# US 11,028,480 B2 · Methods of protecting metallic components against corrosion using chromium-containing thin films > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,028,480 B2 - Document ID: US11028480B2 - Status: Granted - Kind: B2 - Application number: 16/356,700 - Filed: 2019-03-18 - Published: 2019-09-19 - Granted: 2021-06-08 - Earliest claimed: 2018-03-19 - Applicants: Applied Materials, Inc. - Inventors: Thomas Knisley; Mark Saly; David Alexander Britz; David Thompson - Web page: https://patentgrep.com/patent/US11028480B2 ## CPC - F01D 5/288: {Protective coatings for blades} - F23R 3/002: {Wall structures (F23R3/02 and F23R3/007 take precedence)} - C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates} - C23C 16/30: Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides - C23C 16/34: Nitrides {(C23C16/303 takes precedence)} - C23C 16/40: Oxides - C23C 16/405: {of refractory metals or yttrium} - C23C 16/45529: {specially adapted for making a layer stack of alternating different compositions or gradient compositions} - C23C 16/45553: {characterized by the use of precursors specially adapted for ALD} - C23C 16/45555: {applied in non-semiconductor technology} - C23C 16/56: After-treatment - F01D 5/286: {Particular treatment of blades, e.g. to increase durability or resistance against corrosion or erosion (F01D5/288 takes precedence)} - F01D 9/02: Nozzles; Nozzle boxes; Stator blades; Guide conduits {, e.g. individual nozzles (nozzle boxes F01D9/047)} - F01D 25/007: {Preventing corrosion} - F01D 25/12: Cooling - F01D 25/28: Supporting or mounting arrangements, e.g. for turbine casing - F23R 3/28: characterised by the fuel supply (burners F23D) - C07F 11/005: {compounds without a metal-carbon linkage} - F01D 25/145: {Thermally insulated casings} - F05D 2230/314: by chemical vapour deposition - F05D 2230/90: Coating; Surface treatment - F05D 2300/132: Chromium - F05D 2300/21: Oxide ceramics - F05D 2300/226: Carbides - F05D 2300/228: Nitrides - F23R 2900/00018: Manufacturing combustion chamber liners or subparts - F01D: NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES (machines or engines for liquids F03; non-positive displacement pumps F04D) - F23R: GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS (fluidised bed combustion apparatus specially adapted for operation at superatmospheric pressures F23C10/16) - 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 (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) - F05D: INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS ## Abstract Methods for depositing protective coatings on aerospace components are provided and include sequentially exposing the aerospace component to a chromium precursor and a reactant to form a chromium-containing layer on a surface the aerospace component by an atomic layer deposition process. The chromium-containing layer contains metallic chromium, chromium oxide, chromium nitride, chromium carbide, chromium silicide, or any combination thereof. ## Claims ### Claim 1 A method for depositing a coating on an aerospace component, comprising: sequentially exposing the aerospace component to a chromium precursor and a reactant to form a chromium-containing layer on a surface of the aerospace component by an atomic layer deposition process; and forming a nanolaminate film stack on the surface of the aerospace component, wherein the nanolaminate film stack comprises alternating layers of the chromium-containing layer and a second deposited layer. ### Claim 2 (depends on 1) The method of claim 1, wherein the chromium precursor comprises bis(cyclopentadiene) chromium, bis(pentamethylcyclopentadiene) chromium, bis(isoproplycyclopentadiene) chromium, bis(ethylbenzene) chromium, chromium hexacarbonyl, chromium acetylacetonate, chromium hexafluoroacetylacetonate, a chromium diazadienyl, isomers thereof, complexes thereof, abducts thereof, salts thereof, or any combination thereof. ### Claim 3 (depends on 2) The method of claim 2, wherein the chromium diazadienyl has a chemical formula of: wherein each R and R′ is independently selected from H, C1-C6 alkyl, aryl, acyl, alkylamido, hydrazido, silyl, aldehyde, keto, C2-C4 alkenyl, alkynyl, or substitutes thereof. ### Claim 4 (depends on 1) The method of claim 1, wherein the reactant comprises a reducing agent and the chromium-containing layer comprises metallic chromium. ### Claim 5 (depends on 4) The method of claim 4, wherein the reducing agent comprises hydrogen (H2), ammonia, a hydrazine, an alcohol, a cyclohexadiene, a dihydropyrazine, an aluminum containing compound, abducts thereof, salts thereof, plasma derivatives thereof, or any combination thereof. ### Claim 6 (depends on 1) The method of claim 1, wherein the reactant comprises an oxidizing agent and the chromium-containing layer comprises chromium oxide. ### Claim 7 (depends on 6) The method of claim 6, wherein the oxidizing agent comprises water, oxygen (O2), atomic oxygen, ozone, nitrous oxide, a peroxide, an alcohol, plasmas thereof, or any combination thereof. ### Claim 8 (depends on 1) The method of claim 1, wherein the reactant comprises a nitriding agent and the chromium-containing layer comprises chromium nitride. ### Claim 9 (depends on 8) The method of claim 8, wherein the nitriding agent comprises ammonia, atomic nitrogen, a hydrazine, plasmas thereof, or any combination thereof. ### Claim 10 (depends on 1) The method of claim 1, wherein the reactant comprises a carbon precursor or a silicon precursor and the chromium-containing layer comprises chromium carbide or chromium silicide. ### Claim 11 (depends on 1) The method of claim 1, wherein the second deposited layer comprises aluminum oxide, aluminum nitride, silicon oxide, silicon nitride, silicon carbide, yttrium oxide, yttrium nitride, yttrium silicon nitride, hafnium oxide, hafnium nitride, hafnium silicide, hafnium silicate, titanium oxide, titanium nitride, titanium silicide, titanium silicate, or any combination thereof. ### Claim 12 (depends on 1) The method of claim 1, wherein the chromium-containing layer comprises chromium oxide, chromium nitride, or a combination thereof, and wherein the second deposited layer comprises aluminum oxide, silicon nitride, hafnium oxide, hafnium silicate, or any combination thereof. ### Claim 13 (depends on 1) The method of claim 1, wherein the alternating layers in the nanolaminate film stack comprise from 1 pair to about 50 pairs of the chromium-containing layer and the second deposited layers. ### Claim 14 (depends on 1) The method of claim 1, further comprising annealing the aerospace component and converting the nanolaminate film stack into a coalesced film. ### Claim 15 (depends on 1) The method of claim 1, wherein the aerospace component is a turbine blade, a turbine vane, a support member, a frame, a rib, a fin, a pin fin, a combustor fuel nozzle, a combustor shield, an internal cooling channel, or any combination thereof. ### Claim 16 (depends on 1) The method of claim 1, wherein the surface of the aerospace component is an interior surface of the aerospace component, and wherein the surface of the aerospace component comprises nickel, nickel superalloy, aluminum, chromium, iron, titanium, hafnium, alloys thereof, or any combination thereof. ### Claim 17 A method for depositing a coating on an aerospace component, comprising: forming a nanolaminate film stack on a surface of the aerospace component, wherein the nanolaminate film stack comprises alternating layers of a chromium-containing layer and a second deposited layer; sequentially exposing the aerospace component to a chromium precursor and a first reactant to form the chromium-containing layer on the surface by atomic layer deposition, wherein the chromium-containing layer comprises chromium oxide, chromium nitride, or a combination thereof; and sequentially exposing the aerospace component to a metal or silicon precursor and a second reactant to form the second deposited layer on the surface by atomic layer deposition, wherein the second deposited layer comprises aluminum oxide, aluminum nitride, silicon oxide, silicon nitride, silicon carbide, yttrium oxide, yttrium nitride, yttrium silicon nitride, hafnium oxide, hafnium nitride, hafnium silicide, hafnium silicate, titanium oxide, titanium nitride, titanium silicide, titanium silicate, or any combination thereof. ### Claim 18 A method for depositing a coating on an aerospace component, comprising: sequentially exposing the aerospace component to a chromium precursor and a reactant to form a chromium-containing layer on a surface of the aerospace component by atomic layer deposition, wherein the surface of the aerospace component comprises nickel, nickel superalloy, chromium, iron, titanium, alloys thereof, or any combination thereof; forming a second deposited layer on the chromium-containing layer, wherein the second deposited layer comprises aluminum oxide, aluminum nitride, silicon oxide, silicon nitride, silicon carbide, yttrium oxide, yttrium nitride, yttrium silicon nitride, hafnium oxide, hafnium nitride, hafnium silicide, hafnium silicate, titanium oxide, titanium nitride, titanium silicide, titanium silicate, or any combination thereof; and forming a nanolaminate film stack on the surface of the aerospace component, wherein the nanolaminate film stack comprises alternating layers of the chromium-containing layer and the second deposited layer. ### Claim 19 (depends on 18) The method of claim 18, wherein the surface of the aerospace component is an interior surface of the aerospace component, and wherein the aerospace component is a turbine blade, a turbine vane, a support member, a frame, a rib, a fin, a pin fin, a combustor fuel nozzle, a combustor shield, an internal cooling channel, or any combination thereof. ### Claim 20 (depends on 18) The method of claim 18, wherein the chromium-containing layer comprises metallic chromium, chromium oxide, chromium nitride chromium carbide, or chromium silicide.