US20060177676A1 - Heat-insulation material and arrangement of a heat-insulation layer containing said heat-insulation material - Google Patents

Heat-insulation material and arrangement of a heat-insulation layer containing said heat-insulation material Download PDF

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Publication number
US20060177676A1
US20060177676A1 US10/566,980 US56698004A US2006177676A1 US 20060177676 A1 US20060177676 A1 US 20060177676A1 US 56698004 A US56698004 A US 56698004A US 2006177676 A1 US2006177676 A1 US 2006177676A1
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Prior art keywords
thermal barrier
insulating material
barrier coating
thermally insulating
luminophore
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US10/566,980
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English (en)
Inventor
Ulrich Bast
Wolfgang Rossner
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Siemens AG
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Siemens AG
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Assigned to SIEMENS AKTIENGESELLSCHAFT reassignment SIEMENS AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAST, ULRICH, ROSSNER, WOLFGANG
Publication of US20060177676A1 publication Critical patent/US20060177676A1/en
Abandoned legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
    • 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
    • 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
    • C23C4/18—After-treatment

Definitions

  • Thermally insulating material and arrangement of a thermal barrier coating incorporating said thermally insulating material are provided.
  • the invention relates to a thermally insulating material for a thermal barrier coating of a substrate for limiting heat transfer between the substrate and an environment of the substrate, the thermally insulating material having at least one luminophore which can be excited to emit luminescent light at a particular emission wavelength, and the luminophore having at least one metal oxide with at least one trivalent metal A.
  • the thermally insulating material an arrangement of at least one thermal barrier coating incorporating the thermally insulating material on a substrate is specified.
  • a thermally insulating material and an arrangement of this kind are known from EP 1 105 550 B1.
  • the substrate is a component in a gas turbine.
  • the substrate is made of metal.
  • High temperatures in excess of 1200° C. occurring in a gas turbine in the environment of the component may cause the metal of the component to be damaged.
  • a thermal barrier coating (TBC) is deposited on the component.
  • TBC thermal barrier coating ensures that a reduced heat exchange takes place between the metal substrate and the environment, causing a metal surface of the component to heat less strongly.
  • a surface temperature occurs which is lower than the temperature in the environment of the component.
  • the thermally insulating material constitutes a base material of the thermal barrier coating.
  • the mechanical and thermal properties of the thermal barrier coating depend essentially on the properties of the thermally insulating material.
  • the base material of the known thermal barrier coating is a metal oxide.
  • the metal oxide is, for example, an yttrium stabilized zirconium oxide (YSZ).
  • YSZ yttrium stabilized zirconium oxide
  • This thermally insulating material has a thermal conductivity of between 1 and 3 W/mK.
  • the layer thickness of the thermal barrier coating is approximately 250 ⁇ m.
  • a metal oxide in the form of an yttrium aluminum granate is specified as the thermally insulating material.
  • a metal-alloy interlayer (bond coat) is deposited on the surface of the component.
  • a ceramic interlayer of a ceramic material such as aluminum oxide can be additionally disposed between the thermal barrier coating and the component.
  • thermoluminescent indicator is embedded in the thermal barrier coating.
  • This indicator is a luminescent material (luminophore) which can be stimulated to emit a luminescent light with a particular emission wavelength by excitation with excitation light of a particular excitation wavelength.
  • the excitation light is, for example, UV light.
  • the emission light is, for example, visible light.
  • the luminophore used is a so-called recombination luminescence material.
  • the luminescent process is initiated by electronic transitions between energy states of the activator.
  • a luminophore of this kind consists, for example, of a solid with a crystal lattice (host lattice) in which a so-called activator is embedded.
  • the solid body is doped with the activator.
  • the activator participates together with the entire solid body in the luminescent process of the luminophore.
  • the base material of the thermal barrier coating is doped with an activator.
  • a thermal barrier coating consisting of the luminophore is present.
  • the activator used is a rare earth element. In the case of yttrium stabilized zirconium oxide, the rare earth element is typically europium.
  • the thermally insulating material yttrium aluminum granate is doped with the rare earth elements dysprosium or terbium.
  • the known thermal barrier coating utilizes the fact that an emission property of the luminescent light of the luminophore, e.g. an emission intensity or emission decay time, is dependent on the temperature of the luminophore. On the basis of this dependence, the luminophore can be used to indicate the temperature of the thermal barrier coating. To ensure that this relationship can be established, the thermal barrier coating is optically accessible to excitation light in the UV range. It is simultaneously ensured that the luminescent light of the luminophore can be radiated and detected by the thermal barrier coating.
  • an emission property of the luminescent light of the luminophore e.g. an emission intensity or emission decay time
  • a single thermal barrier coating containing the luminophore is disposed on the substrate.
  • an additional thermal barrier coating which is transparent to the excitation light and the luminescent light of the luminophore is deposited on the thermal barrier coating. The luminescent light of the luminophore can penetrate the additional thermal barrier coating.
  • thermal barrier coating consisting of one of the abovementioned thermally insulating luminescent materials is limited to an operating temperature of approximately 1200° C. These thermally insulating materials are therefore unsuitable for future gas turbine generations where the operating temperature will have to be increased to improve efficiency.
  • the object of the present invention is therefore to specify a thermally insulating luminescent material, which is stable above a temperature of 1200° C., for a thermal barrier coating of a substrate.
  • thermally insulating material for a thermal barrier coating of a substrate for reducing heat transfer between the substrate and an environment of the substrate, the thermally insulating material having at least one luminophore which can be excited to emit luminescent light at a particular emission wavelength, and the luminophore having at least one metal oxide with at least one trivalent metal A.
  • the thermally insulating material is characterized in that the metal oxide is a mixed oxide selected from the perovskite group with the empirical formula AA′O 3 and/or pyrochlore with the empirical formula A 2 B 2 O 7 , A′ being a trivalent metal and B a tetravalent metal.
  • This object is also achieved by an arrangement of at least one thermal barrier coating on a substrate for reducing heat transfer between the substrate and an environment of the substrate, the thermal barrier coating containing the described thermally insulating material incorporating the luminophore.
  • a thermal barrier coating consisting of a perovskite and/or a pyrochlore (pyrochlore phase) is characterized by high stability at temperatures in excess of 1200° C. These stable thermal barrier coatings have a luminophore.
  • the thermal barrier coating can be a single or multiphase system.
  • Single phase means that a TBC ceramic phase constituted by the thermally insulating material essentially consists of the luminophore only.
  • the thermally insulating material of the thermal barrier coating is the luminophore.
  • the thermally insulating material and the luminophore are different.
  • the thermally insulating material contains luminophoric particles from the luminophore.
  • the ceramic phase is constituted by different materials.
  • the luminophoric particles are preferably distributed homogeneously over the thermal barrier coating. It is advantageous, moreover, if the thermally insulating material and the luminophore consist of an essentially identical kind of solid. The luminophore and the thermally insulating material consist of the same metal oxide. The two materials differ solely in respect of their optical characteristics. The luminophore is doped, for example, for this purpose.
  • the luminophore is a recombination luminescence material, the emission of the luminescent light being preferably based on the presence of an activator.
  • an activator or a plurality of activators the emission properties of the luminophore, such as the emission wavelength and the emission intensity, can be varied relatively easily.
  • the luminophore has an activator selected from the cerium and/or europium and/or dysprosium and/or terbium group. Because of their ion radii, rare earth elements can generally be easily incorporated in the crystal lattice of perovskites and pyrochlores. Activators in the form of rare earth elements are therefore generally suitable. The rare earth elements specified have shown themselves to be particularly good activators.
  • the proportion of activator in the luminophore is up to 10 mol %.
  • the proportion is preferably less than 2 mol %, e.g. 1 mol %. This low proportion of activator has been found sufficient to achieve a usable emission intensity of the luminophore while retaining the thermal and mechanical stability of a thermal barrier layer produced using the luminophore.
  • the trivalent metal A and/or the trivalent metal A′ is a rare earth element Re.
  • the trivalent metal A and/or the trivalent metal A′ is specifically a rare earth element selected from the lanthanum and/or gadolinium and/or samarium group. Other rare earth elements are likewise conceivable.
  • an activator in the form of a rare earth element can be easily incorporated in the crystal lattice of the perovskite or pyrochlore because of the similar ion radii.
  • One of the trivalent metals A and A′ of the perovskite is a main group or subgroup element.
  • the tetravalent metal B of the pyrochlore is likewise a main or subgroup element. In both cases, mixtures of different main and subgroup elements can be provided.
  • the rare earth elements and the main or subgroup elements preferably assume different positions in the perovskite or pyrochlore crystal lattice, aluminum having been found to be particularly advantageous as a trivalent main group element. Together with rare earth elements, aluminum forms, for example, a perovskite which produces a mechanically and thermally stable thermal barrier coating.
  • the perovskite is therefore a rare earth aluminate.
  • the empirical formula is ReAlO 3 , with Re standing for a rare earth element.
  • the rare earth aluminate is preferably a gadolinium lanthanum aluminate.
  • the empirical formula is typically Gd 0.25 La 0.75 AlO 3 .
  • the subgroup elements hafnium and/or titanium and/or zirconium are used as the tetravalent metal B of the pyrochlore.
  • the pyrochlore is therefore advantageously selected from the rare earth titanate and/or rare earth hafnate and/or rare earth zirconate group.
  • the rare earth zircbnate is specifically selected from the gadolinium zirconate and/or samarium zirconate group.
  • the preferred empirical formulae are Gd 2 Zr 2 O 7 and Sm 2 Zr 2 O 7 .
  • the rare earth hafnate is preferably lanthanum hafnate.
  • the empirical formula is La 2 Hf 2 O 7 .
  • the luminophore is optically excited to emit luminescent light, said luminophore being irradiated with excitation light of a particular excitation wavelength. By absorbing the excitation light, the luminophore is excited to emit luminescent light.
  • the excitation light is e.g. UV light and the luminescent light low-energy visible light.
  • the excitation of the luminophore with excitation light lends itself to checking the condition of a luminophore-containing thermal barrier coating optically accessible to the excitation light and the luminescent light. For this purpose, e.g. only the thermal barrier coating containing the luminophore is deposited on the substrate.
  • thermal barrier coating in a particular embodiment in respect of the arrangement of thermal barrier coating on the substrate, at least one other thermal barrier coating is present which is essentially luminophore-free, essentially free meaning that, due to a very low proportion of luminophore, no analyzable luminescent light can be detected.
  • the additional thermal barrier coating can be disposed between the substrate and the thermal barrier coating containing the luminophore.
  • the outer thermal barrier coating is formed by the thermal barrier coating containing the luminophore. Any transmission property of the additional thermal barrier coating in respect of the luminescent light and/or the excitation light is irrelevant.
  • the thermal barrier coating containing the luminophore is optically accessible. A solution of this kind is advantageous, for example, for a thermal barrier coating comprising a pyrochlore.
  • an additional thermal barrier coating consisting of an yttrium stabilized zirconium oxide is deposited directly on the metallic interlayer.
  • the thermal barrier coating containing the luminophore is deposited over this additional thermal barrier coating.
  • the additional thermal barrier coating can also be transparent to the excitation light and the luminescent light of the luminophore.
  • the excitation light and the luminescent light can penetrate through the additional thermal barrier coating.
  • the thermal barrier coating can be disposed between the additional thermal barrier coating and the substrate. Due to the transmission property of the additional thermal barrier coating, the thermal barrier coating containing-the luminophore is continuously optically accessible. In this way, as in the cases in which only the thermal barrier coating containing the luminophore is present or the thermal barrier coating containing the luminophore forms the outer thermal barrier coating of a multilayer structure, the condition of the thermal barrier coating can be determined by observing one of the emission properties of the luminescent light. Thus, for example, the temperature of the thermal barrier coating can be indicated.
  • the additional thermal barrier coating is opaque to the excitation light for stimulating the luminophore to emit luminescent light and/or to the luminescent light of the luminophore. Because of the transmission or absorption properties of the additional thermal barrier coating, the excitation light and/or the luminescent light cannot penetrate, or only a small portion of it can penetrate, the additional thermal barrier coating. In a particular embodiment, the thermal barrier coating is disposed between the substrate and the additional thermal barrier coating in such a way that the excitation light of the luminophore and/or the luminescent light of the luminophore can essentially only reach the environment of the substrate through orifices in the additional thermal barrier coating.
  • Such orifices are, for example, cracks or gaps in the additional thermal barrier coating. Also conceivable is an orifice caused by erosion of other thermally insulating material of the additional thermal barrier coating. These orifices can easily be made visible by illuminating the arrangement with the excitation light. At the locations in which the UV light reaches the thermal barrier coating through the orifices, the luminophore is excited to emit luminescent light. The luminescent light passes again through the orifices to the environment of the substrate where it can be detected. Because of the orifices, luminescent light occurs which stands out clearly from the background.
  • the thermal barrier coating of a substrate used in the equipment can be checked in a simple and reliable manner in the way described.
  • the equipment can be e.g. a gas turbine, the substrate e.g. a gas turbine blade.
  • the multilayer system comprised of the thermal barrier coatings is disposed on the turbine blade. By illuminating the turbine blade and observing the luminescent light of the luminophore, the locations in the additional, outermost thermal barrier coating which have orifices become visible.
  • the condition of the thermal barrier coating may be checked during operation of the equipment.
  • a combustion chamber of the above-described gas turbine in which the turbine blades are installed is provided with a window through which the luminescence of the luminophore can be observed.
  • the occurrence of luminescent light indicates that the additional, outermost thermal barrier coating of at least one turbine blade has a crack or gap or is eroded.
  • a further advantage of the described arrangement is that, as a result of advanced erosion, the thermally insulating material containing the luminophore is also eroded away.
  • the luminophore can be detected in an exhaust gas of the gas turbine. This is an indication that erosion has advanced as far as the thermal barrier coating containing the luminophore.
  • the substrate is a component of an internal combustion engine, such as a diesel engine.
  • the internal combustion engine is a gas turbine, the substrate being e.g. a tile with which a combustion chamber of the gas turbine is clad.
  • the substrate is in particular a blade of the gas turbine, it being conceivable that the different substrates are provided with thermal barrier coatings containing luminophores which emit different luminescent light, thereby enabling the component on which damage is present to be easily determined.
  • any coating process can be used.
  • the coating process is in particular plasma spray coating. It can also be a vapor deposition process, such as PVD (physical vapor deposition) or CVD (chemical vapor deposition). Using the method described, thermal barrier coatings with layer thicknesses of 50 to 600 ⁇ m or more can be deposited.
  • the materials used are stable at temperatures of over 1200° C., making them particularly suitable for use in internal combustion engines, e.g. in a gas turbine.
  • the metal oxides used are selectively doped with activators, thereby yielding thermal barrier coatings containing luminescent substances that are thermally and mechanically stable even at temperatures above 1200° C. and which can be used to check the condition of the thermal barrier coatings during operation but also when the substrate is not in operation.
  • FIGS. 1 to 3 each show a detail of a lateral cross-section of an arrangement of a thermal barrier coating comprising a thermally insulating material containing a luminophore.
  • the arrangement 1 consists of a substrate 2 on which a thermal barrier coating 3 is disposed ( FIG. 1 ).
  • the substrate 2 is a turbine blade of a gas turbine.
  • the turbine blade is made of metal.
  • temperatures of over 1200° C. can occur during operation of the gas turbine.
  • the thermal barrier coating 3 is present in order to prevent the surface 8 of the substrate 2 from overheating.
  • the thermal barrier coating 3 is used to limit heat transfer between the substrate 2 and the environment 7 of the substrate 2 .
  • a metal alloy interlayer 4 (bond coat) is deposited between the thermal barrier coating 3 and the substrate 2 .
  • the thermal barrier coating 3 , the interlayer 4 and possibly the additional thermal barrier coating 5 are deposited on the surface 8 of the substrate 2 using a plasma spray process.
  • the thermally insulating material of the thermal barrier coating 3 is a metal oxide in the form of a rare earth aluminate with the empirical formula Gd 0.25 La 0.75 AlO 3 .
  • the rare earth aluminate is mixed with 1 mol % Eu 2 O 3 .
  • the rare earth aluminate has the activator europium in a proportion of 1 mol %. Exciting the luminophore with UV light results in a red luminescent light with an emission maximum at around 610 nm.
  • the excitation wavelength is typically 254 nm.
  • the rare earth aluminate is doped with 1 mol % terbium, resulting in a luminophore with green luminescent light having an emission wavelength at 544 nm.
  • the thermal barrier coating 3 consists of a pyrochlore.
  • the pyrochlore is a gadolinium zirconate with the empirical formula Gd 2 Zr 2 O 7 .
  • the pyrochlore is mixed with 1 mol % Eu 2 O 3 .
  • the gadolinium zirconate has the activator europium in a proportion of 1 mol %.
  • an additional thermal barrier coating 5 is present between the bond coat 4 and the thermal barrier coating 3 containing the luminophore.
  • the additional thermal barrier coating 5 consists of yttrium stabilized zirconium oxide.
  • a multilayer structure is likewise present ( FIG. 3 ).
  • the thermal barrier coating 3 containing the luminophore is disposed between the additional thermal barrier coating 5 and the substrate 2 .
  • the additional thermal barrier coating 5 is opaque to the excitation light and/or the luminescent light of the luminophore. The luminescent light of the luminophore can only be detected in the environment of the substrate if the additional thermal barrier coating 5 has an orifice 6 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Luminescent Compositions (AREA)
  • Laminated Bodies (AREA)
  • Thermal Insulation (AREA)
US10/566,980 2003-08-13 2004-07-28 Heat-insulation material and arrangement of a heat-insulation layer containing said heat-insulation material Abandoned US20060177676A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10337287.3 2003-08-13
DE10337287 2003-08-13
PCT/EP2004/051632 WO2005019370A2 (de) 2003-08-13 2004-07-28 Wärmedämmstoff und anordnung einer wärmedämmschicht mit dem wärmedämmstoff

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US20080102012A1 (en) * 2006-10-04 2008-05-01 Sharp Kabushiki Kaisha Phosphor
US20090202864A1 (en) * 2005-08-24 2009-08-13 Feist Joerg Peter Luminescent material compositions and structures incorporating the same
US20100248079A1 (en) * 2006-08-14 2010-09-30 Toyo Seikan Kaisha, Ltd. Coil spring for a fuel cell
JP2010242109A (ja) * 2007-05-07 2010-10-28 Siemens Ag パイロクロア相と酸化物とを有する２層層組織
US8158428B1 (en) * 2010-12-30 2012-04-17 General Electric Company Methods, systems and apparatus for detecting material defects in combustors of combustion turbine engines
RU2464175C2 (ru) * 2007-05-07 2012-10-20 Сименс Акциенгезелльшафт Керамический порошок, керамический слой и многослойная система с пирохлорной фазой и оксидами
US9395301B2 (en) 2014-10-02 2016-07-19 General Electric Company Methods for monitoring environmental barrier coatings
WO2017148839A1 (de) * 2016-02-29 2017-09-08 Siemens Aktiengesellschaft Beschichtung mit temperatursensor sowie damit beschichtetes bauteil
WO2017148729A1 (de) * 2016-02-29 2017-09-08 Siemens Aktiengesellschaft Beschichtung mit temperatursensor sowie damit beschichtetes bauteil
WO2017218759A1 (en) 2016-06-15 2017-12-21 The Penn State Research Foundation Thermal barrier coatings
US9964455B2 (en) 2014-10-02 2018-05-08 General Electric Company Methods for monitoring strain and temperature in a hot gas path component

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EP1790754A1 (de) 2005-11-24 2007-05-30 Siemens Aktiengesellschaft Schichtsystem mit Gadolinium-Mischkristall-Pyrochlorphase
EP1806432A1 (de) * 2006-01-09 2007-07-11 Siemens Aktiengesellschaft Schichtsystem mit zwei Pyrochlorphasen
EP1818424A1 (de) * 2006-02-09 2007-08-15 Siemens Aktiengesellschaft Verfahren zur Herstellung einer Schicht mit thermographischem Leuchtstoff und ein Schichtsystem
GB2439389A (en) * 2006-06-22 2007-12-27 Southside Thermal Sciences Multi layer coatings
DE502007005837D1 (de) * 2007-05-07 2011-01-13 Siemens Ag Zweilagiges Schichtsystem mit Pyrochlorphase und Oxiden
FR3030751B1 (fr) * 2014-12-17 2019-06-14 Safran Procede de controle de l'etat d'une barriere thermique par endoscopie

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US9045830B2 (en) 2005-08-24 2015-06-02 New Sts Limited Luminescent material compositions and structures incorporating the same
US20090202864A1 (en) * 2005-08-24 2009-08-13 Feist Joerg Peter Luminescent material compositions and structures incorporating the same
US20100248079A1 (en) * 2006-08-14 2010-09-30 Toyo Seikan Kaisha, Ltd. Coil spring for a fuel cell
US20080102012A1 (en) * 2006-10-04 2008-05-01 Sharp Kabushiki Kaisha Phosphor
JP2010242109A (ja) * 2007-05-07 2010-10-28 Siemens Ag パイロクロア相と酸化物とを有する２層層組織
RU2464175C2 (ru) * 2007-05-07 2012-10-20 Сименс Акциенгезелльшафт Керамический порошок, керамический слой и многослойная система с пирохлорной фазой и оксидами
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