a small grain size could be important for maintaining local aluminum-chromium oxide uniformity over large temperature cycles. Additional dopants may be used to improve oxide adherence and integrity of the oxide coating-metal substrate interface.
Coating Application
Degreasing or alkaline cleaning pretreatment of the substrate may be required depending on processing history. Alternatively, native oxides or smut can be removed by initial cathodic treatment in acidic or alkaline aqueous solution.
The polynuclear formulation(s) containing Al(III) and/or Cr(III) can be applied by known solution-based coating methods, including dipping or soaking, painting, spraying, spin-coating, flow-through internal passages and surface, or (pulse) electrophoresis, where the positively-charged polynuclear clusters are deposited on the negatively-charged aluminum alloy substrate (cathode). The addition of a surfactant is another way to promote wetting of the surface layer. An electrical bias may be applied on the component substrates to facilitate infiltration or deposition of the polynuclear clusters using an electrophoretic driving force. This may be used for the uniform coating of non-line-of-sight surfaces and complex geometry surfaces.
The solution(s) may be applied to components in a single layer or in several successive layers, to build up to a targeted coating thickness. If more than one liquid coating feed is used, they can be applied separately by any coating method, one before the other, or jointly, using any combination of application methods.
The oxide phases present in the coating depend on the heat treatment conditions used. Ramp-up over temperatures of about 100 to about 500° C. will cause any remaining water, ligands, and non-metallic counter-ions or additives present in the coating to desorb or to decompose. During drying the polynuclear clusters first condense to form Al(III) or Cr(III) trihydroxide phases. The heat treatments convert the film 60 of amorphous aluminum trihydroxide layers into alumina; progressing to aluminum oxide hydroxide (pseudo-boehmite or boehmite) above 212° F./100° C., transition aluminas above 570° F./300° C. (progressing from γ-Al2O3 to δ-Al2O3 and then to θ-Al2O3 with increasing temperature), and α-alumina (corundum) above 1832° F./1000° C. Heat treatments also facilitate diffusion bonding and adhesion of the aluminum-chromium oxide layer with the substrate.
During thermal treatment, the chromia trihydroxides dehydrate and convert into the hexagonal chromia (eskolaite) at around 600° C. In mixed phases, chromia will form first and act as a template for α-Al2O3 formation as low as 280° C. Depending on the grain size, high temperature heat treatment conditions (above 1000° C.) may be required to fully homogenize the aluminum-chromium oxide solid solution at the atomic level. Thermal treatment in vacuum or noble gas atmospheres may be used to accelerate phase transformations and densification.
Phase transformation for nanocrystalline materials may be likely to occur at lower temperatures, because of the increased contribution of the surface energy component. For example, the phase transformation and melting temperatures of nanocrystalline materials smaller than 50 nanometers in diameter, decrease dramatically with decreasing grain size.
Coating Characteristics
An aluminum-chromium oxide coating provides protection for operation of a metal component in corrosive and oxidative conditions over a wide temperature range. A mixed sesquioxide phase preferred, as it is dense, corrosion-resistant, and refractory. However, a mixture of Cr2O3 with metastable amorphous or transition Al2O3 phases, where partial Cr substitution may occur on the latter, may provide good corrosion-protection, if it is not possible to incorporate the Al into a fully-dense mixed hexagonal phase. This is because the coating thermal treatment conditions may be limited to preserve the substrate alloy temper and thermal history. Laser or cathodic micro-arc treatments may be used to locally consolidate the oxide coating without substantially heating the substrate.
Chromia provides corrosion-resistance to sulfate species and oxidation resistance at intermediate temperatures (˜700-1000° C.). Alumina provides protection against high temperature oxidation above 1000° C., and provides a stable matrix that suppresses chromium diffusivity and volatility. Aluminum-based sesquioxide phases have stability against Al evaporation and sintering.
The total coating thickness may range from 0.005 to 5 microns. The thickness depends on the concentration of polynuclear clusters in the liquid coating formation(s), the coating application method(s), the number of applications, and the post treatment conditions. The upper limit for the coating thickness is that which has been observed to tolerate elastic strain energy due to thermal mismatch, without failing by spalling.
In true bulk solutions, chromia-alumina has a miscibility gap upon cooling that has a critical point at about 30.5 mol % Cr2O3 and 1271° C. The temperature of this gap varies with grain size. Nanoscale grains and dopants can lower the temperature and breadth of this miscibility gap. Dopants may also be used to retard or accelerate phase separation. Below this gap, spinodal decomposition may result in the formation of Al-rich α1 (˜8 mol % Cr2O3) and Cr-rich α2 (˜58 mol % Cr2O3) phases. However, since atomic diffusion is slow, spinoidal decomposition may take weeks and may not be fully substantiated in thermal cycling of the deployed metal component.
Spinoidal decomposition within the miscibility gap is spontaneous and occurs by local segregation in the hexagonal phase (001) direction, resulting in a nanoscale (<10 nm thick) lamellar distribution of Cr-rich and Al-rich phases without a significant change in structure. A laminated phase structure may be good for providing corrosion-protection against sulfate species at lower temperatures, while stabilizing the coating composition. This phase separation results in a volume contraction, which may be beneficial for compensating for the thermal mismatch between the metal alloy substrate with a larger coefficient of thermal expansion and the protective oxide overlayers having much lower coefficients of thermal expansion. This contraction during phase separation upon cooling could constitute a strain energy release mechanism that may prevent coating cracking and spalling. Alternatively, the coating can contain a mixture of alumina and chromia grains that are locally segregated at the atomic or nano-scale, but homogeneous in composition at higher length scales.
Although a combination of features is shown in the illustrated examples, not all of them need to be combined to realize the benefits of various embodiments of this disclosure. In other words, a system designed according to an embodiment of this disclosure will not necessarily include all of the features shown in any one of the Figures or all of the portions schematically shown in the Figures. Moreover, selected features of one example embodiment may be combined with selected features of other example embodiments.
The preceding description is exemplary rather than limiting in nature. Variations and modifications to the disclosed examples may become apparent to those skilled in the art that do not necessarily depart from this disclosure. The scope of legal protection given to this disclosure can only be determined by studying the following claims.
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