WO2005112603A2 - Durable thermal barrier coating having low thermal conductivity - Google Patents

Durable thermal barrier coating having low thermal conductivity Download PDF

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Publication number
WO2005112603A2
WO2005112603A2 PCT/US2005/000725 US2005000725W WO2005112603A2 WO 2005112603 A2 WO2005112603 A2 WO 2005112603A2 US 2005000725 W US2005000725 W US 2005000725W WO 2005112603 A2 WO2005112603 A2 WO 2005112603A2
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Prior art keywords
article
ceramic
ceramic coating
metallic
dissolved
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PCT/US2005/000725
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French (fr)
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WO2005112603A3 (en
Inventor
Yourong Liu
Paul Lawton
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Chromalloy Gas Turbine Corporation
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Publication date
Priority claimed from US10/756,209 external-priority patent/US20050153160A1/en
Application filed by Chromalloy Gas Turbine Corporation filed Critical Chromalloy Gas Turbine Corporation
Priority to CN200580002278.1A priority Critical patent/CN101291806B/en
Priority to KR1020067012337A priority patent/KR101166150B1/en
Priority to EP05779119.6A priority patent/EP1729959B1/en
Priority to CA2549091A priority patent/CA2549091C/en
Priority to JP2006549494A priority patent/JP4717013B2/en
Publication of WO2005112603A2 publication Critical patent/WO2005112603A2/en
Publication of WO2005112603A3 publication Critical patent/WO2005112603A3/en

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/284—Selection of ceramic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • 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
    • 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
    • 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
    • F05D2300/20—Oxide or non-oxide ceramics
    • F05D2300/21—Oxide ceramics
    • F05D2300/2118—Zirconium oxides

Definitions

  • the present invention relates generally to the field of thermal barrier coatings that are used in elevated temperature applications such as gas turbine engines.
  • this invention relates to a thermal insulating ceramic coating, which has a low thermal conductivity as well as a long service life, and to the metallic articles such as turbine components, (e.g. blades and vanes) that the coatings are applied to prevent the components from overheating during high temperature operation.
  • thermal barrier coatings having low thermal conductivity to insulate effectively the thermal transfer to the components used in gas turbine engines, as well as providing a coated component having a long service life.
  • Efforts have been made to lower the thermal conductivity of thermal barrier coatings by modifying the chemistry and microstructure of current 7YSZ thermal barrier coating systems as disclosed in EP0816526A2, US Patent 6071628, US Patent 5846605, US Patent 6183884B1, US Patent 5792521, US Patent 5687679, W01/63008 and US Patent 6284323B1.
  • thermal barrier coatings decreased thermal conductivity of thermal barrier coatings to various extents with the minimum reported to be about half the thermal conductivity of typical 7 wt% yttria stabilized zirconia (7YSZ). It is a main object of this invention to decrease thermal conductivity of thermal barrier coatings by providing a new ceramic material with low thermal conductivity. This invention also provides a method of applying such a thermal barrier coating system onto the metallic parts providing increased thermal insulation capability and prolonged durability, as well as increased erosion resistance.
  • Fig. 1 shows the ceramic coating, Nd x Zr 1-x O y with Z dissolved in, which was applied by EBPVD onto a metallic bond coat
  • Fig. 2 shows the ceramic coating, Nd x Zr 1-x O y with Z dissolved in, applied in a layered microstructure.
  • Figures 3(a) and 3(b) shows a protective ceramic top coat on the ceramic coating, Nd x Zr 1-x O y with Z dissolved in.
  • this invention provides a thermal barrier ceramic coating for application to a metallic article, with the ceramic coating having a formula of Nd x Zr 1-x O y with Z dissolved in, where O ⁇ x ⁇ 0.5 and 1.75 ⁇ y ⁇ 2 and Z is an oxide of a metal selected from the group consisting of Y, Mg, Ca, Hf and mixtures thereof.
  • Z is yttria and at least 6 weight percent of yttria is added.
  • This invention provides a thermal barrier ceramic coating having a formula of Nd x Z - x O y with Z dissolved in, where 0 ⁇ x ⁇ 0.5, 1.75 ⁇ y ⁇ 2, and Z is an oxide of a metal selected from the group consisting of Y, Mg, Ca, Hf and mixtures thereof.
  • the ceramic is formed by doping oxides of Nd and the selected metal oxides into a host zirconia ceramic forming a non-pyrochlore crystal structure.
  • a preferred embodiment is where Z is yttria.
  • the Nd x Zr 1-x O y ceramic coating with yttria dissolved in can be prepared by doping 2 to 15 mole % of Nd 2 0 3 , preferably up to 7 moles %.
  • the yttria level generally is from 2 to 14 mole %, preferably at least 6 wt %.
  • hafnium is also added, generally at a level of from about 0.5 to 6 wt %, preferably 1.5 to 4 wt %.
  • the ceramic coating of this invention is applied to a metallic article providing a thermal barrier coating with low thermal conductivity, resistance to erosion and high resistance to cyclic oxidation providing increased durability.
  • the coating contains up to 7 mole % of neodymia, e.g. 2 to 7 mole %.
  • the lower level of neodymia is believed to provide a coating with increased erosion resistance.
  • Higher levels of rare earth oxides provide thermal barrier coatings which spall earlier in cyclic oxidational testing.
  • An example is a coating with 7 mole % of Nd 2 0 3 and 5 mole % Y 2 0 3 (8 wt %).
  • the coating has at least 6 wt % of yttria, preferably 6 to 10 wt %, optimally 6 to 8 wt % dissolved in.
  • the higher level of yttria is believed to provide a further reduction in thermal conductivity due to higher concentration of oxygen vacancies in the matrix lattice structure, which will enhance phonon scattering.
  • a phase transformation from high temperature to ambient temperature was found in the system of Nd-Zr without yttria or with low levels of yttria which could cause premature spallation of the coatings.
  • the addition of at least 6 wt % of yttria avoids the premature spallation caused by phase transformation in the TBC system.
  • Another benefit of doping at least 6 wt % Y 2 0 3 is to increase the toughness of the ceramic coatings material.
  • the tougher ceramic coating containing at least 6 wt % yttria also provides good erosion resistance.
  • the addition of at least 6 wt % yttria to the ceramic coating provides a coating with lower thermal conductivity and greater durability due to its improved phase stability, increased toughness, erosion resistance and resistance to cyclic oxidation.
  • One example is a coating with 10 mole % of Nd 2 0 3 and 6 wt % Y 2 0 3 doped into Zr0 2 .
  • hafnia along with yttria has the further advantage of reducing thermal conductivity and strengthening the ceramic material providing an increased resistance to erosion and thermal shock.
  • An example is the further addition of about 3 wt % of hafnia (Hf0 2 ) to the above example formulations.
  • the ceramic coating of this invention has a low thermal conductivity generally within the range of about 0.78 to 1.02 W/mK from 600°C to 1100°C. This thermal conductivity is around 50% of the measured thermal conductivity of a typical 7YSZ coating (1.65-2.22 W/mK from 600°C to 1100°C).
  • the ceramic coating of this invention has a high resistance to cyclic oxidation.
  • the ceramic coatings Nd x Zr 1-x O y with Z dissolved in include air plasma thermal spray (APS), low pressure plasma spray (LPPS), high velocity oxygen fuel (HVOF), sputtering and electron beam physical vapor deposition (EBPVD), etc.
  • the ceramic coating is applied by electron beam physical vapor deposition (EBPVD) due to the columnar microstructure with inter-column gaps produced.
  • the ceramic coating can be deposited as a straight columnar microstructure or a saw tooth microstructure or a layered microstructure or mix of thereof for further reduction in thermal conductivity.
  • the ceramic coating is applied to a thickness within the range of about 5 to 500 ⁇ m, preferably about 25 to 400 ⁇ m.
  • the ceramic coating can have at least 2 layers, preferably from 5 to 100 layers, each at least about 1 ⁇ m thick, preferably about 5 to 25 ⁇ m thick.
  • the process of applying the ceramic coating by EBPVD is similar to that of applying 7YSZ in production.
  • the evaporating source in a crucible is a solid ingot of the Nd x Zr 1-x O y with Z dissolved in, which is sintered zirconia doped with neodymia and the selected metal oxide.
  • the layered microstructure of the ceramic coating, Nd x Zr ⁇ _ x O y with Z dissolved in, is applied by evaporating the solid ingots from two crucibles under controlled gun on/off program of electron beam physical vapor deposition.
  • the ceramic coating, Nd x Zri. x O y with yttria dissolved in with 6-8wt% YSZ at the top is deposited by evaporating the solid ingot of Nd x Zr 1-x O y with Z dissolved in from one crucible and 6-8wt% YSZ ingot from another crucible by electron beam physical vapor deposition.
  • the metallic bond coat is applied onto the metallic article, such as a nickel or cobalt based superalloys prior to deposition of the ceramic coating.
  • the metallic bond coat can be a MCrAlY alloy, wherein M is Ni, Co or mixtures thereof. Such alloys have a broad composition of 10 to 35% chromium, 5 to 15% aluminum, 0.01 to 1% yttrium, or hafnium, or lanthanum, with M being the balance. Minor amounts of other elements such as Ta or Si may also be present.
  • the MCrAlY bond coat can be applied by EBPVD, though sputtering, low pressure plasma or high velocity oxy fuel spraying or entrapment plating may also be used.
  • the metallic bond coat can be comprised of an intermetallic aluminide such as nickel aluminide or platinum aluminide.
  • the aluminide bond coating can be applied by standard commercially available aluminide processes whereby aluminum is reacted at the substrate surface to form an aluminum intermetallic compound, which provides a reservoir for the growth of an alumina scale oxidation resistant layer.
  • the aluminide coating is predominately composed of aluminum intermetallic [e.g., NiAl, CoAl and (Ni, Co) Al phase] formed by reacting aluminum vapor species, aluminum rich alloy powder or surface layer with the substrate elements in the outer layer of the superalloy component. This layer is typically well bonded to the substrate.
  • Aluminizing may be accomplished by one of several conventional prior art techniques, such as, the pack cementation process, spraying, chemical vapor deposition, electrophoresis, sputtering, and appropriate diffusion heat treatments.
  • Other beneficial elements can also be incorporated into diffusion aluminide coatings by a variety of processes.
  • Beneficial elements include Pt, Pd, Si, Hf, Y and oxide particles, such as alumina, yttria, hafnia, for enhancement of alumina scale adhesion, Cr and Mn for hot corrosion resistance, Rh, Ta and Cb for diffusional stability and/or oxidation resistance and Ni, Co for increasing ductility or incipient melting limits.
  • the coating phases adjacent to the alumina scale will be platinum aluminide and/or nickel-platinum aluminide phases (on a Ni-base superalloy).
  • an alumina (i.e., aluminum oxide) layer is formed over the metallic bond coat.
  • This alumina layer provides both oxidation resistance and a bonding surface for a ceramic coating.
  • the alumina layer may be formed before the ceramic coating is applied, during application of the coating or subsequently by heating the coated article in an oxygen containing atmosphere at a temperature consistent with the temperature capability of the superalloy, or by exposure to the turbine environment.
  • the sub-micron thick alumina scale will thicken on the aluminide surface by heating the material to normal turbine exposure conditions.
  • the thickness of the alumina scale is preferably sub-micron (up to about one micron).
  • the alumina layer may also be deposited by chemical vapor deposition following deposition of the metallic bond coat. Alternatively, the metallic bond coat may be eliminated if the substrate is capable of forming a highly adherent alumina scale or layer. Examples of such substrates are very low sulfur ( ⁇ 1 ppm) single crystal superalloys, such as PWA 1487 and Rene N5, which also contain 0.1% yttrium to enhance adhesion of the thermally grown alumina scale.
  • FIG. 1 shows the ceramic coating, Nd x Z - x Oy with Z dissolved in, 40 which was applied by EBPVD onto a metallic bond coat 20, such as a MCrAlY and/or platinum modified aluminide.
  • the bond coat 20 was applied to the metallic article 10, of nickel or cobalt based superalloys prior to the application of the ceramic coating 40.
  • the bond coat 20 provides strong adhesion between the metallic substrate 10 and the ceramic coating 40.
  • the ceramic coating adheres to the bond coat 20 through a thermally grown alumina film 30 on the bond coat 20.
  • Figure 2 shows the ceramic coating, Nd ⁇ Zr 1-x O y with Z dissolved in, 40 applied in a layered microstructure.
  • FIGS 3(a) and 3(b) show a protective ceramic top coat 50 which is coated after the columnar ceramic coating Nd x Z - x O y with Z dissolved in 40, to provide increased erosion resistance on the top surface which is subject to hot gas impact during turbine engine operation.
  • This protective ceramic top coat can be a dense and/or wide column of ceramic coating Nd x Zr ⁇ x Oy with Z dissolved in, or alternatively, layer 50 could also be 6-8wt% YSZ.
  • This protective ceramic top coat, 50 for erosion resistance generally has a thickness of about 5 to 50 ⁇ m preferably about 10 to 25 ⁇ m thick.
  • a protective top coat of 7YSZ with an appropriate thickness for erosion resistance on the ceramic coating, Nd x Zr 1-v O y with Z dissolved in, provides a thermal conductivity which is equivalent to the ceramic coating without the protective ceramic top coat.
  • the ceramic coating system of this invention provides many advantages for use in gas turbine engines. The reduction in thermal conductivity of 50 percent can reduce the thickness required for the thermal barrier coating (TBC) by approximately one half for the same degree of thermal insulation. This will lower the cost of the TBC due to the time saved in applying the coating, ingot material savings and energy savings in production. Decreasing in the coating thickness will also lower the weight of the gas turbine component, e.g. blades and vanes, which can provide a significant reduction in the weight of the disk that holds these components.
  • TBC thermal barrier coating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

This invention provides a thermal barrier ceramic coating for application to a metallic article, with the ceramic coating having a formula of NdxZr1-xOywith Z dissolved in , where 0<x<0.5 and 1.75<y<2 and wherein Z is an oxide of a metal selected from the group consisting of Y, Mg, Ca, Hf and mixtures thereof. In one embodiment Nd is added at a level up to 7 mole %. In another embodiment Z is yttrium and is added at a level of at least 6wt%.

Description

DURABLE THERMAL BARRIER COATING HAVING LOW THERMAL CONDUCTIVITY
FIELD OF THE INVENTION The present invention relates generally to the field of thermal barrier coatings that are used in elevated temperature applications such as gas turbine engines. In particular, this invention relates to a thermal insulating ceramic coating, which has a low thermal conductivity as well as a long service life, and to the metallic articles such as turbine components, (e.g. blades and vanes) that the coatings are applied to prevent the components from overheating during high temperature operation.
BACKGROUND OF THE INVENTION Advanced gas turbine engines are continuously pursuing higher thrust and efficiency by the use of increased operating temperatures. However, the demand of increasing temperature is limited by the ability of most advanced nickel and cobalt based superalloy turbine blades and vanes to maintain their mechanical strength when exposed to the heat, oxidation, erosion and corrosion environment. Thus it is desirable to increase turbine engine operating temperatures, while decreasing the heat transfer to the metallic parts. One approach is to apply a thermal barrier coating onto the turbine blades and vanes to insulate the components from the high temperature operating environment. The ability of the thermal barrier coating to decrease the temperature to the metallic substrate depends upon the thermal conductivity of the thermal barrier coating. It is therefore desirable to develop thermal barrier coatings having low thermal conductivity to insulate effectively the thermal transfer to the components used in gas turbine engines, as well as providing a coated component having a long service life. Efforts have been made to lower the thermal conductivity of thermal barrier coatings by modifying the chemistry and microstructure of current 7YSZ thermal barrier coating systems as disclosed in EP0816526A2, US Patent 6071628, US Patent 5846605, US Patent 6183884B1, US Patent 5792521, US Patent 5687679, W01/63008 and US Patent 6284323B1. These approaches decreased thermal conductivity of thermal barrier coatings to various extents with the minimum reported to be about half the thermal conductivity of typical 7 wt% yttria stabilized zirconia (7YSZ). It is a main object of this invention to decrease thermal conductivity of thermal barrier coatings by providing a new ceramic material with low thermal conductivity. This invention also provides a method of applying such a thermal barrier coating system onto the metallic parts providing increased thermal insulation capability and prolonged durability, as well as increased erosion resistance.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the ceramic coating, NdxZr1-xOy with Z dissolved in, which was applied by EBPVD onto a metallic bond coat Fig. 2 shows the ceramic coating, NdxZr1-xOy with Z dissolved in, applied in a layered microstructure. Figures 3(a) and 3(b) shows a protective ceramic top coat on the ceramic coating, NdxZr1-xOy with Z dissolved in.
SUMMARY OF THE INVENTION Briefly, this invention provides a thermal barrier ceramic coating for application to a metallic article, with the ceramic coating having a formula of NdxZr1-xOy with Z dissolved in, where O<x<0.5 and 1.75<y<2 and Z is an oxide of a metal selected from the group consisting of Y, Mg, Ca, Hf and mixtures thereof. In a one embodiment up to 7 mole % of neodymia is in the coating. In another embodiment Z is yttria and at least 6 weight percent of yttria is added.
DETAILED DESCRIPTION OF THE INVENTION This invention provides a thermal barrier ceramic coating having a formula of NdxZ -xOy with Z dissolved in, where 0<x <0.5, 1.75<y<2, and Z is an oxide of a metal selected from the group consisting of Y, Mg, Ca, Hf and mixtures thereof. The ceramic is formed by doping oxides of Nd and the selected metal oxides into a host zirconia ceramic forming a non-pyrochlore crystal structure. A preferred embodiment is where Z is yttria. The NdxZr1-xOy ceramic coating with yttria dissolved in can be prepared by doping 2 to 15 mole % of Nd203, preferably up to 7 moles %. The yttria level generally is from 2 to 14 mole %, preferably at least 6 wt %. In a further embodiment along with the yttria, hafnium is also added, generally at a level of from about 0.5 to 6 wt %, preferably 1.5 to 4 wt %. The ceramic coating of this invention is applied to a metallic article providing a thermal barrier coating with low thermal conductivity, resistance to erosion and high resistance to cyclic oxidation providing increased durability. In one preferred embodiment the coating contains up to 7 mole % of neodymia, e.g. 2 to 7 mole %. The lower level of neodymia is believed to provide a coating with increased erosion resistance. Higher levels of rare earth oxides provide thermal barrier coatings which spall earlier in cyclic oxidational testing. An example is a coating with 7 mole % of Nd203 and 5 mole % Y203 (8 wt %). In another preferred embodiment the coating has at least 6 wt % of yttria, preferably 6 to 10 wt %, optimally 6 to 8 wt % dissolved in. The higher level of yttria is believed to provide a further reduction in thermal conductivity due to higher concentration of oxygen vacancies in the matrix lattice structure, which will enhance phonon scattering. In addition, a phase transformation from high temperature to ambient temperature was found in the system of Nd-Zr without yttria or with low levels of yttria which could cause premature spallation of the coatings. The addition of at least 6 wt % of yttria avoids the premature spallation caused by phase transformation in the TBC system. Another benefit of doping at least 6 wt % Y203 is to increase the toughness of the ceramic coatings material. Cracks were found within the ceramic coating without yttria or with low levels of yttria (less than 6 wt %) under thermal cycle impact. The tougher ceramic coating containing at least 6 wt % yttria also provides good erosion resistance. Thus the addition of at least 6 wt % yttria to the ceramic coating provides a coating with lower thermal conductivity and greater durability due to its improved phase stability, increased toughness, erosion resistance and resistance to cyclic oxidation. One example is a coating with 10 mole % of Nd203 and 6 wt % Y203 doped into Zr02. The further addition of hafnia along with yttria has the further advantage of reducing thermal conductivity and strengthening the ceramic material providing an increased resistance to erosion and thermal shock. An example is the further addition of about 3 wt % of hafnia (Hf02) to the above example formulations. The ceramic coating of this invention has a low thermal conductivity generally within the range of about 0.78 to 1.02 W/mK from 600°C to 1100°C. This thermal conductivity is around 50% of the measured thermal conductivity of a typical 7YSZ coating (1.65-2.22 W/mK from 600°C to 1100°C). In addition the ceramic coating of this invention has a high resistance to cyclic oxidation. Techniques for applying the ceramic coatings, NdxZr1-xOy with Z dissolved in include air plasma thermal spray (APS), low pressure plasma spray (LPPS), high velocity oxygen fuel (HVOF), sputtering and electron beam physical vapor deposition (EBPVD), etc. In a preferred embodiment the ceramic coating is applied by electron beam physical vapor deposition (EBPVD) due to the columnar microstructure with inter-column gaps produced. The ceramic coating can be deposited as a straight columnar microstructure or a saw tooth microstructure or a layered microstructure or mix of thereof for further reduction in thermal conductivity. Generally, the ceramic coating is applied to a thickness within the range of about 5 to 500 μm, preferably about 25 to 400 μm. In a layered microstructure, the ceramic coating can have at least 2 layers, preferably from 5 to 100 layers, each at least about 1 μm thick, preferably about 5 to 25 μm thick. The process of applying the ceramic coating by EBPVD is similar to that of applying 7YSZ in production. The evaporating source in a crucible is a solid ingot of the NdxZr1-xOy with Z dissolved in, which is sintered zirconia doped with neodymia and the selected metal oxide. The layered microstructure of the ceramic coating, NdxZrι_xOy with Z dissolved in, is applied by evaporating the solid ingots from two crucibles under controlled gun on/off program of electron beam physical vapor deposition. The ceramic coating, NdxZri. xOy with yttria dissolved in with 6-8wt% YSZ at the top is deposited by evaporating the solid ingot of NdxZr1-xOy with Z dissolved in from one crucible and 6-8wt% YSZ ingot from another crucible by electron beam physical vapor deposition. For increased adhesion a metallic bond coat is applied onto the metallic article, such as a nickel or cobalt based superalloys prior to deposition of the ceramic coating. The metallic bond coat can be a MCrAlY alloy, wherein M is Ni, Co or mixtures thereof. Such alloys have a broad composition of 10 to 35% chromium, 5 to 15% aluminum, 0.01 to 1% yttrium, or hafnium, or lanthanum, with M being the balance. Minor amounts of other elements such as Ta or Si may also be present. The MCrAlY bond coat can be applied by EBPVD, though sputtering, low pressure plasma or high velocity oxy fuel spraying or entrapment plating may also be used. Alternatively, the metallic bond coat can be comprised of an intermetallic aluminide such as nickel aluminide or platinum aluminide. The aluminide bond coating can be applied by standard commercially available aluminide processes whereby aluminum is reacted at the substrate surface to form an aluminum intermetallic compound, which provides a reservoir for the growth of an alumina scale oxidation resistant layer. Thus the aluminide coating is predominately composed of aluminum intermetallic [e.g., NiAl, CoAl and (Ni, Co) Al phase] formed by reacting aluminum vapor species, aluminum rich alloy powder or surface layer with the substrate elements in the outer layer of the superalloy component. This layer is typically well bonded to the substrate. Aluminizing may be accomplished by one of several conventional prior art techniques, such as, the pack cementation process, spraying, chemical vapor deposition, electrophoresis, sputtering, and appropriate diffusion heat treatments. Other beneficial elements can also be incorporated into diffusion aluminide coatings by a variety of processes. Beneficial elements include Pt, Pd, Si, Hf, Y and oxide particles, such as alumina, yttria, hafnia, for enhancement of alumina scale adhesion, Cr and Mn for hot corrosion resistance, Rh, Ta and Cb for diffusional stability and/or oxidation resistance and Ni, Co for increasing ductility or incipient melting limits. In the specific case of platinum modified diffusion aluminide coating layers, the coating phases adjacent to the alumina scale will be platinum aluminide and/or nickel-platinum aluminide phases (on a Ni-base superalloy). Through oxidation an alumina (i.e., aluminum oxide) layer is formed over the metallic bond coat. This alumina layer provides both oxidation resistance and a bonding surface for a ceramic coating. The alumina layer may be formed before the ceramic coating is applied, during application of the coating or subsequently by heating the coated article in an oxygen containing atmosphere at a temperature consistent with the temperature capability of the superalloy, or by exposure to the turbine environment. The sub-micron thick alumina scale will thicken on the aluminide surface by heating the material to normal turbine exposure conditions. The thickness of the alumina scale is preferably sub-micron (up to about one micron). The alumina layer may also be deposited by chemical vapor deposition following deposition of the metallic bond coat. Alternatively, the metallic bond coat may be eliminated if the substrate is capable of forming a highly adherent alumina scale or layer. Examples of such substrates are very low sulfur (<1 ppm) single crystal superalloys, such as PWA 1487 and Rene N5, which also contain 0.1% yttrium to enhance adhesion of the thermally grown alumina scale. Fig. 1 shows the ceramic coating, NdxZ -xOy with Z dissolved in, 40 which was applied by EBPVD onto a metallic bond coat 20, such as a MCrAlY and/or platinum modified aluminide. The bond coat 20 was applied to the metallic article 10, of nickel or cobalt based superalloys prior to the application of the ceramic coating 40. The bond coat 20 provides strong adhesion between the metallic substrate 10 and the ceramic coating 40. The ceramic coating adheres to the bond coat 20 through a thermally grown alumina film 30 on the bond coat 20. Figure 2 shows the ceramic coating, NdχZr1-x Oy with Z dissolved in, 40 applied in a layered microstructure. The interface boundaries between the layers are another potential source of phonon scattering for thermal conductivity reduction. Figures 3(a) and 3(b) show a protective ceramic top coat 50 which is coated after the columnar ceramic coating NdxZ -x Oy with Z dissolved in 40, to provide increased erosion resistance on the top surface which is subject to hot gas impact during turbine engine operation. This protective ceramic top coat can be a dense and/or wide column of ceramic coating NdxZr^xOy with Z dissolved in, or alternatively, layer 50 could also be 6-8wt% YSZ. This protective ceramic top coat, 50 for erosion resistance, generally has a thickness of about 5 to 50 μm preferably about 10 to 25 μm thick. A protective top coat of 7YSZ with an appropriate thickness for erosion resistance on the ceramic coating, NdxZr1-vOy with Z dissolved in, provides a thermal conductivity which is equivalent to the ceramic coating without the protective ceramic top coat. The ceramic coating system of this invention provides many advantages for use in gas turbine engines. The reduction in thermal conductivity of 50 percent can reduce the thickness required for the thermal barrier coating (TBC) by approximately one half for the same degree of thermal insulation. This will lower the cost of the TBC due to the time saved in applying the coating, ingot material savings and energy savings in production. Decreasing in the coating thickness will also lower the weight of the gas turbine component, e.g. blades and vanes, which can provide a significant reduction in the weight of the disk that holds these components. Depositing the same thickness of the ceramic coating will allow an increased operating temperature to be achieved without overheating the metallic parts allowing the engine to operate a higher thrust and efficiency. The increased insulating capabilities of the ceramic coating could also reduce the requirements for air cooling the part. This invention is generally applicable to any metallic article which uses thermal barrier coating system, and includes various modifications according to the principles of this invention.

Claims

WHAT IS CLAIMED 1. A metallic article comprising a metallic substrate and a thermal barrier ceramic coating on its surface with the ceramic coating having
Figure imgf000014_0001
with Z dissolved in, where 0<x<0.5 and 1.75<y<2 with up to 7 moles % of Nd203 in the ceramic coating and Z is an oxide of a metal selected from the group consisting of Y. Mg, Ca, Hf and mixtures thereof.
2. Article of Claim 1 wherein Z is Y with at least 6 wt % of yttria dissolved in.
3. Article of Claim 2 further comprising hafnia dissolved in.
4. Article of Claim 2 with from 2 to 7 mole % of Nd203 and 6 to 10 wt % of yttria dissolved in. 5. Article of Claim 4 further comprising 0.
5 to 6 wt % of hafnia dissolved in.
6. Article of Claim 1 further comprising a metallic bond coat between the ceramic coating and the metallic substrate.
7. Article of Claim 6 wherein the metallic bond coat is a MCrAlY, wherein M is selected from Ni and/or Co.
8. Article of Claim 6 wherein the metallic bond coat is an intermetallic aluminide.
9. Article of Claim 1 wherein the ceramic coating has a columnar microstructure.
10. Article of Claim 9 wherein the columnar microstructure is a straight or a saw tooth structure.
11. Article of Claim 1 wherein the ceramic coating has a layered microstructure.
12. Article of Claim 1 further comprising a protective ceramic top coat overlaying the ceramic coating.
13. Article of Claim 12 wherein the protective ceramic top coat is a dense or a wide columnar microstructure.
14. Article of Claim 12 wherein the protective ceramic top coat is 6 to 8 wt% YSZ.
15. Article of Claim 1 wherein the ceramic coating has a thermal conductivity of from about 0.78 to 1.02 W/mK from 600°C to ll00°C.
16. Article of Claim 1 wherein the ceramic coating has been applied by EBPVD, air plasma spray or HVOF.
17. Article of Claim 1 wherein the metallic article is a turbine component.
18. Article of Claim 17 wherein the turbine component has a metallic substrate of a nickel or cobalt based superalloy.
19. Article of Claim 1 wherein the ceramic coating has a thickness within the range of about 5 to 500 μm.
20. Article of Claim 6 wherein the protective ceramic top coat has a thickness of about 5 to 50 μm.
21. A metallic article comprising a metallic substrate and a thermal barrier ceramic coating on its surface, the ceramic coating having a formula of NdxZr1-xOy with yttria dissolved in wherein 0<x<0.5 and 1.75<y<2, with at least 6 wt % of yttria dissolved in.
22. Article of Claim 21 further comprising hafnia dissolved in.
23. Article of Claim 21 having 6 to 10 wt % of yttria dissolved in and 2 to 15 mole % Nd203.
24. Article of Claim 23 further comprising 0.5 to 6 wt % of hafnia dissolved in.
25. Article of Claim 21 wherein the ceramic has a non- pyrochlore crystal structure.
26. Article of Claim 21 further comprising a metallic bond coat between the ceramic coating and the metallic substrate.
27. Article of Claim 26 wherein the metallic bond coat is a MCrAlY, wherein M is selected from Ni and/or Co.
28. Article of Claim 26 wherein the metallic bond coat is intermetallic aluminide.
29. Article of Claim 21 wherein the ceramic coating has a columnar microstructure.
30. Article of Claim 29 wherein the columnar microstructure is a straight or a saw tooth structure.
31. Article of Claim 21 wherein the ceramic coating has a layered microstructure.
32. Article of Claim 21 further comprising a protective ceramic top coat overlaying the ceramic coating.
33. Article of Claim 32 wherein the protective ceramic top coat is a dense or a wide columnar microstructure.
34. Article of Claim 32 wherein the protective ceramic top coat is 6-8wt% YSZ having a thickness of about 5 to 50 μm.
35. Article of Claim 21 wherein the ceramic coating has a thermal conductivity of from about 0.72 to 1.02 W/mK from 600°C to 1100°C.
36. Article of Claim 21 wherein the ceramic coating has been applied by EBPVD, air plasma spray or HVOF.
37. Article of Claim 21 wherein the metallic article is a turbine component.
38. Article of Claim 37 wherein the turbine component has a metallic substrate of a nickel or cobalt based superalloy.
39. A method for applying a thermal barrier ceramic coating to a metallic article comprising: forming a ceramic having a formula NdxZr1-x Oy with yttria dissolved in, wherein 0<x<0.5 and 1.75<y<2 with at least 6 wt % of yttria dissolved in, by doping yttria and neodymia into a zirconia ceramic; and applying the ceramic as a coating onto the metallic article.
40. Method of Claim 39 wherein the ceramic is applied by electron beam physical vapor deposition.
41. Method of Claim 39 wherein 2 to 7 mole % of Nd203 and 6 to 10 wt % Y203 are doped into Zr02.
42. Method of Claim 39 further comprising doping hafnia into a zirconia ceramic.
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