US3890456A - Process of coating a gas turbine engine alloy substrate - Google Patents

Process of coating a gas turbine engine alloy substrate Download PDF

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US3890456A
US3890456A US386266A US38626673A US3890456A US 3890456 A US3890456 A US 3890456A US 386266 A US386266 A US 386266A US 38626673 A US38626673 A US 38626673A US 3890456 A US3890456 A US 3890456A
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noble metal
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aluminum oxide
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Ray R Dils
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Raytheon Technologies Corp
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United Aircraft Corp
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01DNON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D21/00Shutting-down of machines or engines, e.g. in emergency; Regulating, controlling, or safety means not otherwise provided for
    • F01D21/003Arrangements for testing or measuring
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321Coatings 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings 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
    • C23C28/341Coatings 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 carbide layer
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings 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
    • C23C28/345Coatings 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings 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
    • C23C28/345Coatings 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
    • C23C28/3455Coatings 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01DNON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12Blades
    • F01D5/28Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288Protective coatings for blades
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/923Physical dimension
    • Y10S428/924Composite
    • Y10S428/926Thickness of individual layer specified
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12451Macroscopically anomalous interface between layers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611Oxide-containing component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12875Platinum group metal-base component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495Thickness [relative or absolute]
    • Y10T428/24967Absolute thicknesses specified
    • Y10T428/24975No layer or component greater than 5 mils thick

Definitions

  • ABSTRACT A method of coating a gas turbine engine alloy sub strate comprising depositing a rare earth and aluminum-containing alloy initial layer to a thickness sufficient to produce and maintain an adherent irregular aluminum oxide, mechanically working the surface of the initial layer to induce irregularity and angular topography in the aluminum oxide to be produced, oxidizing the initial layer to produce a sufficiently thick and irregular aluminum oxide layer to establish mechanical adherence ofa noble metal layer and prevent alloying between the initial layer and the noble metal layer, depositing a noble metal layer on the oxidized layer to a thickness of approximately 0.1-0.2 mils and oxidatively treating the coated substrate to cause additional growth of the oxide layer to metallurgically insulate the noble metal layer from the substrate and the initial metal layer.
  • the present invention relates to the treatment of metals and alloys and more particularly relates to a method for coating gas turbine engine components either partially, as in the form of a thin strip array to provide surface temperature or surface strain sensors therefor, or completely to provide improved resistance of the component to high temperature sulfidation or oxidation.
  • the present invention relates to a method of coating a nickelbase, cobalt-base or iron-base gas turbine engine alloy.
  • the invention contemplates a method comprising l) depositing a rare earth and aluminum containing alloy initial layer to a thickness sufficient to produce and maintain an adherent irregular aluminum oxide, preferably NiCrAlY, CoCrAlY or FeCrAlY to a thickness of0.5-5.0 mils, (2) mechanically working the surface of the initial layer to induce irregularity and angular topography in the aluminum oxide to be produced, preferably by grit blasting or peening, (3) oxidizing the mechanically worked initial layer to produce a sufficiently thick and irregular aluminum oxide layer to promote mechanical adherence of a noble metal layer and to prevent alloying between the initial layer and the noble metal layer, preferably by an oxidation treatment to form an oxide layer 0.050.1 mil thick such as heating, in air, for 70-170 hours at 1900F, (4) depositing a noble metal layer on the oxidized initial layer to
  • the noble metal coating is in the form of an array of first and second thin strip elements, the noble metal of the first thin strip element, preferably platinum, having a large temperature coefficient of resistivity with respect to the noble metal of the second thin strip element and the second thin strip element, preferably an alloy consisting essentially of 8l2 weight percent W, balance Pt, having a large strain coefficient of resistivity with respect to the first or in the form of an array consisting of the strain sensitive element, 8l2 weight percent W, balance Pt, and a sputtered Pt/Pt-Rh thermocouple located near the center of the strain sensitive element.
  • a protective layer of aluminum oxide or calcium stabilized zirconia may be provided, preferably by RF sputtering thereover.
  • the basic method disclosed herein is particularly useful for overcoating gas turbine components to provide increased resistance to sulfidation as well as to high temperature ox dat on.
  • an electric field is superimposed across the aluminum oxide layer with the noble metal layer as the anode and the substrate as the cathode.
  • FIG. 1(a) is a plan view showing noble metal test elements on a flat disk
  • FIG. 1(b) is a plan view showing an incomplete fourjunction sensor on a flat disk
  • FIG. He is a plan view showing a completed fourjunction sensor on a flat disk
  • FIG. 1(d) is a side elevational view of a threejunction sensor array on an erosion bar
  • FIG. 2 is a chart showing sensor accuracy
  • FIGS. 3(a) and 3(b) are perspective views of a turbine blade having large scale sensor arrays on their surface;
  • FIGS. 4(a) and 4(b) are diagrammatic plan views of small scale sensor arrays near cooling holes
  • FIG. 5 is a diagrammatic plan view of a two-element strain sensor
  • FIG. 6 is a perspective view, partly cross-sectionally enlarged, ofa turbine component showing the imposition of an electric field across the oxide coating.
  • the nickel-base, cobalt-base and iron-bas gas turbine engine alloys are those strong, high temperature materials suitable for use in gas turbine engine applications.
  • Typical of the alloys which may be coated according to the present invention are the so-called nickei-base and cobalt-base superalloys, viz., those which generally contain 5-25 weight percent Cr, 5-15 weight percent Mo, Ta or W and 2-8 weight percent Al and Ti.
  • Also useful as substrates are the high temperature iron-base alloys such as the austenitic stainless steels or Kanthal A (5.5 Al, 22 Cr, balance Fe).
  • the first step is the deposition of an initial layer of an alloy onto a gas turbine engine alloy substrate.
  • the initial layer is any rare earth or rare earth particle-containing alloy which can form an adherent irregular aluminum oxide.
  • the initial layer contains no more than approximately 2 percent, by weight, of the rare earth metal and approxi- 1.1ately 5-25 percent, by weight, aluminum and preferably consists of a coating such as NiCrAIY (20-35 weight percent Cr, 15-20 weight percent Al, 0.05-0.3 Y, balance Ni), CoCrAlY (19-24 weight percent Cr,
  • the second step in the construction of the coating is the mechanical working of the initial layer to induce the growth of an adherent metal oxide with an extremely irregular and angular topography.
  • the subsequently deposited noble metal layer is primarily mechanically bonded to the initial layer and any method of surface preparation which will induce the growth of an irregular oxide will promote its mechanical adherence thereto.
  • Grit blasting of the surface with various sizes of grit is considered a satisfactory technique. as is peening.
  • the initial layer is oxidized to produce a sufficiently thick and irregular oxide to promote the mechanical adherence of the noble metal layer, and to provide a sufficiently small number of paths through the oxide to the substrate to eliminate alloying between the initial layer and the noble metal layer.
  • the oxide layer must be thin enough to permit rapid reoxidation of the specimen, provide oxide dimensions representative of the oxides grown in the turbine environment in order not to perturb the heat flow in the system and minimize the reduction of the turbine component life due to the oxidation treatment. It has been found that oxides from 0.05-0.l mil thick which are grown in air for generally 70-300 hours at I900F fulfill the above requirements. However, it will be appreciated that any oxidation treatment which produces an oxide dimension approximating the above range is considered suitable.
  • the next step comprises the deposition of a noble metal layer to form a noble metal thermocouple.
  • noble metal is meant such elements or alloys as those of platinum, rhodium or palladium.
  • Each layer is deposited, preferably by sputtering, to a thickness sufficient to be stable and durable in harsh environments yet thin enough to permit oxygen diffusion through the layer in order to insulate it during the subsequent oxidation treatment described below. It has been established that noble metal thicknesses between 0.1 and 0.2 satisfy these requirements.
  • the adherence of the noble metal layer increases with increasing sputtering substrate temperature.
  • some uses of sensors require high resolution spacial distributions of thermocouple functions on the surface of a component and these sensor arrays are best obtained by low temperature masking procedures. Thus the entire range of sputtering substrate temperatures, from room temperature to the melting point of the substrate may be utilized.
  • the fifth step in the process is the electrical insulation of the noble metal layer from the substrate and the initial layer. It has been found that oxidation in air for approximately 30 hours at I900F is sufficient to achieve this result.
  • the last step in the construction of a sensor is the formation of relatively thick terminals at the ends of the sputtered noble metal leads to permit lead wires to be directly connected, as by spot welding. thereto. Terminal thicknesses between 0.2-0.5 mil are sufficient to obtain a durable connection between the sensors and 0.003 mil diameter lead wires. The width of the terminals is smaller than the original width of the sputtered leads to prevent loss of the electrical insulation of the sensor.
  • surface temperature sensors made according to the present invention have provided metal surface temperatures from 0F to the melting point of several nickel-, cobaltor iron-base alloys with the accuracy of special grade platinum/platinum-rhodium thermocouples.
  • the presence of the sensor on the surface of a component did not significantly perturb the heat flow from the gas stream to the component or the heat flow within the component.
  • the bandwidth of information was limited only by the relative amplitudes of the signal and the equivalent input noise of the associated electronics. In general, useful information may be received over a several kilohertz bandwidth. Tests indicated that the sensors are usually durable.
  • Example Simple sensor elements 10 on flat disks l2 and an erosion bar 14 are shown in FIG. 1.
  • the flat disks comprised a substrate of the nickel-base alloy B1900 (nominal composition, by weight percent, 8 Cr, 10 Co, 1 Ti, 6 Al, 6 Mo, 0.l l C, 4.3 Ta, 0.15 B, 0.07 Zr, balance Ni) and a sputtered initial layer three mils thick of FeCr- AlY which had been mechanically worked by a No. 320 grit blast and subsequently oxidized in air for hours at 1900F to grow an aluminum oxide 0.1 mil thick.
  • Platinum test elements 16, 40 mils wide, 750 mils long and 0.l mil thick were sputtered on the flat disk 12 shown in FIG. 1(a).
  • FIG. 1(d) shows a three-junction sensor array on an erosion bar.
  • any desirable array of thermoelectric junctions can be sputtered on a turbine component. Since the initial layer coating and oxide are common to high temperature turbine components, the only real change in the component configuration is due to the sputtered noble metal layer having a thickness of 0.0001-0.0002 inch.
  • the narrowband (steady state) thermal impedance of a 0.000! inch platinum element is 2.14 X 10 of the boundary layer impedance when h 1000 BTU/ft hrR.
  • the thickness of the noble metal layer is small with respect to the thickness of the boundary layer and therefore does not alter the structure of the boundary layer.
  • the platinum element narrowband impedance is 7.5 X 10 of the impedance of a 0.050 inch section of a nickel-base alloy.
  • the broadband response near the turbine component surface is limited by the oxide layer.
  • a harmonic temperature wave travelling across a 0.0001 inch oxide layer is attenuated to He of the initial amplitude of the wave at the surface.
  • the reduction in wave amplitude across the sensor is less than six percent. Therefore, the sensor elements do not affect narrowband or broadband measurements; the useful bandwidth of the information is determined by the relative amplitudes of the signal and the equivalent input noise of the associated electronics.
  • the width of the sputtered sensors is extremely small, in this case over 300 times smaller than the width of conventional thermocouples used by placement in slots in airfoils to measure temperatures near the airfoil surfaces.
  • the sputtered sensor width is over I times smaller than the conventional strain and temperature sensors presently applied externally to airfoil surfaces.
  • thermoelectric voltage generated by a sputtered Pt/Pt-IO percent Rh sensor like the one shown in FIG. 1(c) and a special grade Pt/Pt-IO percent Rh thermocouple is presented in FIG. 2.
  • the specimen was cycled from room temperature to 2000F in random temperature intervals for two months. At each temperature, the specimen and standard thermocouple were equilibriated for at least four hours before the temperature was measured. The indicated errors are within those expected between different special grade Pt/Ptl0 percent Rh thermocouples. There appear to be no extraordinary errors associated with the sputtered sensors.
  • Platinum test elements such as those shown in FIG. 1(a) were cycled several hundred times from 2000F to room temperature in a stationary gas. The thermal cycling had no effect on the test elements which remained electrically insulated from the substrate and strongly bonded to the substrate oxide.
  • a Pt/Pt-IO percent Rh sensor sputtered on a rod was cycled over 5000 times from l800F to room temperature in a moderate velocity gas stream (Ma 05). Although the substrate was extensively cracked and plastically deformed causing a loss of electrical insulation between the sensor and the substrate, the sensor remained strongly bonded to the substrate oxide.
  • the sensors of the present invention are able to withstand extensive gradual or rapid plastic deformation.
  • platinum test elements sputtered on flat disks such as those of FIG. 1(a) were deformed approximately IO percent to concave and convex shapes, yet remained attached to the substrate and electrically insulated therefrom.
  • the sensors can be quite heavily scratched or abraded. Even if the units are inordinately handled so that a loss of insulation between the sensor elements and the substrate results, they may be re paired by reoxidizing the components.
  • a platinum test element was struck repeatedly with a ballpeen hammer so that the sensor element was grounded to the substrate. The element was nevertheless subsequently electrically insulated from the substrate by oxidizing the component for 20 hours at 1900F.
  • the surface temperature sensors of the present invention provide data which cannot be obtained by state-of-the-art techniques of the gas turbine industry.
  • the sensor units provide steady state temperatures of the external surfaces of both static or rotating components either in or out of the gas path.
  • Sensor arrays to measure large-scale span and radial temperature dis tributions are shown in FIGS. 3(a) and 3(b).
  • lscale sensor arrays to obtain local surface temperatures near an individual cooling hole are shown in FIGS. 4(a) and 4(b).
  • the sensors provide the actual surface temperatures in the engine and, correspondingly, detailed experimental evaluations of the present analytical models of heat transfer in the engine.
  • the units may be applied to surfaces of details or subassemblies prior to final fabrication steps.
  • internal surface temperatures of a split blade may be obtained by application to the internal surfaces of each half before the halves are bonded together.
  • Large-scale heat flows in the blade can be obtained from combinations of internal and external surface sensor arrays.
  • the sensor units provide broadband surface temperatures and the surface temperature fluctuations important to turbine component oxidation may be obtained.
  • Arrays of the sensors provide broadband correlations between temperature fluctuations at different locations on an airfoil. Direct, broadband evidence of the location, stability and efficiency of transpiration cooling jets may also be obtained.
  • the present invention also contemplates the production of two element strain sensors for use in gas turbines.
  • a typical array is shown in FIG. 5.
  • the process steps for making the two-element strain sensor include the six steps described above for the surface tempera ture sensors except that the sputtering of the noble metal layer is done with two different metals to form separately the first thin strip element 22 and the second thin strip element 24.
  • the first element 22 must have a large temperature coefficient of resistivity relative to the second element and is preferably platinum while the second element must have a large strain coefficient of resistivity relative to the first element and is preferably a platinum alloy containing 8-12 weight percent tungsten.
  • the strain sensor may be constructed with a strain sensitive element as described and a sputtered Pt/Pt-Rh thermocouple located near the center of the strain sensitive element.
  • a protective layer of aluminum oxide or calcium stabilized zirconia is deposited, preferably by sputtering, to a minimum thickness sufficient to protect the sensor element from the environment, e.g., to 0.1-0.5 mil.
  • the basic five-step procedure for producing surface temperature sensors, surface strain sensors and a simple gas turbine component coating for protection against sulfidation it may be utilized, with the addition of a step wherein an electric field is superimposed across the oxide to prevent high temperature oxidation.
  • the field acts to cancel the electromechanical gradient which occurs naturally within the oxide and which provides the driving force for cation and/or anion motion in the oxide.
  • the noble metal layer preferably platinum, is the anode and the metallic coating is the cathode which is at the engine ground potential as shown in FIG. 6. Fields on the order of 10 volts/cm are sufficient to reduce the rate of oxidation.
  • a specimen having a FeCrAlY coating was prepared with No. 320 grit blast and preoxidized for 24 hours at 2000F. Three 0.1 mil Pt electrodes were sputtered on the oxidized surface and the specimen was rcoxidized for 24 hours at 2000F. Positive and negative potentials were applied to two electrodes and the specimens were again oxidized. After an oxidation of 120 hours at 2000F in the presence of the electric fields, the specimens were cross sectioned and measurements were made of the oxides beneath each electrode including the electrode to which no voltage had been applied.
  • the voltage at which oxidation ceases should be the voltage equivalent of the change in free energy of the oxidation reaction which, in the case of aluminum oxide, is approximately 2.1 volts.
  • a noble metal layer selected from the group consisting of platinum, rhodium, palladium and alloys thereof on said oxidized initial layer to a thickness of approximately 0.1-0.2 mil;
  • a method of coating an alloy substrate selected from the group consisting of the nickel-base, cobaltbase and iron-base gas turbine engine alloys comprisdepositing an initial rare earth and aluminumcontaining alloy layer on said substrate to a thickness of approximately 0.5-5.0 mils, said initial layer being an alloy selected from the group consisting of, by weight, 2035% Cr, 15-20% Al, ODS-0.3% Y, balance Ni; 19-24% Cr, 13-17% A], 0.60.9% Y, balance Co; 25-29% Cr, 12-14% Al, 06-09% Y, balance Fe; and 25% Cr, 15% Ni, 5% Ta, 5% A1, 0.1% Y, balance Co;
  • oxidizing said initial layer to produce an irregular aluminum oxide layer approximately 0.05O.l mil thick to promote mechanical adherence of a noble metal layer and to prevent alloying between said initial layer and said noble metal layer; depositing a noble metal layer selected from the group consisting of platinum, rhodium, palladium and alloys thereof on said oxidized initial layer to a thickness of approximately 0.1-0.2 mil; and
  • said noble metal layer is deposited in the form of a thin strip array of thermoelectric junctions with thickened end portions suitable for use as terminal connections whereby said coating acts as a surface temperature sensor.
  • said noble metal layer is deposited in an array of first and second thin strip elements, said first thin strip element having a large temperature coefficient of resistivity with respect to the second thin strip element and said second thin strip element having a large strain coefficient of resistivity with respect to the first whereby said coating acts as a surface strain sensor.
  • said noble metal layer is deposited in the form of a thin strip element having a large strain coefficient of resistivity and a ther mocouple adjacent the center of the thin strip element.
  • said aluminum oxide iron-base gas turbine engine alloys having a first rare layer having an irregular surface; and earth and aluminum-containing nickel-, cobaltor irona noble metal layer selected from the group consistbase alloy layer approximately 0.55.0 mils thick, said ing of platinum, rhodium, palladium and alloys layer containing up to 2%, by weight, rare earth metal 5 thereof approximately 0.1-0.2 mil thick mechaniand approximately, 5-25%, by weight.
  • aluminum the cally bonded, by virtue of said irregular surface, to improvement which comprises: said aluminum oxide layer.

Abstract

A method of coating a gas turbine engine alloy substrate comprising depositing a rare earth and aluminum-containing alloy initial layer to a thickness sufficient to produce and maintain an adherent irregular aluminum oxide, mechanically working the surface of the initial layer to induce irregularity and angular topography in the aluminum oxide to be produced, oxidizing the initial layer to produce a sufficiently thick and irregular aluminum oxide layer to establish mechanical adherence of a noble metal layer and prevent alloying between the initial layer and the noble metal layer, depositing a noble metal layer on the oxidized layer to a thickness of approximately 0.1-0.2 mils and oxidatively treating the coated substrate to cause additional growth of the oxide layer to metallurgically insulate the noble metal layer from the substrate and the initial metal layer.

Description

United States Patent 1 Dils PROCESS OF COATING A GAS TURBINE ENGINE ALLOY; SUBSTRATE Ray R. Dils, Madison, Conn.
United Aircraft Corporation, East Hartford, Conn.
Filed: Aug. 6, 1973 Appl. No.: 386,266
Inventor:
Assignee:
References Cited UNITED STATES PATENTS 2/1953 Weinrich 117/71 X l/1961 Greene et a1. 117/131 X 9/1961 Hanink et al. 117/131 X 11/1964 Freeman et a1. 117/13ORX 4/1966 .laremus et a1 29/573 X 1111970 Talboom et al..,.... 29/1835 7/1972 Evans et a]. 29/194 10/1972 Kanter 117/131 X 1 June 17, 1975 3,754,903 8/1973 Goward et a1. 751m FORElGN PATENTS OR APPLICATIONS 854,570 ll/1960 United Kingdom 29 573 Primary Examiner-Thomas .1. Herbert, Jr. Assistant Examiner-Bruce H. Hess Attorney, Agent, or Firmlohn D. Del Ponti [57] ABSTRACT A method of coating a gas turbine engine alloy sub strate comprising depositing a rare earth and aluminum-containing alloy initial layer to a thickness sufficient to produce and maintain an adherent irregular aluminum oxide, mechanically working the surface of the initial layer to induce irregularity and angular topography in the aluminum oxide to be produced, oxidizing the initial layer to produce a sufficiently thick and irregular aluminum oxide layer to establish mechanical adherence ofa noble metal layer and prevent alloying between the initial layer and the noble metal layer, depositing a noble metal layer on the oxidized layer to a thickness of approximately 0.1-0.2 mils and oxidatively treating the coated substrate to cause additional growth of the oxide layer to metallurgically insulate the noble metal layer from the substrate and the initial metal layer.
14 Claims, 11 Drawing Figures 57- 07 11464022 [40 (/V/t/ZT/J/VS' PATENTEDJUN 17 ms SiiEH @R 6% aw @N/Z PROCESS OF COATING A GAS TURBINE ENGINE ALLOY SUBSTRATE BACKGROUND OF THE INVENTION The present invention relates to the treatment of metals and alloys and more particularly relates to a method for coating gas turbine engine components either partially, as in the form of a thin strip array to provide surface temperature or surface strain sensors therefor, or completely to provide improved resistance of the component to high temperature sulfidation or oxidation.
One of the problems facing the gas turbine industry has been the need for sensors to provide accurate data such as the steady state temperature of static or rotating components either in or out of the gas path. The severe operating environment of gas turbine components presents particularly difficult problems in view not only of the requirement that the temperature cycling of the engine be withstood but also that there be compatibility with the substrate component and no perturbation of the airflow near or heat flow to the component. As will be appreciated, a sensor on a turbine airfoil capable of obtaining accurate broadband turbine temperatures including those in excess of 2000F without perturbing airflow is an important step forward in the art.
SUMMARY OF THE INVENTION The present invention relates to a method of coating a nickelbase, cobalt-base or iron-base gas turbine engine alloy. The invention contemplates a method comprising l) depositing a rare earth and aluminum containing alloy initial layer to a thickness sufficient to produce and maintain an adherent irregular aluminum oxide, preferably NiCrAlY, CoCrAlY or FeCrAlY to a thickness of0.5-5.0 mils, (2) mechanically working the surface of the initial layer to induce irregularity and angular topography in the aluminum oxide to be produced, preferably by grit blasting or peening, (3) oxidizing the mechanically worked initial layer to produce a sufficiently thick and irregular aluminum oxide layer to promote mechanical adherence of a noble metal layer and to prevent alloying between the initial layer and the noble metal layer, preferably by an oxidation treatment to form an oxide layer 0.050.1 mil thick such as heating, in air, for 70-170 hours at 1900F, (4) depositing a noble metal layer on the oxidized initial layer to a thickness to form a noble metal thermocouple, preferably approximately 0.l-0.2 mil and (5) oxidatively treating the coated substrate to cause additional growth of the oxidized initial layer to metallurgically insulate the noble metal layer from the substrate and the initial layer. In the production of surface temperature sensors on the substrate, the noble metal coating is in the form of a suitable thin strip array of thermoelectric junctions having thickened end portions suitable for use as terminal connections.
In the production of surface strain sensors on the substrate, the noble metal coating is in the form of an array of first and second thin strip elements, the noble metal of the first thin strip element, preferably platinum, having a large temperature coefficient of resistivity with respect to the noble metal of the second thin strip element and the second thin strip element, preferably an alloy consisting essentially of 8l2 weight percent W, balance Pt, having a large strain coefficient of resistivity with respect to the first or in the form of an array consisting of the strain sensitive element, 8l2 weight percent W, balance Pt, and a sputtered Pt/Pt-Rh thermocouple located near the center of the strain sensitive element. To reduce the rate of oxidation of the Pt-W alloy element above app.oximately l500F. a protective layer of aluminum oxide or calcium stabilized zirconia may be provided, preferably by RF sputtering thereover.
The basic method disclosed herein is particularly useful for overcoating gas turbine components to provide increased resistance to sulfidation as well as to high temperature ox dat on. In order to reduce or prevent further growth of the aluminum oxide layer on the component, an electric field is superimposed across the aluminum oxide layer with the noble metal layer as the anode and the substrate as the cathode.
RIEF DESCRIPTION OF THE DRAWINGS An understanding of the invention will become more apparent to those skilled in the art by reference to the following detailed description when viewed in light of the accompanying drawings, wherein:
FIG. 1(a) is a plan view showing noble metal test elements on a flat disk;
FIG. 1(b) is a plan view showing an incomplete fourjunction sensor on a flat disk;
FIG. He) is a plan view showing a completed fourjunction sensor on a flat disk;
FIG. 1(d) is a side elevational view of a threejunction sensor array on an erosion bar;
FIG. 2 is a chart showing sensor accuracy;
FIGS. 3(a) and 3(b) are perspective views of a turbine blade having large scale sensor arrays on their surface;
FIGS. 4(a) and 4(b) are diagrammatic plan views of small scale sensor arrays near cooling holes;
FIG. 5 is a diagrammatic plan view ofa two-element strain sensor; and
FIG. 6 is a perspective view, partly cross-sectionally enlarged, ofa turbine component showing the imposition of an electric field across the oxide coating.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The nickel-base, cobalt-base and iron-bas gas turbine engine alloys are those strong, high temperature materials suitable for use in gas turbine engine applications. Typical of the alloys which may be coated according to the present invention are the so-called nickei-base and cobalt-base superalloys, viz., those which generally contain 5-25 weight percent Cr, 5-15 weight percent Mo, Ta or W and 2-8 weight percent Al and Ti. Also useful as substrates are the high temperature iron-base alloys such as the austenitic stainless steels or Kanthal A (5.5 Al, 22 Cr, balance Fe).
In the production of surface temperature sensors on gas turbine engine components, the first step is the deposition of an initial layer of an alloy onto a gas turbine engine alloy substrate. The initial layer is any rare earth or rare earth particle-containing alloy which can form an adherent irregular aluminum oxide. In general, the initial layer contains no more than approximately 2 percent, by weight, of the rare earth metal and approxi- 1.1ately 5-25 percent, by weight, aluminum and preferably consists of a coating such as NiCrAIY (20-35 weight percent Cr, 15-20 weight percent Al, 0.05-0.3 Y, balance Ni), CoCrAlY (19-24 weight percent Cr,
13-17 weight percent Al, 0.6-0.9 Y, balance Co), FeCrAlY (25-29 weight percent Cr, 12-14 weight percent Al, 0.6-0.9 Y, balance Fe) or an alloy such as 25 Cr, 15 Ni, 5 Ta, 5 A1, 0.1 Y, balance Co. In some cases it is desirable to use alloys with the same base metal in the substrate and initial layer, e.g., FeCrAlY with ironbase alloys, CoCrAlY with cobalt-base alloys, etc. However. in general. various combinations may be utilized. The initial layer thickness must only be thick enough to produce and maintain an adherent metal oxide, preferably approximately 0.5-5 mils. and may be deposited by conventional techniques as by sputtering or evaporation.
The second step in the construction of the coating is the mechanical working of the initial layer to induce the growth of an adherent metal oxide with an extremely irregular and angular topography. The subsequently deposited noble metal layer is primarily mechanically bonded to the initial layer and any method of surface preparation which will induce the growth of an irregular oxide will promote its mechanical adherence thereto. Grit blasting of the surface with various sizes of grit is considered a satisfactory technique. as is peening.
In the third step of the construction of the sensors, the initial layer is oxidized to produce a sufficiently thick and irregular oxide to promote the mechanical adherence of the noble metal layer, and to provide a sufficiently small number of paths through the oxide to the substrate to eliminate alloying between the initial layer and the noble metal layer. The oxide layer must be thin enough to permit rapid reoxidation of the specimen, provide oxide dimensions representative of the oxides grown in the turbine environment in order not to perturb the heat flow in the system and minimize the reduction of the turbine component life due to the oxidation treatment. It has been found that oxides from 0.05-0.l mil thick which are grown in air for generally 70-300 hours at I900F fulfill the above requirements. However, it will be appreciated that any oxidation treatment which produces an oxide dimension approximating the above range is considered suitable.
The next step comprises the deposition of a noble metal layer to form a noble metal thermocouple. By noble metal is meant such elements or alloys as those of platinum, rhodium or palladium. Each layer is deposited, preferably by sputtering, to a thickness sufficient to be stable and durable in harsh environments yet thin enough to permit oxygen diffusion through the layer in order to insulate it during the subsequent oxidation treatment described below. It has been established that noble metal thicknesses between 0.1 and 0.2 satisfy these requirements. The adherence of the noble metal layer increases with increasing sputtering substrate temperature. However, some uses of sensors require high resolution spacial distributions of thermocouple functions on the surface of a component and these sensor arrays are best obtained by low temperature masking procedures. Thus the entire range of sputtering substrate temperatures, from room temperature to the melting point of the substrate may be utilized.
The fifth step in the process is the electrical insulation of the noble metal layer from the substrate and the initial layer. It has been found that oxidation in air for approximately 30 hours at I900F is sufficient to achieve this result.
The last step in the construction of a sensor is the formation of relatively thick terminals at the ends of the sputtered noble metal leads to permit lead wires to be directly connected, as by spot welding. thereto. Terminal thicknesses between 0.2-0.5 mil are sufficient to obtain a durable connection between the sensors and 0.003 mil diameter lead wires. The width of the terminals is smaller than the original width of the sputtered leads to prevent loss of the electrical insulation of the sensor.
As discussed in the following specific example, surface temperature sensors made according to the present invention have provided metal surface temperatures from 0F to the melting point of several nickel-, cobaltor iron-base alloys with the accuracy of special grade platinum/platinum-rhodium thermocouples. The presence of the sensor on the surface of a component did not significantly perturb the heat flow from the gas stream to the component or the heat flow within the component. The bandwidth of information was limited only by the relative amplitudes of the signal and the equivalent input noise of the associated electronics. In general, useful information may be received over a several kilohertz bandwidth. Tests indicated that the sensors are usually durable.
Example Simple sensor elements 10 on flat disks l2 and an erosion bar 14 are shown in FIG. 1. The flat disks comprised a substrate of the nickel-base alloy B1900 (nominal composition, by weight percent, 8 Cr, 10 Co, 1 Ti, 6 Al, 6 Mo, 0.l l C, 4.3 Ta, 0.15 B, 0.07 Zr, balance Ni) and a sputtered initial layer three mils thick of FeCr- AlY which had been mechanically worked by a No. 320 grit blast and subsequently oxidized in air for hours at 1900F to grow an aluminum oxide 0.1 mil thick. Platinum test elements 16, 40 mils wide, 750 mils long and 0.l mil thick were sputtered on the flat disk 12 shown in FIG. 1(a). The platinuml 0 weight percent rhodium elements 18 of a fourjunction sensor array were sputtered on the flat disk as shown in FIG. 1(b) followed by the sputtering of a platinum element 20 across the Pt-10 percent Rh elements 18 to complete the sensor as shown in FIG. 1(c). FIG. 1(d) shows a three-junction sensor array on an erosion bar. As will be appreciated, any desirable array of thermoelectric junctions can be sputtered on a turbine component. Since the initial layer coating and oxide are common to high temperature turbine components, the only real change in the component configuration is due to the sputtered noble metal layer having a thickness of 0.0001-0.0002 inch. The platinum and platinumrhodium elements of FIG. 1 do not significantly affect the heat flow from the gas stream to the component or the heat flow within the component. For example, the narrowband (steady state) thermal impedance of a 0.000! inch platinum element is 2.14 X 10 of the boundary layer impedance when h 1000 BTU/ft hrR. In addition, the thickness of the noble metal layer is small with respect to the thickness of the boundary layer and therefore does not alter the structure of the boundary layer. The platinum element narrowband impedance is 7.5 X 10 of the impedance of a 0.050 inch section of a nickel-base alloy. The broadband response near the turbine component surface is limited by the oxide layer. At 15 khz, a harmonic temperature wave travelling across a 0.0001 inch oxide layer is attenuated to He of the initial amplitude of the wave at the surface. At the same frequency, the reduction in wave amplitude across the sensor is less than six percent. Therefore, the sensor elements do not affect narrowband or broadband measurements; the useful bandwidth of the information is determined by the relative amplitudes of the signal and the equivalent input noise of the associated electronics.
It will be appreciated that the width of the sputtered sensors is extremely small, in this case over 300 times smaller than the width of conventional thermocouples used by placement in slots in airfoils to measure temperatures near the airfoil surfaces. The sputtered sensor width is over I times smaller than the conventional strain and temperature sensors presently applied externally to airfoil surfaces.
The measurement errors of sputtered sensors of the present invention were maintained within the limits of error for special grade Pt/Pt-Rh thermocouples. A comparison of the thermoelectric voltage generated by a sputtered Pt/Pt-IO percent Rh sensor like the one shown in FIG. 1(c) and a special grade Pt/Pt-IO percent Rh thermocouple is presented in FIG. 2. The specimen was cycled from room temperature to 2000F in random temperature intervals for two months. At each temperature, the specimen and standard thermocouple were equilibriated for at least four hours before the temperature was measured. The indicated errors are within those expected between different special grade Pt/Ptl0 percent Rh thermocouples. There appear to be no extraordinary errors associated with the sputtered sensors.
Durability of the sensors of the instant invention was proven. During several months of testing, no indication of signal deterioration due to extended exposure at high temperatures was observed. In one experiment a sensor was gradually cycled from 2000F to room temperature for two months. The specimen holder failed but the sensor itself remained intact.
Platinum test elements such as those shown in FIG. 1(a) were cycled several hundred times from 2000F to room temperature in a stationary gas. The thermal cycling had no effect on the test elements which remained electrically insulated from the substrate and strongly bonded to the substrate oxide. In another experiment a Pt/Pt-IO percent Rh sensor sputtered on a rod was cycled over 5000 times from l800F to room temperature in a moderate velocity gas stream (Ma 05). Although the substrate was extensively cracked and plastically deformed causing a loss of electrical insulation between the sensor and the substrate, the sensor remained strongly bonded to the substrate oxide.
The sensors of the present invention are able to withstand extensive gradual or rapid plastic deformation. In one series of tests, platinum test elements sputtered on flat disks such as those of FIG. 1(a) were deformed approximately IO percent to concave and convex shapes, yet remained attached to the substrate and electrically insulated therefrom. The sensors can be quite heavily scratched or abraded. Even if the units are inordinately handled so that a loss of insulation between the sensor elements and the substrate results, they may be re paired by reoxidizing the components. In one example, a platinum test element was struck repeatedly with a ballpeen hammer so that the sensor element was grounded to the substrate. The element was nevertheless subsequently electrically insulated from the substrate by oxidizing the component for 20 hours at 1900F.
Overall, the surface temperature sensors of the present invention provide data which cannot be obtained by state-of-the-art techniques of the gas turbine industry. The sensor units provide steady state temperatures of the external surfaces of both static or rotating components either in or out of the gas path. Sensor arrays to measure large-scale span and radial temperature dis tributions are shown in FIGS. 3(a) and 3(b). Sma|lscale sensor arrays to obtain local surface temperatures near an individual cooling hole are shown in FIGS. 4(a) and 4(b). In either case, the sensors provide the actual surface temperatures in the engine and, correspondingly, detailed experimental evaluations of the present analytical models of heat transfer in the engine.
Due to the rugged nature of the sensors, the units may be applied to surfaces of details or subassemblies prior to final fabrication steps. For example, internal surface temperatures of a split blade may be obtained by application to the internal surfaces of each half before the halves are bonded together. Large-scale heat flows in the blade can be obtained from combinations of internal and external surface sensor arrays.
The sensor units provide broadband surface temperatures and the surface temperature fluctuations important to turbine component oxidation may be obtained. Arrays of the sensors provide broadband correlations between temperature fluctuations at different locations on an airfoil. Direct, broadband evidence of the location, stability and efficiency of transpiration cooling jets may also be obtained.
The present invention also contemplates the production of two element strain sensors for use in gas turbines. A typical array is shown in FIG. 5. The process steps for making the two-element strain sensor include the six steps described above for the surface tempera ture sensors except that the sputtering of the noble metal layer is done with two different metals to form separately the first thin strip element 22 and the second thin strip element 24. The first element 22 must have a large temperature coefficient of resistivity relative to the second element and is preferably platinum while the second element must have a large strain coefficient of resistivity relative to the first element and is preferably a platinum alloy containing 8-12 weight percent tungsten. Alternatively, the strain sensor may be constructed with a strain sensitive element as described and a sputtered Pt/Pt-Rh thermocouple located near the center of the strain sensitive element. To reduce the rate of oxidation of the Pt-W alloy element above approximately l500F, a protective layer of aluminum oxide or calcium stabilized zirconia is deposited, preferably by sputtering, to a minimum thickness sufficient to protect the sensor element from the environment, e.g., to 0.1-0.5 mil.
In addition to the utilization of the basic five-step procedure for producing surface temperature sensors, surface strain sensors and a simple gas turbine component coating for protection against sulfidation, it may be utilized, with the addition of a step wherein an electric field is superimposed across the oxide to prevent high temperature oxidation. The field acts to cancel the electromechanical gradient which occurs naturally within the oxide and which provides the driving force for cation and/or anion motion in the oxide. The noble metal layer, preferably platinum, is the anode and the metallic coating is the cathode which is at the engine ground potential as shown in FIG. 6. Fields on the order of 10 volts/cm are sufficient to reduce the rate of oxidation. In one test, it was experimentally ob served that a one volt potential across a l u lcm) oxide significantly reduces the rate of oxidation. A specimen having a FeCrAlY coating was prepared with No. 320 grit blast and preoxidized for 24 hours at 2000F. Three 0.1 mil Pt electrodes were sputtered on the oxidized surface and the specimen was rcoxidized for 24 hours at 2000F. Positive and negative potentials were applied to two electrodes and the specimens were again oxidized. After an oxidation of 120 hours at 2000F in the presence of the electric fields, the specimens were cross sectioned and measurements were made of the oxides beneath each electrode including the electrode to which no voltage had been applied. The results indicated that with the platinum electrode as the anode, a field of approximately 8 X volts/cm reduced the rate of oxidation by a factor of two whereas with the platinum electrode as the cathode, a field of approximately 1.2 X 10 volts/cm increased the rate of oxidation by a factor of three.
It was determined that with the noble metal layer as the anode, the rate of oxidation decreases as the voltage increases until the electrochemical gradient and the opposing electrical field balance and oxidation ceases. The voltage at which oxidation ceases should be the voltage equivalent of the change in free energy of the oxidation reaction which, in the case of aluminum oxide, is approximately 2.1 volts.
What has been set forth above is intended primarily as exemplary to enable those skilled in the art in the practice of the invention and it should therefore be understood that, within the scope of the appended claims, the invention may be practiced in other ways than as specifically described.
What is claimed is:
1. In a method for coating nickel-base, cobalt-base or iron-base gas turbine engine alloy substrates having an initial rare earth and aluminum-containing nickel, cobaltor iron-base alloy coating approximately 0.5-5.0 mils thick thereon, said initial coating containing no more than 2%, by weight, rare earth metal and approximately 5-257r, by weight, aluminum, the improvement which comprises:
mechanically working the surface of said initial layer to induce irregularity and angular topography in the aluminum oxide to be produced; oxidizing said initial layer to produce an irregular aluminum oxide layer approximately 0.05-0.l mil thick to promote mechanical adherence of a noble metal layer and to prevent alloying between said initial layer and said noble metal layer;
depositing a noble metal layer selected from the group consisting of platinum, rhodium, palladium and alloys thereof on said oxidized initial layer to a thickness of approximately 0.1-0.2 mil; and
oxidizing said coated substrate to cause additional growth of said oxidized initial layer to metallurgically insulate said noble metal layer from said substrate and said initial layer.
2. A method of coating an alloy substrate selected from the group consisting of the nickel-base, cobaltbase and iron-base gas turbine engine alloys comprisdepositing an initial rare earth and aluminumcontaining alloy layer on said substrate to a thickness of approximately 0.5-5.0 mils, said initial layer being an alloy selected from the group consisting of, by weight, 2035% Cr, 15-20% Al, ODS-0.3% Y, balance Ni; 19-24% Cr, 13-17% A], 0.60.9% Y, balance Co; 25-29% Cr, 12-14% Al, 06-09% Y, balance Fe; and 25% Cr, 15% Ni, 5% Ta, 5% A1, 0.1% Y, balance Co;
mechanically working the surface of said initial layer to induce irregularity and angular topography in the aluminum oxide layer to be produced;
oxidizing said initial layer to produce an irregular aluminum oxide layer approximately 0.05O.l mil thick to promote mechanical adherence of a noble metal layer and to prevent alloying between said initial layer and said noble metal layer; depositing a noble metal layer selected from the group consisting of platinum, rhodium, palladium and alloys thereof on said oxidized initial layer to a thickness of approximately 0.1-0.2 mil; and
oxidizing said coated substrate to cause additional growth of said oxidized initial layer to metallurgically insulate said noble metal layer from said substrate and said initial layer.
3. The method of claim 2 wherein said mechanical working comprises grit blasting.
4. The method of claim 2 wherein said mechanical working comprises peening.
5. The method of claim 2 wherein said initial layer is heated in air at approximately 1900F for -3100 hours,
6. The method of claim 5 wherein said noble metal layer is deposited by sputtering.
7. The method of claim 6 wherein said noble metal layer is deposited in the form of a thin strip array of thermoelectric junctions with thickened end portions suitable for use as terminal connections whereby said coating acts as a surface temperature sensor.
8. The method of claim 7 wherein said noble metal layer is deposited in an array of first and second thin strip elements, said first thin strip element having a large temperature coefficient of resistivity with respect to the second thin strip element and said second thin strip element having a large strain coefficient of resistivity with respect to the first whereby said coating acts as a surface strain sensor.
9. The method of claim 8 wherein platinum is deposited as the first thin strip element and an alloy consisting essentially of 8-12 weight percent tungsten, balance platinum is deposited as the second thin strip ele ment.
10. The invention of claim 9 wherein said second thin strip element is coated with a protective oxide layer selected from the group consisting of aluminum oxide and calcium stabilized zirconia.
11. The method of claim 7 wherein said noble metal layer is deposited in the form of a thin strip element having a large strain coefficient of resistivity and a ther mocouple adjacent the center of the thin strip element.
12. The method of claim 6 wherein an electric field is imposed across the aluminum oxide layer to prevent further growth thereof, said noble metal layer being the anode and said substrate being the cathode therefor.
13. The method of claim 12 wherein a voltage potential of approximately 2.1 volts is impressed across said aluminum oxide layer.
14. In a coating for the nickel-base, cobalt-base and to said first metal alloy layer, said aluminum oxide iron-base gas turbine engine alloys having a first rare layer having an irregular surface; and earth and aluminum-containing nickel-, cobaltor irona noble metal layer selected from the group consistbase alloy layer approximately 0.55.0 mils thick, said ing of platinum, rhodium, palladium and alloys layer containing up to 2%, by weight, rare earth metal 5 thereof approximately 0.1-0.2 mil thick mechaniand approximately, 5-25%, by weight. aluminum, the cally bonded, by virtue of said irregular surface, to improvement which comprises: said aluminum oxide layer.
a layer of aluminum oxide 005-0.] mil thick bonded

Claims (14)

1. IN A METHOD FOR COATING NICKEL-BASE, COBALT-BASE OR IRONBASE GAS TURBINE ENGINE ALLOY SUBSTRATES HAVING AN INITIAL RARE EARTH AND ALUMINUM-CONTAINING NICKEL-, COBALT- OR IRON-BASE
2. A method of coating an alloy substrate selected from the group consisting of the nickel-base, cobalt-base and iron-base gas turbine engine alloys comprising: depositing an initial rare earth and aluminum-containing alloy layer on said substrate to a thickness of approximately 0.5-5.0 mils, said initial layer being an alloy selected from the group consisting of, by weight, 20-35% Cr, 15-20% Al, 0.05-0.3% Y, balance Ni; 19-24% Cr, 13-17% Al, 0.6-0.9% Y, balance Co; 25-29% Cr, 12-14% Al, 0.6-0.9% Y, balance Fe; and 25% Cr, 15% Ni, 5% Ta, 5% Al, 0.1% Y, balance Co; mechanically working the surface of said initial layer to induce irregularity and angular topography in the aluminum oxide layer to be produced; oxidizing said initial layer to produce an irregular aluminum oxide layer approximately 0.05-0.1 mil thick to promote mechanical adherence of a noble metal layer and to prevent alloying between said initial layer and said noble metal layer; depositing a noble metal layer selected from the group consisting of platinum, rhodium, palladium and alloys thereof on said oxidized initial layer to a thickness of approximately 0.1-0.2 mil; and oxidizing said coated substrate to cause additional growth of said oxidized initial layer to metallurgically insulate said noble metal layer from said substrate and said initial layer.
3. The method of claim 2 wherein said mechanicaL working comprises grit blasting.
4. The method of claim 2 wherein said mechanical working comprises peening.
5. The method of claim 2 wherein said initial layer is heated in air at approximately 1900*F for 70-300 hours.
6. The method of claim 5 wherein said noble metal layer is deposited by sputtering.
7. The method of claim 6 wherein said noble metal layer is deposited in the form of a thin strip array of thermoelectric junctions with thickened end portions suitable for use as terminal connections whereby said coating acts as a surface temperature sensor.
8. The method of claim 7 wherein said noble metal layer is deposited in an array of first and second thin strip elements, said first thin strip element having a large temperature coefficient of resistivity with respect to the second thin strip element and said second thin strip element having a large strain coefficient of resistivity with respect to the first whereby said coating acts as a surface strain sensor.
9. The method of claim 8 wherein platinum is deposited as the first thin strip element and an alloy consisting essentially of 8-12 weight percent tungsten, balance platinum is deposited as the second thin strip element.
10. The invention of claim 9 wherein said second thin strip element is coated with a protective oxide layer selected from the group consisting of aluminum oxide and calcium stabilized zirconia.
11. The method of claim 7 wherein said noble metal layer is deposited in the form of a thin strip element having a large strain coefficient of resistivity and a thermocouple adjacent the center of the thin strip element.
12. The method of claim 6 wherein an electric field is imposed across the aluminum oxide layer to prevent further growth thereof, said noble metal layer being the anode and said substrate being the cathode therefor.
13. The method of claim 12 wherein a voltage potential of approximately 2.1 volts is impressed across said aluminum oxide layer.
14. In a coating for the nickel-base, cobalt-base and iron-base gas turbine engine alloys having a first rare earth and aluminum-containing nickel-, cobalt- or iron-base alloy layer approximately 0.5-5.0 mils thick, said layer containing up to 2%, by weight, rare earth metal and approximately, 5-25%, by weight, aluminum, the improvement which comprises: a layer of aluminum oxide 0.05-0.1 mil thick bonded to said first metal alloy layer, said aluminum oxide layer having an irregular surface; and a noble metal layer selected from the group consisting of platinum, rhodium, palladium and alloys thereof approximately 0.1-0.2 mil thick mechanically bonded, by virtue of said irregular surface, to said aluminum oxide layer.
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US4446199A (en) * 1982-07-30 1984-05-01 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Overlay metallic-cermet alloy coating systems
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US3957608A (en) * 1974-01-15 1976-05-18 Cockerill-Ougree-Providence Et Esperance-Longdoz, En Abrege "Cockerill" Process for the surface oxidisation of aluminum
USRE33876E (en) * 1975-09-11 1992-04-07 United Technologies Corporation Thermal barrier coating for nickel and cobalt base super alloys
US4248940A (en) * 1977-06-30 1981-02-03 United Technologies Corporation Thermal barrier coating for nickel and cobalt base super alloys
US4399199A (en) * 1979-02-01 1983-08-16 Johnson, Matthey & Co., Limited Protective layer
US4414249A (en) * 1980-01-07 1983-11-08 United Technologies Corporation Method for producing metallic articles having durable ceramic thermal barrier coatings
US4321310A (en) * 1980-01-07 1982-03-23 United Technologies Corporation Columnar grain ceramic thermal barrier coatings on polished substrates
US4321311A (en) * 1980-01-07 1982-03-23 United Technologies Corporation Columnar grain ceramic thermal barrier coatings
US4401697A (en) * 1980-01-07 1983-08-30 United Technologies Corporation Method for producing columnar grain ceramic thermal barrier coatings
US4405660A (en) * 1980-01-07 1983-09-20 United Technologies Corporation Method for producing metallic articles having durable ceramic thermal barrier coatings
US4405659A (en) * 1980-01-07 1983-09-20 United Technologies Corporation Method for producing columnar grain ceramic thermal barrier coatings
WO1981001983A1 (en) * 1980-01-07 1981-07-23 United Technologies Corp Columnar grain ceramic thermal barrier coatings on polished substrates
WO1981001982A1 (en) * 1980-01-07 1981-07-23 United Technologies Corp Columnar grain ceramic thermal barrier coatings
US4477538A (en) * 1981-02-17 1984-10-16 The United States Of America As Represented By The Secretary Of The Navy Platinum underlayers and overlayers for coatings
US4451496A (en) * 1982-07-30 1984-05-29 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Coating with overlay metallic-cermet alloy systems
US4446199A (en) * 1982-07-30 1984-05-01 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Overlay metallic-cermet alloy coating systems
US4741975A (en) * 1984-11-19 1988-05-03 Avco Corporation Erosion-resistant coating system
US4761346A (en) * 1984-11-19 1988-08-02 Avco Corporation Erosion-resistant coating system
US4851300A (en) * 1988-05-09 1989-07-25 United Technologies Corporation Precoat for improving platinum thin film adhesion
US4854196A (en) * 1988-05-25 1989-08-08 General Electric Company Method of forming turbine blades with abradable tips
US5215597A (en) * 1989-08-08 1993-06-01 The United States Of America As Represented By The United States Department Of Energy Method for bonding thin film thermocouples to ceramics
US5077140A (en) * 1990-04-17 1991-12-31 General Electric Company Coating systems for titanium oxidation protection
EP0471505A2 (en) * 1990-08-11 1992-02-19 Johnson Matthey Public Limited Company Coated article, its use and method of making the same
EP0471505B1 (en) * 1990-08-11 1996-10-02 Johnson Matthey Public Limited Company Coated article, its use and method of making the same
US5267605A (en) * 1990-09-06 1993-12-07 Doty Scientific, Inc. Microtube array space radiator
EP0679733A2 (en) * 1994-03-25 1995-11-02 Johnson Matthey Public Limited Company Coated article
EP0679733A3 (en) * 1994-03-25 1996-12-04 Johnson Matthey Plc Coated article.
US5756223A (en) * 1994-03-25 1998-05-26 Johnson Matthey Public Limited Company Coated article
US5484263A (en) * 1994-10-17 1996-01-16 General Electric Company Non-degrading reflective coating system for high temperature heat shields and a method therefor
US5545437A (en) * 1994-10-17 1996-08-13 General Electric Company Method for forming a non-degrading refective coating system for high temperature heat shields
US5817371A (en) * 1996-12-23 1998-10-06 General Electric Company Thermal barrier coating system having an air plasma sprayed bond coat incorporating a metal diffusion, and method therefor
US6020075A (en) * 1996-12-23 2000-02-01 General Electric Company Thermal barrier coating system
US6261422B1 (en) * 2000-01-04 2001-07-17 Ionica, Llc Production of hollowed/channeled protective thermal-barrier coatings functioning as heat-exchangers
US6607789B1 (en) 2001-04-26 2003-08-19 General Electric Company Plasma sprayed thermal bond coat system
US20040202886A1 (en) * 2002-09-23 2004-10-14 Siemens Westinghouse Power Corporation Method and apparatus for instrumenting a gas turbine component having a barrier coating
US6838157B2 (en) * 2002-09-23 2005-01-04 Siemens Westinghouse Power Corporation Method and apparatus for instrumenting a gas turbine component having a barrier coating
US7270890B2 (en) 2002-09-23 2007-09-18 Siemens Power Generation, Inc. Wear monitoring system with embedded conductors
US20050198967A1 (en) * 2002-09-23 2005-09-15 Siemens Westinghouse Power Corp. Smart component for use in an operating environment
US20050287386A1 (en) * 2002-09-23 2005-12-29 Siemens Westinghouse Power Corporation Method of instrumenting a component
US7572524B2 (en) 2002-09-23 2009-08-11 Siemens Energy, Inc. Method of instrumenting a component
US9284647B2 (en) * 2002-09-24 2016-03-15 Mitsubishi Denki Kabushiki Kaisha Method for coating sliding surface of high-temperature member, high-temperature member and electrode for electro-discharge surface treatment
US9187831B2 (en) 2002-09-24 2015-11-17 Ishikawajima-Harima Heavy Industries Co., Ltd. Method for coating sliding surface of high-temperature member, high-temperature member and electrode for electro-discharge surface treatment
US20060035068A1 (en) * 2002-09-24 2006-02-16 Ishikawajima-Harima Heavy Industries Co., Ltd. Method for coating sliding surface of high-temperature member, high-temperature member and electrode for electro-discharge surface treatment
US20100086398A1 (en) * 2002-09-24 2010-04-08 Ihi Corporation Method for coating sliding surface of high-temperature member, high-temperature member and electrode for electro-discharge surface treatment
US20100124490A1 (en) * 2002-10-09 2010-05-20 Ihi Corporation Rotating member and method for coating the same
US20040101022A1 (en) * 2002-11-22 2004-05-27 General Electric Company Systems and methods for determining conditions of articles and methods of making such systems
US7004622B2 (en) * 2002-11-22 2006-02-28 General Electric Company Systems and methods for determining conditions of articles and methods of making such systems
EP1538432A1 (en) * 2003-11-13 2005-06-08 Harco Laboratories Inc. Extended temperature range thermal variable-resistance device
US7915994B2 (en) 2003-11-13 2011-03-29 Harco Laboratories, Inc. Thermal variable resistance device with protective sheath
US20050104712A1 (en) * 2003-11-13 2005-05-19 Habboosh Samir W. Extended temperature range thermal variable-resistance device
US20060139142A1 (en) * 2003-11-13 2006-06-29 Harco Laboratories, Inc. Extended temperature range heater
US7061364B2 (en) 2003-11-13 2006-06-13 Harco Labratories, Inc. Thermal variable resistance device with protective sheath
US20060202792A1 (en) * 2003-11-13 2006-09-14 Habboosh Samir W Thermal variable resistance device with protective sheath
US7026908B2 (en) 2003-11-13 2006-04-11 Harco Laboratories, Inc. Extended temperature range thermal variable-resistance device
US7782171B2 (en) 2003-11-13 2010-08-24 Harco Laboratories, Inc. Extended temperature range heater
EP1571431A1 (en) * 2004-03-04 2005-09-07 Harco Laboratories Inc. Thermal variable resistance device with protective sheath
US8004423B2 (en) 2004-06-21 2011-08-23 Siemens Energy, Inc. Instrumented component for use in an operating environment
US20100117859A1 (en) * 2004-06-21 2010-05-13 Mitchell David J Apparatus and Method of Monitoring Operating Parameters of a Gas Turbine
US20100226756A1 (en) * 2004-06-21 2010-09-09 Siemens Power Generation, Inc. Instrumented component for use in an operating environment
US8742944B2 (en) 2004-06-21 2014-06-03 Siemens Energy, Inc. Apparatus and method of monitoring operating parameters of a gas turbine
US20080054645A1 (en) * 2006-09-06 2008-03-06 Siemens Power Generation, Inc. Electrical assembly for monitoring conditions in a combustion turbine operating environment
US7368827B2 (en) 2006-09-06 2008-05-06 Siemens Power Generation, Inc. Electrical assembly for monitoring conditions in a combustion turbine operating environment
US7969323B2 (en) 2006-09-14 2011-06-28 Siemens Energy, Inc. Instrumented component for combustion turbine engine
US20100226757A1 (en) * 2006-09-14 2010-09-09 Siemens Power Generation, Inc. Instrumented component for combustion turbine engine
US9071888B2 (en) 2007-11-08 2015-06-30 Siemens Aktiengesellschaft Instrumented component for wireless telemetry
US8519866B2 (en) 2007-11-08 2013-08-27 Siemens Energy, Inc. Wireless telemetry for instrumented component
US20110133949A1 (en) * 2007-11-08 2011-06-09 Ramesh Subramanian Instrumented component for wireless telemetry
US8797179B2 (en) 2007-11-08 2014-08-05 Siemens Aktiengesellschaft Instrumented component for wireless telemetry
US20110133950A1 (en) * 2007-11-08 2011-06-09 Ramesh Subramanian Instrumented component for wireless telemetry
DE102008052380B4 (en) * 2008-10-20 2012-09-20 Siemens Aktiengesellschaft Turbine blade and turbine blade for a turbine and method for directly determining the erosion progress of a turbine blade
US8906181B2 (en) * 2011-06-30 2014-12-09 United Technologies Corporation Fan blade finishing
US20130058791A1 (en) * 2011-09-02 2013-03-07 General Electric Company Protective coating for titanium last stage buckets
US9267218B2 (en) * 2011-09-02 2016-02-23 General Electric Company Protective coating for titanium last stage buckets
US10392717B2 (en) 2011-09-02 2019-08-27 General Electric Company Protective coating for titanium last stage buckets
US9325388B2 (en) 2012-06-21 2016-04-26 Siemens Energy, Inc. Wireless telemetry system including an induction power system
US9420356B2 (en) 2013-08-27 2016-08-16 Siemens Energy, Inc. Wireless power-receiving assembly for a telemetry system in a high-temperature environment of a combustion turbine engine
US20170211185A1 (en) * 2016-01-22 2017-07-27 Applied Materials, Inc. Ceramic showerhead with embedded conductive layers

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