EP0266299B1 - Thermal barrier coating system - Google Patents

Thermal barrier coating system Download PDF

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Publication number
EP0266299B1
EP0266299B1 EP87630212A EP87630212A EP0266299B1 EP 0266299 B1 EP0266299 B1 EP 0266299B1 EP 87630212 A EP87630212 A EP 87630212A EP 87630212 A EP87630212 A EP 87630212A EP 0266299 B1 EP0266299 B1 EP 0266299B1
Authority
EP
European Patent Office
Prior art keywords
coating
bond coat
thermal barrier
ceramic
zirconia
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87630212A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0266299A3 (en
EP0266299A2 (en
Inventor
Raymond William Vine
Keith Douglas Sheffler
Charles Edward Bevan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RTX Corp
Original Assignee
United Technologies Corp
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Filing date
Publication date
Application filed by United Technologies Corp filed Critical United Technologies Corp
Publication of EP0266299A2 publication Critical patent/EP0266299A2/en
Publication of EP0266299A3 publication Critical patent/EP0266299A3/en
Application granted granted Critical
Publication of EP0266299B1 publication Critical patent/EP0266299B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides

Definitions

  • the present invention concerns a method of applying a durable thermal barrier coating to a metallic substrate and a sheet metal gas turbine combustor.
  • the present invention relates to plasma sprayed ceramic thermal barrier coatings used to protect substrates from elevated temperatures.
  • Gas turbine engines derive their thrust or other power output by the combustion of fuels. Since engine power and economy both improve with increased temperature, there has been a persistent trend in the gas turbine engine field toward increased engine operating temperatures. For many years this trend was accommodated by the development of improved materials. Whereas early gas turbine engines were based mainly on alloys derived from common steels, the modern gas turbine engine relies on nickel and cobalt base superalloys in many critical applications. It appears for the moment that property limits for metallic materials are being approached or perhaps have been reached, but the demand for increased temperature capability continues. While work is underway to develop ceramic turbine materials, this work is at a very preliminary stage and many difficulties must be overcome before ceramics play a structural role in gas turbine engines.
  • the currently favored ceramic constituent is zirconia, but because zirconia undergoes a phase transformation at about 982°C (1800°F), it is necessary to make additions to the zirconia to provide a stable or at least controlled microstructure at increasing temperature.
  • Patents which appear particularly pertinent to this subject area include US-A-4,055,705 which suggests a thermal barrier coating system using a NiCrAlY bond coat and a zirconia based ceramic coating which may contain, for example, 12% yttria for stabilization.
  • US-A-4,248,940 describes a similar thermal barrier coating, but with emphasis on the type of thermal barrier coating in which the composition of the coating is graded from 100% metal at the bond coat to 100% ceramic at the outer surface.
  • This patent describes the use of MCrAlY bond coats, including NiCoCrAlY, and mentions the use of yttria stabilized zirconia.
  • US-A-4,328,285 describes a ceramic thermal barrier coating using a CoCrAlY or NiCrAlY bond coat with ceria stabilized zirconia.
  • US-A-4,335,190 describes a thermal barrier coating in which a NiCrAlY or CoCrAlY bond coat has a sputtered coating of yttria stabilized zirconia on which is plasma sprayed a further coating of yttria stabilized zirconia.
  • US-A-4,402,992 describes a method for applying a ceramic thermal barrier coating to hollow turbine hardware containing cooling holes without blockage of the holes.
  • the specifics of the coating mentioned are a NiCrAlY or a CoCrAly bond coat with yttria stabilized zirconia.
  • US-A-4,457,948 describes a method for producing a favorable crack pattern in a ceramic thermal barrier coating to enhance its durability.
  • the coating mentioned has a NiCrAlY bond coat and a fully yttria stabilized zirconia coating.
  • US-A-4,485,151 describes another ceramic thermal barrier coating in which the bond coat comprises NiCrAlY or CoCrAlY, but wherein the yttrium constituent may be replaced by ytterbium.
  • the ceramic constituent is partially yttria or ytterbium stabilized zirconia.
  • US-A-4,535,033 is a continuation-in-part application of the previously mentioned US-A-4,485,151 and deals with a ceramic thermal barrier coating in which zirconia is stabilized by ytterbia.
  • the method of applying a thermal barrier coating of the present invention is defined as shown in claim 1.
  • the sheet metal gas turbine combustor of the present invention is defined as shown in claim 2. It is an object of this invention to disclose a ceramic thermal barrier coating having surprisingly enhanced durability relative to similar ceramic thermal barrier coatings known in the art.
  • a NiCoCrAlY bond coat is plasma sprayed, in air, on the surface of the substrate to be protected, after the substrate surface has been properly prepared.
  • the ceramic consists of yttria partially stabilized zirconia, containing about 7% yttria to provide the proper degree of stabilization, plasma sprayed in air on the previously applied NiCoCrAlY bond coat.
  • the resultant coating has surprisingly enhanced durability relative to similar thermal barrier coatings which employ other types of MCrAlY bond coats and ceramic top coats.
  • the use of 7% yttria stabilized zirconia permits the coating to be used at elevated temperatures compared to other thermal barrier coatings which have employed other zirconia stabilizers or other amounts of yttria.
  • the use of air plasma spraying as opposed to low pressure chamber plasma spraying eliminates substrate preheating and post spray heat treatment.
  • the invention is particularly pertinent to coating of sheet metal parts which are prone to distortion in heat treatment.
  • Figure 1 is a bar chart depicting the hours to failure in cyclic testing at 1107°C (2025°F) of various combinations of metallic bond coats and ceramic outer coatings applied to sheet metal samples.
  • Figure 2 is a schematic drawing of a gas turbine combustion chamber.
  • Figure 1 depicts the relative life of several different ceramic thermal barrier coatings in a very severe test performed at 1107°C (2025°F).
  • the test comprised a six-minute thermal cycle in which the coated substrate (a sheet metal sample) was heated from 93°C to 1107°C (200°F to 2025°F) in two minutes, held for two minutes at 1107°C (2025°F) and was then forced air cooled in two minutes back down to 93°C (200°F).
  • This illustrates the time to failure in hours, the number of cycles is obtained by multiplying the number of hours by 10.
  • the left-most bar (A) on the chart is a coating which has been used commercially in gas turbine engines at temperatures up to 982°C (1800°F).
  • This coating consists of zirconia (fully) stabilized with about 21% magnesia applied on a CoCrAlY (23%Cr, 13%Al, .65%Y bal Co) bond coat.
  • the left-most coating is a graded coating so that the CoCrAlY composition diminishes through the thickness of the coating from 100% at the bond coat to 0% at the outer coat at the outer surface.
  • the remaining coatings on the chart are non-graded two-layer coatings.
  • the graded coating (A) which displays the shortest life, failed in the graded portion of the coating as a consequence of oxidation of the finely divided metallic constituent which causes swelling of the coating and subsequent spallation.
  • This coating fails in an abnormally short time because of the nature of the coating failure and the severe test conditions, the coating has a normal maximum use temperature of 982°C (1800°F).
  • the next bar (B) on the chart comprises the same ceramic constitutent, zirconia stabilized with 21% magnesia, but this is a two-layer coating in which a 100% ceramic layer is applied to a bond coat.
  • the bond coat is a simple alloy of nickel-22 weight percent aluminum.
  • the third bar (C) on the chart uses the same 21% magnesia stabilized zirconium on a NiCoCrAlY bond coat (nominal composition 23%Co, 17%Cr, 12.5%Al, 0.45%Y bal Ni). This coating had both the bond coat and the ceramic layer deposited by plasma spraying in air. Interestingly enough, the third coating on the chart displays about a 2x improvement in life over the previously mentioned 21% MgO stabilized zirconia coating on Ni-22%Al coating illustrating that the bond coat does affect coating performance.
  • All of the coatings based on 21% magnesia stabilized zirconia appear to fail as a result of destabilization of the ceramic over time by volatilization of the less stable magnesia material at elevated temperatures and/or the effects of microscopic thermal mechanical stresses/racheting with the ultimate formation of the monoclinic crystalline phase of zirconia at temperatures in excess of 1038°C (1900°F).
  • the monoclinic crystal phase is the non-thermal cyclable zirconia that is unstable in gas turbine applications.
  • the last two coatings described in the figure used zirconia partially stabilized with about 7% yttria, this type of stabilized zirconia does not undergo thermal degradation until temperatures in excess of 1204°C (2200°F) are encountered.
  • the fourth bar (D) on the chart uses the 7% yttria partially stabilized zirconia on a NiCoCrAlY (23%Co, 17%Cr, 12.5%Al, 0.45%Y bal Ni) bond coat, but differs from the other coatings in that the metallic constituents were applied by low-pressure plasma spraying, spraying in a chamber in which the gas pressure was reduced to 665 Pa (5 millimeters of mercury) before spraying.
  • This type of low pressure plasma spraying has been shown in the past to provide substantially enhanced thermal barrier coatings containing less oxides and porosity in the metallic bond coating and having better integrity and adherence.
  • One feature of chamber spraying is that the substrate must be preheated to 871°C-982°C (1600°F-1800°F) before spraying.
  • FIG. 2 is a schematic illustration of a gas turbine combustor.
  • plasma spraying metallic bond coating such as NiCoCrAlY, under reduced atmospheric pressures leads to the formation of a weak metallic substrate-metallic bond coating interface which requires a post high temperature heat treatment to form a metallurgical bond between the substrate and bond coat.
  • the heat treatment means that sheet metal constituents which are prone to warpage cannot receive this type of coating.
  • the final bar (E) on the chart illustrates the invention coating performance. It can be seen that the invention coating performance is fully equivalent to that of the best prior coating despite the fact that the invention coating is applied in air and does not receive any subsequent heat treatment.
  • the present invention derives some of its beneficial attributes from the use of the NiCoCrAlY bond coat. This appears to be the case despite the fact that failure occurs in the ceramic coating rather than at the interface between the bond coat and the ceramic coating.
  • the exact mechanism by which the use of a NiCoCrAlY bond coat benefits coating performance is not fully understood, but is undoubtedly related to the enhanced ductility of NiCoCrAlY coatings (as described in US-A-3,928,026) relative to the NiCrAlY and CoCrAlY bond coats which the art has generally favored up until now.
  • the ceramic constituent of the present invention namely, zirconia stabilized with 6% to 8% yttria
  • zirconia stabilized with 6% to 8% yttria is more durable than some of the zirconia coatings which the prior art has used which have been stabilized to different degrees by different additions.
  • This can be seen on the graph by the comparison between the magnesia stabilized zirconia and yttria stabilized zirconia, both of which were applied on a NiCoCrAlY bond coat.
  • Other testing indicates that, tested at 1093°C (2000°F), 7% yttria stabilized zirconia is about twice as durable as 12% yttria stabilized zirconia and about 5x as durable as 20% yttria (fully) stabilized zirconia.
  • the present invention can be applied to superalloy substrates as follows. There is generally no limit on the substrate composition provided, of course, it has the requisite mechanical properties at the intended use temperature.
  • the substrate surface must be clean and properly prepared and this is most easily accomplished by grit blasting the surface to remove all oxide and other contaminants and to leave behind a slightly roughened surface of increased surface area to enhance bonding of the metallic bond coat to the substrate.
  • the bond coat is applied to the substrate by plasma spraying.
  • the plasma spray parameters are the same as those described below for the ceramic constituent.
  • the bond coat material is NiCoCrAlY having a composition falling within the following range 15-40%Co, 10-40%Cr, 6-15%Al, 0-7%Si, 0-2.0%Hf, 0.01-1.0%Y, bal essentially Ni and has a particle size which is preferably within the range 0.044-0.088 mm (-170+325 US std. sieve).
  • the bond coat has a thickness of from 0.076-0.38 mm (0.003-0.015 inches). There is no benefit to be obtained by any increase in bond coat thickness.
  • any bond coat thickness less than about 0.076 mm (0.003 inch) is risky because plasma sprayed coatings of thicknesses much less than about 0.076 mm (0.003 inch) tend to leave exposed substrate areas and the ceramic coating will not properly bond to the exposed substrate. This leads to early catastrophic coating failure by spallation.
  • the plasma spraying of the bond coat to the prepared substrate surface is preferably performed in a timely fashion and preferably no more than about two hours elapses to minimize the possibility of substrate surface contamination, for example, by oxidation.
  • the bond coat coated substrates are then adapted to receive a coating of zirconia stabilized with 6%-8% yttria.
  • the particle size to be sprayed is 60 ⁇ m (micron) (avg)
  • the power flow rate is 50 gm/min
  • the plasma spraying conditions are 35 volts and 800 amps using a mix of argon helium as a carrier gas in a Plasmadyne gun held about 7.6 cm (3 inches) from the surface and translated about 22.2 m/min (74 ft/min) relative to the surface.
  • the application of the ceramic coating to the bond coated substrate is preferably performed within about two hours so as to minimize contamination and other problems.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Laminated Bodies (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
EP87630212A 1986-10-30 1987-10-26 Thermal barrier coating system Expired - Lifetime EP0266299B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US925654 1978-07-17
US92565486A 1986-10-30 1986-10-30

Publications (3)

Publication Number Publication Date
EP0266299A2 EP0266299A2 (en) 1988-05-04
EP0266299A3 EP0266299A3 (en) 1989-05-31
EP0266299B1 true EP0266299B1 (en) 1992-05-13

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ID=25452045

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87630212A Expired - Lifetime EP0266299B1 (en) 1986-10-30 1987-10-26 Thermal barrier coating system

Country Status (8)

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EP (1) EP0266299B1 (es)
JP (1) JP2826824B2 (es)
AU (1) AU594521B2 (es)
CA (1) CA1330638C (es)
DE (2) DE3779045D1 (es)
IL (1) IL84067A (es)
MX (1) MX169998B (es)
SG (1) SG76592G (es)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990002825A1 (en) * 1988-09-06 1990-03-22 Battelle Memorial Institute Metal alloy coatings and methods for applying
US4936745A (en) * 1988-12-16 1990-06-26 United Technologies Corporation Thin abradable ceramic air seal
IL99473A0 (en) * 1990-09-20 1992-08-18 United Technologies Corp Columnar ceramic thermal barrier coating with improved adherence
DE4103994A1 (de) * 1991-02-11 1992-08-13 Inst Elektroswarki Patona Schutzueberzug vom typ metall-keramik fuer einzelteile aus hitzebestaendigen legierungen
EP0526670B1 (en) * 1991-06-21 1995-10-25 Praxair S.T. Technology, Inc. Duplex coatings for various substrates
US5320879A (en) * 1992-07-20 1994-06-14 Hughes Missile Systems Co. Method of forming coatings by plasma spraying magnetic-cerment dielectric composite particles
WO1995022635A1 (en) * 1994-02-16 1995-08-24 Sohl, Charles, E. Coating scheme to contain molten material during gas turbine engine fires
KR100354411B1 (ko) * 1994-10-14 2002-11-18 지멘스 악티엔게젤샤프트 부식,산화및과도한열응력으로부터부품을보호하기위한보호층및그제조방법
DE69707365T2 (de) * 1996-06-27 2002-07-11 United Technologies Corp., Hartford Isolierendes, wärmedämmendes Beschichtungssystem
GB9617267D0 (en) * 1996-08-16 1996-09-25 Rolls Royce Plc A metallic article having a thermal barrier coating and a method of application thereof
DE69732046T2 (de) * 1997-10-30 2005-12-08 Alstom Schutzbeschichtung für hochtemperatur
US7316850B2 (en) 2004-03-02 2008-01-08 Honeywell International Inc. Modified MCrAlY coatings on turbine blade tips with improved durability
US7875370B2 (en) * 2006-08-18 2011-01-25 United Technologies Corporation Thermal barrier coating with a plasma spray top layer
JP2009063072A (ja) * 2007-09-06 2009-03-26 Railway Technical Res Inst ブレーキディスクとその表面改質方法及びブレーキディスクの表面改質装置
EP3060695B1 (en) 2013-10-21 2019-12-11 United Technologies Corporation Ceramic attachment configuration and method for manufacturing same
JP2018162506A (ja) * 2017-03-27 2018-10-18 川崎重工業株式会社 高温部材及びその製造方法
CN113106374A (zh) * 2021-03-19 2021-07-13 航天材料及工艺研究所 一种耐高温高热流冲刷的复合涂层及其制备方法
CN116751473B (zh) * 2023-06-20 2024-06-21 重庆大学 一种耐高温远红外涂料及其制备方法

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
CA1068178A (en) * 1975-09-11 1979-12-18 United Technologies Corporation Thermal barrier coating for nickel base super alloys
US4095003A (en) * 1976-09-09 1978-06-13 Union Carbide Corporation Duplex coating for thermal and corrosion protection
DE2842848C2 (de) * 1977-10-17 1987-02-26 United Technologies Corp., Hartford, Conn. Werkstoff zum Überziehen von Gegenständen
US4269903A (en) * 1979-09-06 1981-05-26 General Motors Corporation Abradable ceramic seal and method of making same
GB2063305B (en) * 1979-10-15 1984-02-01 United Technologies Corp Carbon bearing mcraiy coatings coated articles and method for these coatings
US4321310A (en) * 1980-01-07 1982-03-23 United Technologies Corporation Columnar grain ceramic thermal barrier coatings on polished substrates
SE8401757L (sv) * 1984-03-30 1985-10-01 Yngve Lindblom Metalloxidkeramiska ytskikt pa hog temperaturmaterial
IL75304A (en) * 1984-06-08 1989-03-31 United Technologies Corp Coated superalloy articles and method of strengthening same
US4576874A (en) * 1984-10-03 1986-03-18 Westinghouse Electric Corp. Spalling and corrosion resistant ceramic coating for land and marine combustion turbines

Also Published As

Publication number Publication date
SG76592G (en) 1992-10-02
EP0266299A3 (en) 1989-05-31
IL84067A0 (en) 1988-03-31
JP2826824B2 (ja) 1998-11-18
MX169998B (es) 1993-08-04
AU594521B2 (en) 1990-03-08
CA1330638C (en) 1994-07-12
IL84067A (en) 1992-03-29
AU8050087A (en) 1988-05-05
EP0266299A2 (en) 1988-05-04
DE3779045D1 (de) 1992-06-17
DE266299T1 (de) 1988-09-22
JPS63118059A (ja) 1988-05-23

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