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<ep-patent-document id="EP10251689B1" file="EP10251689NWB1.xml" lang="en" country="EP" doc-number="2336381" kind="B1" date-publ="20140604" status="n" dtd-version="ep-patent-document-v1-4">
<SDOBI lang="en"><B000><eptags><B001EP>ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIROMKCYALTRBGCZEEHUPLSK..HRIS..MTNO....SM..................</B001EP><B005EP>J</B005EP><B007EP>DIM360 Ver 2.41 (21 Oct 2013) -  2100000/0</B007EP></eptags></B000><B100><B110>2336381</B110><B120><B121>EUROPEAN PATENT SPECIFICATION</B121></B120><B130>B1</B130><B140><date>20140604</date></B140><B190>EP</B190></B100><B200><B210>10251689.5</B210><B220><date>20100930</date></B220><B240><B241><date>20111219</date></B241></B240><B250>en</B250><B251EP>en</B251EP><B260>en</B260></B200><B300><B310>638051</B310><B320><date>20091215</date></B320><B330><ctry>US</ctry></B330></B300><B400><B405><date>20140604</date><bnum>201423</bnum></B405><B430><date>20110622</date><bnum>201125</bnum></B430><B450><date>20140604</date><bnum>201423</bnum></B450><B452EP><date>20131220</date></B452EP></B400><B500><B510EP><classification-ipcr sequence="1"><text>C23C   4/04        20060101AFI20131004BHEP        </text></classification-ipcr><classification-ipcr sequence="2"><text>C23C   4/10        20060101ALI20131004BHEP        </text></classification-ipcr><classification-ipcr sequence="3"><text>C23C   4/12        20060101ALI20131004BHEP        </text></classification-ipcr></B510EP><B540><B541>de</B541><B542>Plasmaanwendung von Wärmedämmbeschichtungen mit verringerter Wärmeleitfähigkeit auf der Brennkammer-Hardware</B542><B541>en</B541><B542>Plasma application of thermal barrier coatings with reduced thermal conductivity on combustor hardware</B542><B541>fr</B541><B542>Application de plasma sur des revêtements de barrière thermique à conductivité thermique réduite sur un matériel de chambre de combustion</B542></B540><B560><B561><text>EP-A1- 0 992 603</text></B561><B561><text>EP-A1- 1 550 744</text></B561><B561><text>EP-A1- 1 642 993</text></B561><B561><text>EP-A1- 1 806 436</text></B561><B561><text>EP-A2- 1 621 647</text></B561><B561><text>EP-A2- 1 674 663</text></B561><B561><text>EP-A2- 1 889 940</text></B561><B561><text>EP-A2- 1 889 948</text></B561><B561><text>US-A1- 2003 152 814</text></B561></B560></B500><B700><B720><B721><snm>Zajchowski, Paul H.</snm><adr><str>9 Deerfield Circle</str><city>Enfield, CT 06082</city><ctry>US</ctry></adr></B721><B721><snm>Meier, Susan M.</snm><adr><str>124 Box Mountain Drive</str><city>Vernon, CT 06066</city><ctry>US</ctry></adr></B721><B721><snm>Schlichting, Kevin W.</snm><adr><str>50 Country Lane</str><city>South Glastonbury
CT 06073</city><ctry>US</ctry></adr></B721></B720><B730><B731><snm>United Technologies Corporation</snm><iid>101116296</iid><irf>74.106982</irf><adr><str>United Technologies Building 
One Financial Plaza</str><city>Hartford, CT 06101</city><ctry>US</ctry></adr></B731></B730><B740><B741><snm>Leckey, David Herbert</snm><iid>100034578</iid><adr><str>Dehns 
St Bride's House 
10 Salisbury Square</str><city>London
EC4Y 8JD</city><ctry>GB</ctry></adr></B741></B740></B700><B800><B840><ctry>AL</ctry><ctry>AT</ctry><ctry>BE</ctry><ctry>BG</ctry><ctry>CH</ctry><ctry>CY</ctry><ctry>CZ</ctry><ctry>DE</ctry><ctry>DK</ctry><ctry>EE</ctry><ctry>ES</ctry><ctry>FI</ctry><ctry>FR</ctry><ctry>GB</ctry><ctry>GR</ctry><ctry>HR</ctry><ctry>HU</ctry><ctry>IE</ctry><ctry>IS</ctry><ctry>IT</ctry><ctry>LI</ctry><ctry>LT</ctry><ctry>LU</ctry><ctry>LV</ctry><ctry>MC</ctry><ctry>MK</ctry><ctry>MT</ctry><ctry>NL</ctry><ctry>NO</ctry><ctry>PL</ctry><ctry>PT</ctry><ctry>RO</ctry><ctry>SE</ctry><ctry>SI</ctry><ctry>SK</ctry><ctry>SM</ctry><ctry>TR</ctry></B840><B880><date>20110622</date><bnum>201125</bnum></B880></B800></SDOBI>
<description id="desc" lang="en"><!-- EPO <DP n="1"> -->
<heading id="h0001">BACKGROUND</heading>
<p id="p0001" num="0001">The present disclosure is directed to thermal barrier coatings with reduced thermal conductivity on combustor hardware, which coatings are applied using a plasma.</p>
<p id="p0002" num="0002">Ceramic thermal barrier coatings (TBCs) have been used for many years to extend the life of combustors and high turbine stationary and rotating parts in gas turbine engines. TBCs typically consist of a metallic bond coat and a ceramic top coat applied to a nickel or cobalt based alloy substrate which forms the part being coated. The coatings are typically applied to thicknesses between 5 and 40 mils (0.127 mm and 1.016 mm) and can provide up to 300 degrees F (149°C) temperature reduction to the substrate metal. This temperature reduction translates into improved part durability, higher turbine operating temperatures, and improved turbine efficiency. Typically, the ceramic layer is a 7 wt% yttria stabilized zirconia applied by air plasma spray (APS). New low thermal conductivity coatings have been developed which can provide improved part performance.</p>
<p id="p0003" num="0003">One coating which has been used in the past for TBCs is gadolinia stabilized zirconia based thermal barrier coatings.</p>
<p id="p0004" num="0004">A coating process according to the preamble of claim 1 is disclosed in <patcit id="pcit0001" dnum="EP1642993A"><text>EP-A-1642993</text></patcit>. Further coating processes are disclosed in <patcit id="pcit0002" dnum="EP1806436A"><text>EP-A-1806436</text></patcit> and <patcit id="pcit0003" dnum="EP1889948A"><text>EP-A-1889948</text></patcit>.<!-- EPO <DP n="2"> --></p>
<heading id="h0002">SUMMARY OF THE INVENTION</heading>
<p id="p0005" num="0005">It is desirable to form a thermal barrier coating which has a relatively low thermal conductivity.</p>
<p id="p0006" num="0006">As described herein, there is provided a process for forming a thermal barrier coating as set forth in claim 1.</p>
<p id="p0007" num="0007">Other details of the thermal barrier coatings applied using an air plasma spray technique, as well as advantages attendant thereto, are set forth in the following detailed description and the accompanying drawings.</p>
<heading id="h0003">BRIEF DESCRIPTION OF THE DRAWINGS</heading>
<p id="p0008" num="0008">
<ul id="ul0001" list-style="none">
<li><figref idref="f0001">Figs. 1 and 2</figref> are photomicrographs showing a low conductivity cracked coating formed using a F4 Plasma Spray Gun, which coating includes a ceramic layer consisting of 30 wt% Gd<sub>2</sub>O<sub>3</sub> and 70 wt% ZrO<sub>2</sub> with a air plasma sprayed MCrAlY bond coat);</li>
<li><figref idref="f0002">Fig. 3</figref> is a photomicrograph showing a coating system which includes a metallic bond coat, a ceramic bond coat, and a ceramic top coat formed by a low conductivity coating in which the metallic bond coat is an air plasma-sprayed MCrAlY bond coat, the ceramic bond coat is a 7 YSZ interlayer, and the ceramic top coat is a 30 wt% Gd<sub>2</sub>O<sub>3</sub> - 70 wt% ZrO<sub>2</sub> top layer.</li>
</ul></p>
<heading id="h0004">DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)</heading>
<p id="p0009" num="0009">As described herein, a plasma spray technique is utilized to apply a gadolinia stabilized zirconia based thermal barrier coatings on combustor hardware such as panels, chambers, heat shields, transition ducts, augmenters, etc. The plasma spray technique may be an air plasma spray technique in which a desirable coating microstructure is produced.<!-- EPO <DP n="3"> --></p>
<p id="p0010" num="0010">In air plasma spray, the coating material is propelled toward the surface of the substrate to be coated. The coating material is in the form of a spray. The powder or powders forming the coating material are fed along with carrier gases into a high temperature plasma gas stream. In the plasma gas stream, the powder particles are melted and accelerated toward the surface of the substrate to be coated. The powder particles are fed to a spray gun at a desired feed rate. A carrier gas flow such as an argon gas flow is used to maintain the powder under pressure and facilitate powder feed. The carrier gas flow rate is described in standard cubic feet per hour. Standard conditions may be defined as about room temperature and about one atmosphere of pressure.</p>
<p id="p0011" num="0011">The gases that make up the plasma gas stream comprise a primary gas (such as an argon gas or nitrogen gas) and a secondary gas (such as a hydrogen gas). Helium gas may be used as the secondary gas if desired.</p>
<p id="p0012" num="0012">The process includes the step of translating a spray gun so that the nozzle is positioned at a desired distance from the surface to be coated. The substrate to be coated may be passed through the spray of powder particles emanating from the spray gun.</p>
<p id="p0013" num="0013">The spray gun to be used to form the coatings disclosed herein may include both internal feed and external feed spray guns. Suitable spray guns include the Plasmadyne SG-. 100, Sulzer Metco 3MB, 7 MB, or 9 MB, and the Plasma Technic F-4. The desired coating may also be applied with the high deposition rate Sulzer Metco Triplex gun and/or the Progressive HE100 gun.<!-- EPO <DP n="4"> --></p>
<p id="p0014" num="0014">Zirconia based powder with the additions of rare earth stabilizers, such as gadolinia, have been found to yield coatings having lower thermal conductivities than many current thermal barrier coatings. A powder used in accordance with the invention consists of 3.0 to 14 wt% of at least one of yttria and titania, 15 to 70 wt% gadolinia, and the balance zirconia. The yttria and/or titania, and the gadolinia, improve the thermal barrier coating's ceramic mechanical properties, while still achieving a reduced thermal conductivity ceramic coating. Coatings formed using these powders are shown in <figref idref="f0001">Figs. 1 and 2</figref>.</p>
<p id="p0015" num="0015">If desired, one could apply to a substrate, a coating which has a metallic bond coat, such as a MCrAlY type coating where M is Ni or Co, a ceramic interlayer, such as a 7 YSZ coating, deposited on the metallic bond coat and a ceramic top coat comprising from 15 to 70 wt% gadolinia and the balance zirconia. Such a coating system is illustrated in <figref idref="f0002">Fig. 3</figref>.</p>
<p id="p0016" num="0016">The air plasma spray parameters may be adjusted to produce a coating with a desired level of porosity or a coating with a dense segmented structure. For porous coatings, the coating may have a thermal conductivity which ranges from 3.0 to 10 BTU in/hr ft<sup>2</sup> F (5.2 to 17.3 W/m·K). For segmented coatings, the coating may have a thermal conductivity which ranges from 5.0 to 12.5 BTU in/hr ft<sup>2</sup> F (8.6 to 21.6 W/m·K).</p>
<p id="p0017" num="0017">A useful coating has a porosity in the range of 5.0 to 20%. The desired porosity for the coating may be obtained by altering the gun power settings, the standoff distance, the powder particle size, and the powder feed rate.</p>
<p id="p0018" num="0018">Segmented coatings provide the coating with strain tolerance during operation which leads to increased spallation life. For combustor panel applications, a coating system having a<!-- EPO <DP n="5"> --> segmented microstructure topcoat layer with a ceramic interlayer provides a useful coating system.</p>
<p id="p0019" num="0019">If desired, one can obtain a coating with a dense segmented structure by increasing the power settings and shorten the standoff distance. One can do this by using the settings set forth in columns 6 - 8 of <patcit id="pcit0004" dnum="US5879753A"><text>U.S. patent no. 5,879,753</text></patcit>, which patent is incorporated by reference herein. The relevant disclosure of <patcit id="pcit0005" dnum="US5879753A"><text>US patent no. 5,879,753</text></patcit> appears at the end of the description as Annex 1.</p>
<p id="p0020" num="0020">For example, a useful coating may be applied using the Plasmadyne SG-100 spray gun using an amperage range of 350 to 825 amps, a voltage of 35 to 50 volts applied to a cathode and anode within the plasma-gun body, an argon primary gas flow of 75 - 105 SCFH (35 to 49 l/min), a hydrogen secondary gas flow of 1.0 to 10 SCFH (.47 to 4.7 l/min) or a helium gas flow of 45 - 75 SCFH (21 to 35 l/min), a powder gas flow exiting the gun of 4.0 to 20 SCFH (1.9 to 9.4 l/min), a powder feed rate to the gun of 10 to 40 grams/min., and a gun distance from the surface being coated of from 3.0 to 5.0 inches (71.6 to 127 min). Alternatively, the coatings may be applied with the Plasma Technic F-4 spray gun using an amperage range of from 500 to 700 amps, a voltage of 55 to 65 volts, an argon primary gas flow of 65 to 90 SCFH (30.6 to 45.8 l/min), a hydrogen secondary gas flow of 8 - 22 SCFH (3.8 to 10.3 l/min), a powder gas flow from the spray gun of 6 to 12 SCFH (2.8 to 5.6 l/min), a powder feed rate to the spray gun of 35 - 55 grams/min. and a gun distance from the surface being coated of from 4.0 to 7.0 inches (102 to 178 min).</p>
<p id="p0021" num="0021">One of the benefits of the process of the present invention is the application of a thermal barrier coating having lower thermal conductivity than many current coatings resulting in longer coating life, performance improvements, and cost savings.<!-- EPO <DP n="6"> --></p>
<p id="p0022" num="0022">Burner rig testing of a low conductivity coating formed in accordance with the present disclosure with a ceramic interlayer was found to be 1.6 to 1.9 times better in spallation resistance than without the interlayer. In addition, low conductivity coatings with an interlayer are 1.3 to 1.5 times better in spallation than current coatings.</p>
<p id="p0023" num="0023">In accordance with the foregoing disclosure, there has been provided a plasma application of thermal barrier coatings with reduced thermal conductivity on combustor hardware. While the plasma application of thermal barrier coatings has been described in the context of specific embodiments thereof, other unforeseeable alternatives, modifications, and variations may become apparent to those skilled in the art having read the foregoing description. Accordingly, it is intended to embrace those alternatives, modifications, and variations as fall within the broad scope of the appended claims. In particular, it is possible to use in the process the various process parameters set forth in Annex 1 hereinbelow.</p>
<heading id="h0005">ANNEX 1</heading>
<p id="p0024" num="0024">The processing steps include the selection of certain parameters. These parameters include rotating the fixture at a preselected speed, angling the gun with respect to the substrate, moving the gun at a preselected traverse speed, heating the substrate to a preselected temperature, injecting the coating powder at a preselected rate, and flowing the carrier gas and plasma gases at preselected flow rates. These parameters all influence the structure of the coating and as such should be adjusted to provide uniform coating of compressor blades, or other substrates. In general, it has been found that a close gun-to-substrate spray distance coupled with relatively high spray gun power results in the desired vertical segmentation or<!-- EPO <DP n="7"> --> microcracking of the coating structure. The parameters described herein were tailored for use with an F-4 model air plasma spray gun purchased from Plasma Technics, Inc., now supplied by Sulzer Metco having facilities in Westbury, N.Y., and various diameter cylindrical fixtures depending on substrate configuration. As will be realized, the parameters may vary with the use of a different spray gun and/or fixture. Accordingly, the parameters set forth herein may be used as a guide for selecting other suitable parameters for different operating conditions.</p>
<p id="p0025" num="0025">The process for controllably applying spray coating as flow charted in <figref idref="f0001">FIG. 1</figref>, includes a number of interrelated steps beginning with providing blades having clean, exposed blade tips and protected airfoil and root surfaces typically provided by masking. Conventional cleaning and preparation of the blade tip prior to application of the abrasive layer should be conducted. In the practice of the present invention, for example with a blade tip as shown in the figures, the surface of the blade tip is cleaned and roughened to enhance adherence of subsequently applied coating materials. Such cleaning can include mechanical abrasion such as through a vapor or air blast type process employing dry or liquid carried abrasive particles impacting the surface.</p>
<p id="p0026" num="0026">Prior to cleaning the surface, blades are suitably masked as shown in <patcit id="pcit0006" dnum="USEH10117A" dnum-type="L"><text>U.S. Application Number EH-10117</text></patcit>, <patcit id="pcit0007" dnum="US08994676B"><text>U.S. Ser. No. 08/994,676, filed Dec. 19, 1997</text></patcit>, entitled "Shield and Method for Protecting an Airfoil Surface", by Zajchowski and Diaz, herein incorporated by reference.</p>
<p id="p0027" num="0027">The process includes propelling a spray of particles of softened bond coating medium toward the blade tips. The step of propelling the coating medium includes the step of forming a spray of particles of softened bond coating medium<!-- EPO <DP n="8"> --> in the spray coating apparatus. This step includes flowing bond coat powder and carrier gases into a high-temperature plasma gas stream. In the plasma gas stream, the powder particles are melted and accelerated toward the substrate. Generally, the powder feed rate should be adjusted to provide adequate consistency and amount of bond coating. The bond coat powder feed rate ranges from thirty to fifty-five grams per minute (30 to 55 grams/min). Carrier gas flow (argon gas) is used to maintain the powder under pressure and facilitate powder feed. The carrier gas flow rate ranges from four to eight standard cubic feet per hour (4 to 8 scfh) (1.9 to 3.8 standard liters per minute (SLM)). Standard conditions are herein defined as about room temperature (77 DEG F.) and about one atmosphere of pressure (760 mmHg) (101 kPa).</p>
<p id="p0028" num="0028">The gases that make up the plasma gas stream comprise of a primary gas (argon gas) and a secondary gas (hydrogen gas). Helium gas may also be used as a secondary gas. The primary gas flow rate in the gun ranges from seventy-five to one hundred and fifteen standard cubic feet per hour (75 to 115 scfh) (35 to 54 SLM), while the secondary gas flow rate ranges from ten to twenty-five standard cubic feet per hour (10 to 25 scfh) (4.7 to 12 SLM). Spray gun power generally ranges from thirty to fifty kilowatts (30 to 50 KW).</p>
<p id="p0029" num="0029">The process then includes the step of translating the spray of softened bond coating medium at a distance ranging between about four to six inches (4 to 6") (102 to 152 mm) from the blade tips, between a first and second position. In one embodiment, the spray gun is moved in a direction substantially parallel to the surface of rotation of the holding fixture. Spray gun traverse speed during bond coat deposition ranges from six to twelve inches per minute (6 to 12 in/min) (152 to 305 mm/min).<!-- EPO <DP n="9"> --></p>
<p id="p0030" num="0030">Further, the process includes passing the blades through the spray of particles of softened bond coating medium by rotating the fixture about its axis of rotation. This step includes heating the blades to a temperature of two hundred to four hundred and fifty degrees Fahrenheit (200 DEG to 450 DEG F.) (93 to 232°C) by passing the blades in front of the spray gun and hot plasma gas stream. The step of passing the blades through the spray of particles of softened bond coating medium also includes cooling the blades and the coating layer deposited by rotating them away from the spray gun. Additional cooling of the blades can be provided by directing a cooling air stream or cooling jet on the blades or the fixture. Independent sources of heating can also be provided to heat the blades prior to the blades entering the spray of particles of coating medium. The independent heating source would allow for control of blade temperature without adjusting the spray gun to provide heating. Specifically, during bond coat deposition, the cylindrical fixture rotates at a speed which ranges from twenty to seventy-five revolutions per minute (20 to 75 rpm), depending on substrate diameter. The surface speed of the blades ranges typically from one hundred and twenty-five to three hundred surface feet per minute (125 to 300 sfpm).</p>
<p id="p0031" num="0031">The coating process then includes the step of forming a spray of particles of softened top coating medium. This step includes flowing top coat powder and carrier gases into the high-temperature plasma gas stream. Generally, the powder feed rate should be adjusted to provide adequate mix to cover the substrate, yet not be so great as to reduce melting and crack formation. Top coat powder feed rate ranges from fifteen to forty grams per minute (15 to 40 grams/min). Carrier gas flow (argon gas) is used to maintain the powder under pressure and facilitate powder feed. The flow rate ranges from four to eight standard cubic feet per hour (4 to 8 scfh) (1.9 to 3.8 SLM). As described<!-- EPO <DP n="10"> --> hereinabove, standard conditions are herein defined as about room temperature (77 DEG F.) and about one atmosphere of pressure (760 mmHg) (101 kPa).</p>
<p id="p0032" num="0032">The step of forming a spray of particles of softened top coating medium includes the injection of the top coat powder angled such that it imparts a component of velocity to the powder which is opposite to the direction of flow of the plasma toward the rotating fixture. The projection of the injection angle in a plane perpendicular to the axis of rotation of the holding fixture lies in a range from sixtyfive to eighty-five degrees (65 DEG to 85 DEG ) . This injection angle serves to introduce the top coat powder further back into the plasma plume, thus increasing the residence time of the powder in the plasma gas stream. The increased residence time in the plasma gas stream provides for better melting of the powder particles.</p>
<p id="p0033" num="0033">Primary gas flow (argon gas) in the gun ranges from fifty to ninety standard cubic feet per hour (50 to 90 scfh) (24 to 43 SLM). Similarly, secondary gas flow (hydrogen gas) in the gun ranges from ten to thirty scfh (10 to 30 scfh) (4.7 to 14 SLM). Spray gun power generally ranges from thirty to fifty kilowatts (30 to 50 KW).</p>
<p id="p0034" num="0034">The process further includes the step of translating a spray of softened top coating medium at a distance ranging from three to four inches (3 to 4") (76 to 102 mm) from the blade tips, between a first and second position in a direction substantially normal to the plane of rotation of the holding fixture. Spray gun traverse speed across each part during deposition ranges from two to ten inches per minute (2 to 10 in/min) (50.8 to 254 mm/min). The gun-to-substrate distance may be varied with the intent of maintaining the appropriate temperature level at the substrate surface. A close gun-to-substrate distance is necessary for satisfactory vertical<!-- EPO <DP n="11"> --> microcracking.</p>
<p id="p0035" num="0035">The process further includes the step of passing blades through the spray of particles of softened top coating medium by rotating the fixture about its axis of rotation, wherein the step includes heating the blades by passing the blades in front of the spray gun. The temperature of top coat application is the temperature measured at the substrate at the time of applying the top coating. The temperature of application may vary from three hundred to eight hundred and fifty degrees Fahrenheit (300 DEG F. to 850 DEG F.) (149 to 454°C). The actual temperature of application is preferably maintained at a relatively constant level varying from about +/- five to ten percent (+/- 5% to 10%) of a predetermined temperature, depending upon the size of engine element coated, and the substrate on which the top coating is sprayed.</p>
<p id="p0036" num="0036">The step of passing the blades through the spray of softened particles includes the step of cooling the blades. Additionally, external cooling may be used to control deposition temperature.</p>
<p id="p0037" num="0037">This process results in layers of bond and top coating being sequentially deposited onto the blade tips in a surface of rotation substantially parallel to the surface of rotation which the blades describe when rotating in operating conditions. While the phenomenon is not well understood, it is believed that by depositing coating layers one at a time in an orientation substantially parallel to the surface of rotation that the coating layers will experience in an operating engine, the process confers an advantage as it provides relatively uniform microcracking of the coating in a radial direction. This results in relatively uniform stresses in the coating structure during operative conditions.</p>
</description>
<claims id="claims01" lang="en"><!-- EPO <DP n="12"> -->
<claim id="c-en-01-0001" num="0001">
<claim-text>A process for forming a thermal barrier coating comprising the steps of:
<claim-text>providing a substrate;</claim-text>
<claim-text>depositing a bondcoat layer on said substrate;</claim-text>
<claim-text>depositing a ceramic interlayer on said bond coat layer;</claim-text>
<claim-text>providing a gadolinia stabilized zirconia powder; and</claim-text>
<claim-text>forming a thermal barrier coating having at least one of a porosity in a range of from 5 to 20% and a dense segmented structure on said ceramic interlayer by supplying the gadolinia stabilized powder to a spray gun and using an air plasma spray technique; <b>characterised in that</b>:
<claim-text>said powder providing step comprises providing a powder consisting of from 3.0 to 14 wt% of at least one of yttria and titania, from 15 to 70 wt% gadolinia, and the balance zirconia.</claim-text></claim-text></claim-text></claim>
<claim id="c-en-01-0002" num="0002">
<claim-text>The process according to claim 1, wherein said substrate providing step comprises providing a combustor component.</claim-text></claim>
<claim id="c-en-01-0003" num="0003">
<claim-text>The process according to claim 1, wherein said substrate providing step comprises providing one of a combustor panel, a combustor chamber, a combustor heat shield, a combustor transition duct, and a combustor augmentor.</claim-text></claim>
<claim id="c-en-01-0004" num="0004">
<claim-text>The process according to any preceding claim, wherein said thermal barrier coating forming step comprises using an<!-- EPO <DP n="13"> --> amperage range of 350 to 825 amps, a voltage of 35 to 50 volts, an argon primary gas flow of 75 to 105 SCFH (35 to 49 l/min), at least one of a hydrogen secondary gas flow of 1.0 to 10 SCFH (47 to 4.7 l/min) and a helium secondary gas flow of 45 to 75 SCFH (21 to 35 l/min), a powder gas flow exiting a spray gun of 4.0 to 20 SCFH (1.9 to 9.4 l/min), a powder feed rate to the spray gun of 10 to 40 grams/min., and a gun distance from a surface of the substrate being coated of from 3.0 to 5.0 inches (71.6 to 127 mm).</claim-text></claim>
<claim id="c-en-01-0005" num="0005">
<claim-text>The process according to any one of claims 1 to 3, wherein said thermal barrier coating forming step comprises using an amperage range of from 500 to 700 amps, a voltage of 55 to 65 volts, an argon primary gas flow of 65 to 90 SCFH (30.6 to 45.8 l/min), a hydrogen secondary gas flow of 8 to 22 SCFH (3.8 to 10.3 l/min), a powder gas flow from a spray gun of 6 to 12 SCFH (2.8 to 5.6 l/min), a powder feed rate to the spray gun of 35 to 55 grams/min. and a gun distance from a surface of a substrate being coated of from 4.0 to 7.0 inches (102 to 178 mm).</claim-text></claim>
<claim id="c-en-01-0006" num="0006">
<claim-text>The process according to any preceding claim, wherein said ceramic interlayer depositing step comprises depositing a layer of 7.0 wt% yttria stabilized zirconia.</claim-text></claim>
<claim id="c-en-01-0007" num="0007">
<claim-text>The process according to any preceding claim, wherein said bondcoat layer depositing step comprises depositing a metallic bondcoat layer.</claim-text></claim>
<claim id="c-en-01-0008" num="0008">
<claim-text>The process according to any preceding claim, wherein said thermal barrier coating forming step comprises forming a segmented coating having a thermal conductivity in the range of from 5.0 to 12.5 BTU in/hr ft<sup>2</sup> F (8.6 to 21.6 W/m/K).<!-- EPO <DP n="14"> --></claim-text></claim>
<claim id="c-en-01-0009" num="0009">
<claim-text>The process according to any preceding claim, wherein said thermal barrier coating forming step comprises forming a porous coating having a thermal conductivity in the range of from 3.0 to 10 BTU in/hr ft<sup>2</sup> F (5.2 to 17.3 W/m·K).</claim-text></claim>
</claims>
<claims id="claims02" lang="de"><!-- EPO <DP n="15"> -->
<claim id="c-de-01-0001" num="0001">
<claim-text>Verfahren zur Herstellung einer Wärmebarrierebeschichtung, folgende Schritte aufweisend:
<claim-text>Bereitstellen eines Substrats;</claim-text>
<claim-text>Abscheiden einer Haftvermittlerschicht auf dem Substrat;</claim-text>
<claim-text>Abscheiden einer keramischen Zwischenschicht auf der Haftvermittlerschicht;</claim-text>
<claim-text>Bereitstellen eines Gadoliniumoxid-stabilisierten Zirkoniumdioxid-Pulvers; und</claim-text>
<claim-text>Ausbilden einer Wärmebarrierebeschichtung mit einer Porosität in einem Bereich von 5 bis 20% und/oder einer dichten, segmentierten Struktur auf der keramischen Zwischenschicht durch Zuführen des Gadoliniumoxid-stabilisierten Pulvers zu einem Spritzgerät und durch Verwenden einer Luft-Plasmaspritztechnik;</claim-text>
<claim-text><b>dadurch gekennzeichnet, dass</b>:
<claim-text>der Schritt des Bereitstellens des Pulvers das Bereitstellen eines Pulvers aufweist, das aus von 3,0 bis 14 Gew.% Yttriumoxid und/oder Titandioxid, von 15 bis 70 Gew.% Gadoliniumoxid, und Rest Zirkoniumdioxid besteht.</claim-text></claim-text></claim-text></claim>
<claim id="c-de-01-0002" num="0002">
<claim-text>Verfahren nach Anspruch 1, bei dem der Schritt des Bereitstellens des Substrats das Bereitstellen einer Brennerkomponente umfasst.</claim-text></claim>
<claim id="c-de-01-0003" num="0003">
<claim-text>Verfahren nach Anspruch 1, bei dem der Schritt des Bereitstellens des Substrats das Bereitstellen einer Brennerplatte, einer Brennerkammer, eines Brenner-Hitzeschilds, eines Brenner-Übergangsstrahlrohres oder eines Brenner-Nachbrenners umfasst.</claim-text></claim>
<claim id="c-de-01-0004" num="0004">
<claim-text>Verfahren nach einem vorangehenden Anspruch, bei dem der Schritt des Ausbildens der Wärmebarrierebeschichtung die Verwendung eines Stromstärkebereichs von 350 bis 825 A, einer Spannung von 35<!-- EPO <DP n="16"> --> bis 50 V, einer Argon-Primärgasströmung von 75 bis 105 SCFH (35 bis 49 l/min), einer Wasserstoff-Sekundärgasströmung von 1,0 bis 10 SCFH (47 bis 4,7 l/min) und/oder einer Helium-Sekundärgasströmung von 45 bis 75 SCFH (21 bis 35 l/min), einer Pulver-Gasströmung, die mit 4,0 bis 20 SCFH (1,9 bis 9,4 l/min) aus einem Spritzgerät austritt, einer Pulver-Einspeisegeschwindigkeit zu dem Spritzgerät von 10 bis 40 Gramm/Min, und eines Gerät-Abstands von der Oberfläche des Substrats, das beschichtet wird, von 3,0 bis 5, 0 Zoll (71,6 bis 127 mm) umfasst.</claim-text></claim>
<claim id="c-de-01-0005" num="0005">
<claim-text>Verfahren nach einem der Ansprüche 1 bis 3, bei dem der Schritt des Ausbildens der Wärmebarrierebeschichtung die Verwendung eines Stromstärkebereichs von 500 bis 700 A, einer Spannung von 55 bis 65 V, einer Argon-Primärgasströmung von 65 bis 90 SCFH (30,6 bis 45,8 l/min), einer Wasserstoff-Sekundärgasströmung von 8 bis 22 SCFH (3,8 bis 10,3 l/min), einer Pulver-Gasströmung aus einem Spritzgerät von 6 bis 12 SCFH (2,8 bis 5,6 l/min), einer Pulver-Einspeisegeschwindigkeit zu dem Spritzgerät von 35 bis 55 Gramm/Min und eines Gerät-Abstands von einer Oberfläche eines Substrats, das beschichtet wird, von 4,0 bis 7,0 Zoll (102 bis 178 mm) umfasst.</claim-text></claim>
<claim id="c-de-01-0006" num="0006">
<claim-text>Verfahren nach einem vorangehenden Anspruch, bei dem der Schritt des Abscheidens der keramischen Zwischenschicht das Abscheiden einer Schicht aus mit 7,0 Gew.% Yttriumoxid-stabilisiertem Zirkoniumdioxid umfasst.</claim-text></claim>
<claim id="c-de-01-0007" num="0007">
<claim-text>Verfahren nach einem vorangehenden Anspruch, bei dem der Schritt des Abscheidens der Haftvermittlerschicht das Abscheiden einer metallischen Haftvermittlerschicht umfasst.</claim-text></claim>
<claim id="c-de-01-0008" num="0008">
<claim-text>Verfahren nach einem vorangehenden Anspruch, bei dem der Schritt des Ausbildens der Wärmebarrierebeschichtung das Ausbilden einer segmentierten Beschichtung mit einer Wärmeleitfähigkeit in dem Bereich von 5,0 bis 12,5 BTU in/hr ft<sup>2</sup> F (8,6 bis 21,6 W/m/K) umfasst.<!-- EPO <DP n="17"> --></claim-text></claim>
<claim id="c-de-01-0009" num="0009">
<claim-text>Verfahren nach einem vorangehenden Anspruch, bei dem der Schritt des Ausbildens der Wärmebarrierebeschichtung das Ausbilden einer porösen Beschichtung mit einer Wärmeleitfähigkeit in dem Bereich von 3,0 bis 10 BTU in/hr ft<sup>2</sup> F (5,2 bis 17,3 W/m · K) umfasst.</claim-text></claim>
</claims>
<claims id="claims03" lang="fr"><!-- EPO <DP n="18"> -->
<claim id="c-fr-01-0001" num="0001">
<claim-text>Processus pour former un revêtement formant barrière thermique comprenant les étapes de :
<claim-text>fourniture d'un substrat ;</claim-text>
<claim-text>dépôt d'une couche de liaison sur ledit substrat ;</claim-text>
<claim-text>dépôt d'une intercouche de céramique sur ladite couche de liaison ;</claim-text>
<claim-text>fourniture d'une poudre de zircone stabilisée à l'oxyde de gadolinium ; et</claim-text>
<claim-text>formation d'un revêtement formant barrière thermique ayant au moins l'une d'une porosité dans une plage de 5 à 20 % et d'une structure segmentée dense sur ladite intercouche de céramique en fournissant la poudre stabilisée à l'oxyde de gadolinium à un pistolet de pulvérisation et en utilisant une technique de pulvérisation de plasma d'air ; caractérisé en ce qui :
<claim-text>ladite étape de fourniture de poudre comprend la fourniture d'une poudre constituée par 3,0 à 14 % en poids d'au moins un d'oxyde d'yttrium et d'oxyde de titane, 15 à 70 % en poids d'oxyde de gadolinium, et le reste par de la zircone.</claim-text></claim-text></claim-text></claim>
<claim id="c-fr-01-0002" num="0002">
<claim-text>Processus selon la revendication 1, dans lequel ladite étape de fourniture de substrat comprend la fourniture d'un composant de dispositif de combustion.</claim-text></claim>
<claim id="c-fr-01-0003" num="0003">
<claim-text>Processus selon la revendication 1, ladite étape de fourniture de substrat comprend la fourniture de l'un d'un panneau de dispositif de combustion, d'une chambre de dispositif de combustion, d'une protection thermique de dispositif de combustion, d'un conduit de transition de dispositif de combustion, et d'un dispositif d'augmentation de poussée de dispositif de combustion.</claim-text></claim>
<claim id="c-fr-01-0004" num="0004">
<claim-text>Processus selon l'une quelconque des revendications précédentes, dans lequel ladite étape de<!-- EPO <DP n="19"> --> formation de revêtement formant barrière thermique comprend l'utilisation d'une plage d'ampérage de 350 à 825 ampères, d'une tension de 35 à 50 volts, d'un flux de gaz primaire d'argon de 75 à 105 SCFH (35 à 49 l/minute), d'au moins un d'un flux de gaz secondaire d'hydrogène de 1,0 à 10 SCFH (47 à 4,7 l/minute) et d'un flux de gaz secondaire d'hélium de 45 à 75 SCFH (21 à 35 l/minute), d'un flux de gaz de poudre sortant d'un pistolet de pulvérisation de 4,0 à 20 SCFH (1,9 à 9,4 l/minute), d'un débit d'alimentation en poudre au pistolet de pulvérisation de 10 à 40 grammes/minute, et d'une distance du pistolet à une surface d'un substrat en cours de revêtement de 3,0 à 5,0 pouces (71,6 à 127 mm).</claim-text></claim>
<claim id="c-fr-01-0005" num="0005">
<claim-text>Processus selon l'une quelconque des revendications 1 à 3, dans lequel ladite étape de formation de revêtement formant barrière thermique comprend l'utilisation d'une plage d'ampérage de 500 à 700 ampères, d'une tension de 55 à 65 volts, d'un flux de gaz primaire d'argon de 65 à 90 SCFH (30,6 à 45,8 l/minute), d'un flux de gaz secondaire d'hydrogène de 8 à 22 SCFH (3,8 à 10,3 l/minute), d'un flux de gaz de poudre d'un pistolet de pulvérisation de 6 à 12 SCFH (2,8 à 5,6 l/minute), d'un débit d'alimentation en poudre au pistolet de pulvérisation de 35 à 55 grammes/minute, et d'une distance du pistolet à une surface d'un substrat en cours de revêtement de 4,0 à 7,0 pouces (102 à 178 mm).</claim-text></claim>
<claim id="c-fr-01-0006" num="0006">
<claim-text>Processus selon l'une quelconque des revendications précédentes, dans lequel ladite étape de dépôt d'intercouche de céramique comprend le dépôt d'une couche de 7,0 % en poids de zircone stabilisée à l'oxyde d'yttrium.</claim-text></claim>
<claim id="c-fr-01-0007" num="0007">
<claim-text>Processus selon l'une quelconque des revendications précédentes, dans lequel ladite étape de<!-- EPO <DP n="20"> --> dépôt de couche de liaison comprend le dépôt d'une couche de liaison métallique.</claim-text></claim>
<claim id="c-fr-01-0008" num="0008">
<claim-text>Processus selon l'une quelconque des revendications précédentes, dans lequel ladite étape de formation de revêtement formant barrière thermique comprend la formation d'un revêtement segmenté ayant une conductibilité thermique dans la plage de 5,0 à 12,5 BTU in/heure ft<sup>2</sup> F (8,6 à 21,6 W/m/K).</claim-text></claim>
<claim id="c-fr-01-0009" num="0009">
<claim-text>Processus selon l'une quelconque des revendications précédentes, dans lequel ladite étape de formation de revêtement formant barrière thermique comprend la formation d'un revêtement poreux ayant une conductibilité thermique dans la plage de 3,0 à 10 BTU in/heure ft<sup>2</sup> F (5,2 à 17,3 W/m·K).</claim-text></claim>
</claims>
<drawings id="draw" lang="en"><!-- EPO <DP n="21"> -->
<figure id="f0001" num="1,2"><img id="if0001" file="imgf0001.tif" wi="127" he="219" img-content="drawing" img-format="tif"/></figure><!-- EPO <DP n="22"> -->
<figure id="f0002" num="3"><img id="if0002" file="imgf0002.tif" wi="146" he="187" img-content="drawing" img-format="tif"/></figure>
</drawings>
<ep-reference-list id="ref-list">
<heading id="ref-h0001"><b>REFERENCES CITED IN THE DESCRIPTION</b></heading>
<p id="ref-p0001" num=""><i>This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.</i></p>
<heading id="ref-h0002"><b>Patent documents cited in the description</b></heading>
<p id="ref-p0002" num="">
<ul id="ref-ul0001" list-style="bullet">
<li><patcit id="ref-pcit0001" dnum="EP1642993A"><document-id><country>EP</country><doc-number>1642993</doc-number><kind>A</kind></document-id></patcit><crossref idref="pcit0001">[0004]</crossref></li>
<li><patcit id="ref-pcit0002" dnum="EP1806436A"><document-id><country>EP</country><doc-number>1806436</doc-number><kind>A</kind></document-id></patcit><crossref idref="pcit0002">[0004]</crossref></li>
<li><patcit id="ref-pcit0003" dnum="EP1889948A"><document-id><country>EP</country><doc-number>1889948</doc-number><kind>A</kind></document-id></patcit><crossref idref="pcit0003">[0004]</crossref></li>
<li><patcit id="ref-pcit0004" dnum="US5879753A"><document-id><country>US</country><doc-number>5879753</doc-number><kind>A</kind></document-id></patcit><crossref idref="pcit0004">[0019]</crossref><crossref idref="pcit0005">[0019]</crossref></li>
<li><patcit id="ref-pcit0005" dnum="USEH10117A" dnum-type="L"><document-id><country>US</country><doc-number>EH10117</doc-number><kind>A</kind></document-id></patcit><crossref idref="pcit0006">[0026]</crossref></li>
<li><patcit id="ref-pcit0006" dnum="US08994676B"><document-id><country>US</country><doc-number>08994676</doc-number><kind>B</kind><date>19971219</date></document-id></patcit><crossref idref="pcit0007">[0026]</crossref></li>
</ul></p>
</ep-reference-list>
</ep-patent-document>
