# US 9,765,635 B2 · Erosion and corrosion resistant protective coatings for turbomachinery > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,765,635 B2 - Document ID: US9765635B2 - Status: Granted - Kind: B2 - Application number: 15/234,210 - Filed: 2016-08-11 - Published: 2017-02-02 - Granted: 2017-09-19 - Earliest claimed: 2010-05-28 - Assignees: Nano-Product Engineering, LLC - Applicants: Nano-Product Engineering, LLC - Inventors: Vladimir Gorokhovsky - Web page: https://patentgrep.com/patent/US9765635B2 ## CPC - F01D 5/288: {Protective coatings for blades} - C23C 14/028: {Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing} - C23C 14/0688: {Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides} - C23C 14/325: {Electric arc evaporation} - C23C 14/35: by application of a magnetic field, e.g. magnetron sputtering {(C23C14/3457 takes precedence)} - C23C 24/04: Impact or kinetic deposition of particles - C23C 28/321: {with at least one metal alloy layer} - C23C 28/3215: {at least one MCrAlX layer} - C23C 28/322: {only coatings of metal elements only} - C23C 28/34: {including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates} - C23C 28/341: {with at least one carbide layer} - C23C 28/343: {with at least one DLC or an amorphous carbon based layer, the layer being doped or not} - C23C 28/345: {with at least one oxide layer} - C23C 28/3455: {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} - C23C 28/36: {including layers graded in composition or physical properties} - C23C 28/44: {characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness} - F01D 25/007: {Preventing corrosion} - F05D 2230/312: by plasma spraying - F05D 2250/28: patterned - F05D 2300/22: Non-oxide ceramics - F05D 2300/2284: of titanium - Y02T 50/60: Efficient propulsion technologies, e.g. for aircraft - F01D: NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES (machines or engines for liquids F03; non-positive displacement pumps F04D) - 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) - F05D: INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS - Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION ## Abstract An erosion and corrosion resistant protective coating for turbomachinery application includes at least one ceramic or metal-ceramic coating segment deposited on surface of a conductive metal substrate subjected to a pre-deposition treatment by at least blasting to provide the surface with texture. The erosion and corrosion resistant coating has a plurality of dome-like structures with dome width between in range from about 0.01 μm to about 30 μm. The at least one coating segment is formed by condensation of ion bombardment from a metal-gaseous plasma flow, wherein, at least during deposition of first micron of the coating segment, deposition rate of metal ions is at least 3 μm/hr and kinetic energy of deposited metal ions exceeds 5 eV. ## Claims ### Claim 1 An erosion and corrosion resistant protective coating for turbomachinery applications, comprising: at least one coating segment deposited on a surface of a conductive metal substrate subjected to a pre-deposition treatment by at least blasting to provide the surface with texture, each of the at least one coating segment being ceramic or metal-ceramic and having thickness of at least about 5 μm and hardness in range between about 0.3 GPa and about 80 GPa; the erosion and corrosion resistant coating having surface roughness characterized by Ra<1 μm, and a plurality of dome-like structures with dome width between about 0.01 μm and about 30 μm; and the at least one coating segment being formed by condensation of ion bombardment from a metal-gaseous plasma flow, wherein, at least during deposition of the first micron of the at least one coating segment, deposition rate of metal ions is at least 3 μm/hr and kinetic energy of the metal ions exceeds 5 eV upon deposition. ### Claim 2 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, the dome-like structures including domes with dome width less than about 1 μm. ### Claim 3 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, having a top surface furthest from the conductive metal substrate, surface roughness of the top surface being less than surface roughness of the surface of the conductive metal substrate. ### Claim 4 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, having thickness in range from about 5 μm to about 40 μm. ### Claim 5 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, the at least one coating segment comprising a metal-ceramic coating segment having (a) metal content decreasing with distance from the conductive metal substrate and (b) hardness and elastic modulus increasing with distance from the conductive metal substrate. ### Claim 6 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, the at least one coating segment having concentration of non-metallic elements increasing with distance from the conductive metal substrate. ### Claim 7 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, being discontinuous and forming repeated geometrical shapes separated by narrow uncoated ribbons. ### Claim 8 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, having toughness characterized by H/E>0.02. ### Claim 9 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, the at least one coating segment comprising a metal-ceramic coating segment, the metal-ceramic coating segment including metal and ceramic content blended into one another by concurrent condensation of ion bombardment from at least two metal-gaseous filtered cathodic arc plasma beams overlapped by magnetic fields, wherein, at least during deposition of first micron of the metal-ceramic coating segment, deposition rate of metal ions is at least 3 μm/hr and kinetic energy of the metal ions exceeds 5 eV upon deposition. ### Claim 10 (depends on 9) The erosion and corrosion resistant protective coating of claim 9, the at least one coating segment comprising a monolithic metal-ceramic coating segment. ### Claim 11 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, the at least one coating segment comprising at least one multilayer coating segment, each including one or more bilayers each containing a metal layer overlaid by a ceramic layer. ### Claim 12 (depends on 11) The erosion and corrosion resistant protective coating of claim 11, one of the at least one multilayer coating segment having (a) metal content decreasing with distance from the conductive metal substrate and (b) hardness and elastic modulus increasing with distance from the conductive metal substrate. ### Claim 13 (depends on 11) The erosion and corrosion resistant protective coating of claim 11, the at least one multilayer coating segment comprising a bottom multilayer coating segment and a top multilayer coating segment deposited on the bottom multilayer coating segment, the bottom and top multilayer coating segments having combined thickness of at least about 5 μm, with thickness of the majority of the bilayers of the bottom multilayer coating segment being smaller than the thickness of the bilayers of the top multilayer coating segment. ### Claim 14 (depends on 13) The erosion and corrosion resistant protective coating of claim 13, hardness of the bottom multilayer coating segment being in range from about 0.3 GPa to about 25 GPa, and hardness of the top multilayer coating segment being in range from about 25 GPa to about 80 GPa. ### Claim 15 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, the at least one coating segment comprising at least one multilayer coating segment (i) having thickness in range from about 5 μm to about 500 μm, (ii) including a plurality of bilayers each including a metal layer overlaid by a ceramic layer, (iii) having metal content decreasing with distance from the conductive metal substrate, and (iv) having hardness and elastic modulus increasing with distance from the conductive metal substrate. ### Claim 16 (depends on 15) The erosion and corrosion resistant protective coating of claim 15, ratio of thickness of each metal layer to thickness of ceramic layer overlaid thereon decreasing with distance from the conductive metal substrate. ### Claim 17 (depends on 15) The erosion and corrosion resistant protective coating of claim 15, thickness of each metal layer decreasing with distance from the conductive metal substrate. ### Claim 18 (depends on 15) The erosion and corrosion resistant protective coating of claim 15, the at least one multilayer coating segment comprising a bottom multilayer coating segment and a top multilayer coating segment deposited on the bottom multilayer coating segment, at least one of the multilayer coating segments being within the bottom segment and having thickness of each metal layer between about 0.1 μm and about 5 μm and thickness of each ceramic layer between about 0.2 μm and about 10 μm. ### Claim 19 (depends on 15) The erosion and corrosion resistant protective coating of claim 15, further comprising a monolithic ceramic layer overlaying the at least one multilayer coating segment. ### Claim 20 (depends on 15) The erosion and corrosion resistant protective coating of claim 15, each metal layer being substantially composed of a same metal as the metal component of each ceramic layer. ### Claim 21 (depends on 15) The erosion and corrosion resistant protective coating of claim 15, each metal layer being substantially composed of metal selected from the group consisting of titanium, chromium, vanadium, molybdenum, aluminum, hafnium, zirconium, niobium, tungsten, and alloys thereof. ### Claim 22 (depends on 15) The erosion and corrosion resistant protective coating of claim 15, each ceramic layer including one or more ceramic compounds selected from the group consisting of: carbides of X, nitrides of X, borides of X, oxides of X, silicites of X, oxycarbides of X, and oxynitrides of X, wherein X is a metal selected from the group consisting of titanium, chromium, vanadium, molybdenum, aluminum, hafnium, zirconium, niobium, tungsten, and alloys thereof. ### Claim 23 (depends on 15) The erosion and corrosion resistant protective coating of claim 15, each ceramic layer in a region proximate the conductive metal substrate having lesser concentration of non-metallic elements than each ceramic layer in a region further from the conductive metal substrate. ### Claim 24 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, further comprising a carbon diamond-like coating having a hardness from about 30 to about 80 GPa and thickness from about 5 μm to about 150 μm. ### Claim 25 (depends on 24) The erosion and corrosion resistant protective coating of claim 24, the carbon diamond-like coating including metal and being implemented as a top segment of the at least one coating segment deposited. ### Claim 26 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, further comprising a base metal layer applied to the conductive metal substrate by a method selected from the group consisting of cold spray, thermal spray, HVOF, D-gun, and electroplating to be overlaid by the at least one multilayer coating segment. ### Claim 27 (depends on 26) The erosion and corrosion resistant protective coating of claim 26, the base metal layer having a thickness from about 20 μm to about 1 mm. ### Claim 28 (depends on 1) The erosion and corrosion resistant protective coating of claim 1, each of the at least one coating segment being formed by simultaneous condensation of (i) the metal ions from filtered arc source and (ii) metal atoms from sputtering or evaporation source. ### Claim 29 (depends on 28) The erosion and corrosion resistant protective coating of claim 28, deposition onto the conductive metal substrate of the metal atoms spatially overlapping with deposition onto the conductive metal substrate of the metal ions, while ratio of metal ion flux to combined flux of metal ions and metal atoms being greater than 5%. ### Claim 30 (depends on 29) The erosion and corrosion resistant protective coating of claim 29, the ratio of metal ion flux to combined flux of metal ions and metal atoms decreasing from initial stage of deposition to a later stage of deposition. ### Claim 31 An erosion and corrosion resistant protective coating for turbomachinery applications, comprising: at least one ceramic or metal-ceramic coating segment deposited on a surface of a conductive metal substrate subjected to a pre-deposition treatment by at least blasting to provide the surface of the conductive metal substrate with texture, each ceramic or metal-ceramic coating segment being formed by concurrent condensation of ion bombardment from metal-gaseous plasma flow and at least 95% ionized metal atoms, wherein, at least during deposition of the first micron of the at least one ceramic or metal-ceramic coating segment, the deposition rate of metal ions is at least 3 μm/hr while kinetic energy of metal ions is at least 5 eV upon deposition, each coating segment having a thickness of at least about 5 μm; and an array of dome-like surface structures with a dome width of about 0.01 μm to about 30 μm. ### Claim 32 (depends on 31) The erosion and corrosion resistant protective coating of claim 31, wherein the array of dome-like surface structures forms at least part of a surface of the at least one ceramic or metal-ceramic coating segment furthest from the conductive metal substrate. ### Claim 33 (depends on 31) The erosion and corrosion resistant protective coating of claim 31, the array of dome-like surface structures including domes with a dome width less than about 1 μm. ### Claim 34 (depends on 31) The erosion and corrosion resistant protective coating of claim 31, having a thickness in the range of about 5 μm to about 40 μm. ### Claim 35 (depends on 31) The erosion and corrosion resistant protective coating of claim 31, the pre-deposition treatment comprising blasting to provide the surface with a pattern of cold work spots without changing surface roughness. ### Claim 36 (depends on 31) The erosion and corrosion resistant protective coating of claim 31, the pre-deposition treatment comprising powder spray coating. ### Claim 37 An erosion and corrosion resistant protective coating for turbomachinery applications, comprising: at least one coating segment each being ceramic or metal-ceramic and having thickness of at least about 5 μm and hardness in range between about 0.3 GPa and about 80 GPa; the erosion and corrosion resistant coating having roughness characterized by Ra<1 μm, and dome-like structures with dome width between about 0.01 μm and about 30 μm. ### Claim 38 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, the dome-like structures including domes with dome width less than about 1 μm. ### Claim 39 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, having a top surface furthest from a conductive metal substrate on which the erosion and corrosion resistant coating is formed, surface roughness of the top surface being less than surface roughness of the surface of the conductive metal substrate. ### Claim 40 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, the at least one coating segment comprising a monolithic metal-ceramic coating segment. ### Claim 41 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, the at least one coating segment comprising a metal-ceramic coating segment having (a) metal content decreasing with distance from a conductive metal substrate, on which the erosion and corrosion resistant protective coating is formed, and (b) hardness and elastic modulus increasing with distance from the conductive metal substrate. ### Claim 42 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, the at least one coating segment having concentration of non-metallic elements increasing with distance from the conductive metal substrate. ### Claim 43 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, being discontinuous and forming repeated geometrical shapes separated by narrow uncoated ribbons. ### Claim 44 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, having toughness characterized by H/E>0.02. ### Claim 45 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, the at least one coating segment comprising at least one multilayer coating segment, each including one or more bilayers each containing a metal layer overlaid by a ceramic layer. ### Claim 46 (depends on 45) The erosion and corrosion resistant protective coating of claim 45, one of the at least one multilayer coating segment having (a) metal content decreasing with distance from a conductive metal substrate on which the erosion and corrosion resistant protective coating is formed and (b) hardness and elastic modulus increasing with distance from the conductive metal substrate. ### Claim 47 (depends on 45) The erosion and corrosion resistant protective coating of claim 45, the at least one multilayer coating segment comprising a bottom multilayer coating segment and a top multilayer coating segment deposited on the bottom multilayer coating segment, the bottom and top multilayer coating segments having combined thickness of at least about 5 μm, with thickness of the majority of the bilayers of the bottom multilayer coating segment being smaller than the thickness of the bilayers of the top multilayer coating segment. ### Claim 48 (depends on 47) The erosion and corrosion resistant protective coating of claim 47, hardness of the bottom multilayer coating segment being in range from about 0.3 GPa to about 25 GPa, and hardness of the top multilayer coating segment being in range from about 25 GPa to about 80 GPa. ### Claim 49 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, the at least one coating segment comprising at least one multilayer coating segment (i) having thickness in range from about 5 μm to about 500 μm, (ii) including a plurality of bilayers each including a metal layer overlaid by a ceramic layer, (iii) having metal content decreasing with distance from a conductive metal substrate, on which the erosion and corrosion resistant protective coating is formed, and (iv) having hardness and elastic modulus increasing with distance from the conductive metal substrate. ### Claim 50 (depends on 49) The erosion and corrosion resistant protective coating of claim 49, wherein the ratio of thickness of each metal layer to the thickness of the ceramic layer overlaid thereon decreases with distance from the conductive metal substrate. ### Claim 51 (depends on 49) The erosion and corrosion resistant protective coating of claim 49, wherein the thickness of each metal layer decreases with distance from the conductive metal substrate. ### Claim 52 (depends on 49) The erosion and corrosion resistant protective coating of claim 49, the at least one multilayer coating segment comprising a bottom multilayer coating segment and a top multilayer coating segment deposited on the bottom multilayer coating segment, at least one of the multilayer coating segments being within the bottom segment and having thickness of each metal layer between about 0.1 μm and about 5 μm and thickness of each ceramic layer between about 0.2 μm and about 10 μm. ### Claim 53 (depends on 49) The erosion and corrosion resistant protective coating of claim 49, further comprising a monolithic ceramic layer overlaying the at least one multilayer coating segment. ### Claim 54 (depends on 49) The erosion and corrosion resistant protective coating of claim 49, each metal layer being substantially composed of a same metal as the metal component of each ceramic layer. ### Claim 55 (depends on 49) The erosion and corrosion resistant protective coating of claim 49, each ceramic layer in a region proximate the conductive metal substrate having lesser concentration of non-metallic elements than each ceramic layer in a region further from the conductive metal substrate. ### Claim 56 (depends on 37) The erosion and corrosion resistant protective coating of claim 37, further comprising a carbon diamond-like coating having a hardness from about 30 to about 80 GPa and thickness from about 5 μm to about 150 μm. ### Claim 57 (depends on 56) The erosion and corrosion resistant protective coating of claim 56, the carbon diamond-like coating including metal and being implemented as a top segment of the at least one coating segment deposited.