EP1817528B1 - Method for the production of a thermal shield element - Google Patents
Method for the production of a thermal shield element Download PDFInfo
- Publication number
- EP1817528B1 EP1817528B1 EP05811090.9A EP05811090A EP1817528B1 EP 1817528 B1 EP1817528 B1 EP 1817528B1 EP 05811090 A EP05811090 A EP 05811090A EP 1817528 B1 EP1817528 B1 EP 1817528B1
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- European Patent Office
- Prior art keywords
- heat shield
- shield element
- thermal expansion
- region
- coefficient
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
- F23M5/00—Casings; Linings; Walls
- F23M5/02—Casings; Linings; Walls characterised by the shape of the bricks or blocks used
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23R—GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS
- F23R3/00—Continuous combustion chambers using liquid or gaseous fuel
- F23R3/002—Wall structures
Definitions
- the present invention relates to a heat shield element, in particular a ceramic heat shield element, a method for producing a ceramic heat shield element, a built-up of heat shield elements Heisgasausposed and provided with a Heisgasausposed combustion chamber, which may be formed in particular as a gas turbine combustor.
- the walls of hot gas-carrying combustors, such as gas turbine plants require thermal shielding of their supporting structure against hot gas attack.
- the thermal shielding can be realized, for example, by means of a hot gas lining upstream of the actual combustion chamber wall, for example in the form of a ceramic heat shield.
- a ceramic heat shield Such a Heisgasausstage usually constructed of a number of metallic or ceramic heat shield elements with which the combustion chamber wall is lined flat. Ceramic materials are ideally suited for the construction of a hot gas lining compared to metallic materials because of their high temperature resistance, corrosion resistance and low thermal conductivity.
- a ceramic heat shield is, for example, in EP 0 558 540 B1 described.
- the US 4,485,630 A shows a burner flame tube having a flat first alloy strip having the first heat transfer coefficient C1 and a second planar alloy strip having the heat transfer coefficient C2.
- the US 4,838,030 detects heat shields with 3 layers, a first ceramic layer, a second fibrous steel wool layer and a third metal layer.
- the metal layer has cooling channels.
- a heat shield element which is made of a base material mixture by pressing and subsequent sintering.
- a heat shield element is made of a base material mixture by pressing and subsequent sintering.
- thermal shock-resistant heat shields discloses the EP 1 142 852 A2 .
- a fiber-reinforced composite ceramic as the base body, which is provided on the hot side with a thermally sprayed temperature-resistant layer.
- a gradual structure in the material composition starting from the main body toward the hot side is selected.
- the thermal mobility particular ceramic heat shields must be guaranteed as a result of temperature-dependent expansion, so that no heat shield destructive thermal stresses by obstruction of temperature-dependent strain occur.
- expansion gaps are therefore present to the thermal expansion to enable the heat shield elements.
- the expansion gaps are designed so that they are never completely closed even at maximum temperature of the hot gas. It must therefore be ensured that the hot gas does not reach the load-bearing wall structure of the combustion chamber via the expansion gaps. In order to block the expansion gaps against the entry of hot gas, they are often flushed with a flowing in the direction of the combustion chamber interior air flow.
- air is used as the sealing air, which at the same time serves as cooling air for cooling retaining elements holding the heat shield elements, which leads inter alia to the occurrence of temperature gradients in the region of the edges of a heat shield element. Therefore, in particular with ceramic heat shield elements, even without the contact of adjacent heat shield elements, stresses occur on the hot side, which can lead to cracking and thus adversely affect the life of the heat shield elements.
- metallic heat shield elements have a higher resistance to thermal fluctuations and mechanical loads than ceramic heat shield elements, however, for example in gas turbine combustion chambers, they require complex cooling of the heat shield, since they have a higher thermal conductivity than ceramic heat shield elements.
- metallic heat shield elements are more susceptible to corrosion and, due to their lower temperature stability, can not be subjected to temperatures as high as those of ceramic heat shield elements. In order to minimize the formation of cracks, it is therefore generally endeavored to minimize the thermal load on the heat shield elements of a heat shield.
- a heat shield element has a hot side facing a hot medium, a cold side to be turned away from the hot medium, and circumferential surfaces connecting the hot side with the cold side.
- the hot side, the cold side and the peripheral surfaces limit the material volume of the heat shield element.
- the advantageous heat shield element is characterized in that the volume of material comprises at least two areas of material which differ from each other in their coefficients of thermal expansion.
- the thermal expansion of the material regions can be influenced in a targeted manner.
- the stresses within the heat shield element can be reduced during operation of a heat shield.
- the advantageous heat shield element is designed as a ceramic heat shield element.
- the reduced voltage formation due to the different coefficients of thermal expansion when spatial temperature gradients occur within the ceramic heat shield element leads to a reduced tendency to crack. This reduces the risk in a ceramic heat shield of formation of long cracks, which would lead to an exchange of the heat shield element. In addition, the reduced cracking tendency leads to a longer life of the heat shield elements and thus to a reduction the replacement rates of heat shield elements in hot gas linings.
- At least one material region with a relatively low coefficient of thermal expansion adjoins the hot side of the heat shield element, whereas at least one material region with a relatively high coefficient of thermal expansion adjoins the cold side of the heat shield element.
- On the hot side occur at the transition from the ambient temperature (for example, when a gas turbine plant) to maximum operating temperature (for example, at full load of a gas turbine plant) greater temperature differences than on the cooled cold side of the heat shield element.
- At least one material region with a relatively high coefficient of thermal expansion adjoins the peripheral surface of the heat shield element, and at least one material region with a relatively low coefficient of thermal expansion, viewed from the peripheral surfaces, can be arranged inside the material volume.
- a material region with a relatively low coefficient of thermal expansion on the hot side and a material region with a relatively high coefficient of thermal expansion can also adjoin the cold side. Since, in particular in the area of the peripheral surfaces, the heat shield elements of a heat shield are cooled due to the blocking air flow, high temperature stresses occur in heat shield elements with a homogeneous coefficient of thermal expansion in the area of the peripheral surfaces Heat shield element particularly low operating temperatures arise. The fact that the coefficient of thermal expansion is increased in the region of the peripheral surfaces compared to the interior (seen from the peripheral surfaces) of the heat shield element, the voltages occurring can be reduced.
- adjacent material regions with different coefficients of thermal expansion are configured in such a way that a smooth transition from the thermal expansion coefficient of one material region to the thermal expansion coefficient of the other material region takes place in the zone of the transition from one material region to the other material region. Due to the smooth transition of the thermal expansion coefficient, the risk of destruction of the heat shield during the manufacturing process, in particular during the sintering process, which takes place at elevated, approximately homogeneous temperature, can be reduced.
- the object of the present invention is to provide a method for producing heat shield elements in which the material properties are adapted to the respective different loads and in this case take into account the thermal stresses within the heat shield element.
- the object of the invention is achieved by a method according to claim 1.
- the further claim contains an advantageous development of the invention.
- pressing or casting of a base material mixture takes place and subsequent sintering of the pressed or cast base material mixture.
- the inventive method is characterized in that prior to sintering the pressed or cast base material mixture adjusting the thermal expansion coefficient different material areas. By adjusting the thermal expansion coefficients of different material regions, the resistance of a heat shield element produced by means of the method according to the invention to temperature gradients within the heat shield element can be increased.
- the invention provides to adjust the thermal expansion coefficients by aftertreatment of at least one material area after pressing or casting of the base material mixture and before sintering, which after sintering compared to the rest of the base material mixture changed, for example.
- a relatively low coefficient of thermal expansion should have.
- the aftertreatment can be carried out, for example, by impregnating the at least one material area to be post-treated with a liquid. This approach allows a particularly good definition of material areas, which should have a relation to the rest of the base material mixture modified thermal expansion coefficient.
- the FIG. 1 shows a ceramic heat shield element 1 in a perspective view.
- the heat shield element 1 has a hot side 3, which faces the hot medium after installation of the heat shield element 1 in a heat shield.
- the hot side 3 is opposite the cold side 5 of the heat shield element 1, which faces after installation in a heat shield of the supporting structure of the combustion chamber wall and thus faces away from the hot medium.
- Hot side 3 and cold side 5 are connected to each other via first peripheral surfaces 7 and second peripheral surfaces 9.
- the second peripheral surfaces 9 have grooves 11 into which retaining clips (not shown) connected to the supporting structure of the combustion chamber wall can engage in order to hold the heat shield element in position after installation in a ceramic hot gas lining.
- the first peripheral surfaces 7, however, have no groove.
- the hot side 3, the cold side 5, the first peripheral surfaces 7 and the second peripheral surfaces 9 enclose the material volume of the heat shield element, which provides the thermal shielding effect.
- FIG. 2a A first embodiment of the heat shield element is shown in FIG. 2a shown in section.
- the cut runs along from the line AA FIG. 1 , It can be seen the hot side 13, the cold side 15 and the groove-free peripheral surfaces 17 of the heat shield element 10 of the first embodiment.
- the heat shield element 10 has a first material region 19 and second material regions 21, which differ from the material region 19 by their thermal expansion coefficient.
- the thermal expansion coefficient of the material regions 21 is greater than the thermal expansion coefficient of the material region 19. In this sense, the material region 19 has a relatively low thermal expansion coefficient, whereas the material regions 21 have a relatively high coefficient of thermal expansion.
- the load-bearing structure of the combustion chamber wall is lined with a number of heat shield elements 10 area-covering.
- the heat shield elements 10 are attached to one another in such a way that expansion gaps remain between adjacent heat shield elements 10. These expansion gaps serve to allow expansion of the heat shield elements 10 during operation of the combustion chamber due to the high operating temperatures without the heat shield elements 10 touching each other.
- the relatively cool material regions 21 in a conventional heat shield element would be subject to stress due to their relatively low thermal expansion from the hot central region 19 experiencing greater thermal expansion, and could crack when exceeding the material strength.
- the cracks would emanate from the edges of the heat shield and extend toward the heat shield interior. Such cracking can reduce the life of a heat shield element.
- the stresses are reduced, in particular in the cool peripheral regions, since the material regions 21 have a higher coefficient of thermal expansion than the central material region 19.
- the higher temperature of the central material region 19 is thus due to the larger thermal expansion coefficient of the material regions 21 in the region of the peripheral surfaces 17th balanced.
- the thermal expansion coefficients of the material regions 19 and 21 and the extent of these material regions in the material volume of the heat shield element 10 can be numerically optimized in such a way that the stresses in the heat shield element 10 are minimized.
- the expansion of the material regions 21 can be determined with relatively high coefficients of thermal expansion, by first performing a calculation of the temperature field which is established in the desired operating state under corresponding boundary conditions in the heat shield element. Subsequently, on the basis of this result, the size of the regions 21 for the selected coefficient of thermal expansion can be adjusted such that a minimization of the stresses in the heat shield element 10 takes place.
- you can too the thermal expansion coefficients and the expansions of the material areas are simultaneously optimized.
- FIG. 2a In the area of the groove-free circumferential surfaces 17 of the heat shield element, material regions 21 with an increased thermal expansion coefficient and reduced thermal conductivity compared to the central material region 19 are present. Additionally or alternatively, the heat shield element 10 can also have material regions 20 with an increased thermal expansion coefficient and reduced thermal conductivity in the region of the second peripheral surfaces compared to the central material region 19, ie in the region of the peripheral surfaces (18). Fig. 2b ).
- FIG. 3 A second embodiment of the heat shield element is in FIG. 3 shown in section.
- the section runs along the in FIG. 1 represented line AA. Accordingly, the hot side 113, the cold side 115 and the groove-free peripheral surfaces 117 of the heat shield element 110 can be seen.
- the heat shield element 110 has on the hot side a material region 119 with a relatively low coefficient of thermal expansion and a relatively low thermal conductivity. On the cold side, it has a material region 121 with a thermal expansion coefficient which is increased compared to the hot-side material region 119, an increased thermal conductivity and increased mechanical strength.
- This embodiment takes into account the fact that the hot side 113 of a heat shield element during operation of a combustion chamber is exposed to a higher temperature than the generally cooled cold side 115. In the heat shield element 110, therefore, a temperature gradient forms from the hot side 113 to the cold side 115 out. The lower temperature of the cold side material portion 121 is then during operation of the combustion chamber by its compared to the hot side Material range 119 compensated higher thermal expansion coefficient. Stress due to the temperature gradient can therefore be reliably avoided.
- FIG. 4 A third embodiment of the heat shield element is shown in FIG FIG. 4 shown in section.
- the section runs along the in FIG. 1 represented line AA. Accordingly, the cold side 213, the hot side 215 and the groove-free peripheral surfaces 217 of the heat shield element 210 can be seen.
- the heat shield element 210 has a first, hot-side material region 219 having a first coefficient of thermal expansion, peripheral second material regions 221 having a second thermal expansion coefficient, and a cold-side material region 223 having a third coefficient of thermal expansion.
- the second and the third thermal expansion coefficient may also be identical.
- the heat shield element shown here there are relatively abrupt transitions between the different material regions and thus relatively abrupt transitions between different thermal expansion coefficients.
- the areas with different coefficients of expansion should, if possible, not be in the form of sharp boundaries of the material properties, but rather in the form of smooth transitions of the material properties in order to avoid the risk of destruction of the heat shield during the manufacturing process, in particular during sintering. which occurs at elevated, largely homogeneous temperature, to avoid.
- FIGS. 5a and 5b A manufacturing method for heat shield elements will now be described with reference to FIGS FIGS. 5a and 5b described.
- a material mixture 419 is placed in a mold 440, 450 and then pressed.
- the result is a green body 410 of the heat shield element.
- This green compact 410 is in FIG. 5b shown. It can be seen the hot side 413, the cold side 415 and the groove-free peripheral surfaces 417 of the green body 410.
- the green body 410 is impregnated with a liquid which influences the sintering process.
- the liquid is selected such that the impregnated regions 421 after sintering have a higher coefficient of thermal expansion than the non-impregnated region 419.
- the grooved peripheral surfaces of the green body 410 (in FIG Fig. 5b not visible) are soaked to increase the thermal expansion coefficient of the corresponding areas.
- the result of with regard to the FIGS. 5a and 5b described method is a heat shield element, as in FIG. 2 is shown.
- the mold When pressing the heat shield element, the mold can be filled horizontally or vertically and the filling of material mixtures using stencils done.
- the mold can be placed or filled at any angle.
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Description
Die vorliegende Erfindung betrifft ein Hitzeschildelement, insbesondere ein keramisches Hitzeschildelement, ein Verfahren zum Herstellen eines keramischen Hitzeschildelementes, eine aus Hitzeschildelementen aufgebaute Heisgasauskleidung sowie eine mit einer Heisgasauskleidung versehene Brennkammer, die insbesondere als Gasturbinenbrennkammer ausgebildet sein kann.The present invention relates to a heat shield element, in particular a ceramic heat shield element, a method for producing a ceramic heat shield element, a built-up of heat shield elements Heisgasauskleidung and provided with a Heisgasauskleidung combustion chamber, which may be formed in particular as a gas turbine combustor.
Die Wände von heißgasführenden Brennkammern, beispielsweise von Gasturbinenanlagen erfordern eine thermische Abschirmung ihrer tragenden Struktur gegen Heißgasangriff. Die thermische Abschirmung kann beispielsweise durch eine der eigentlichen Brennkammerwand vorgelagerte Heisgasauskleidung, bspw. in Form eines keramischen Hitzeschildes, realisiert werden. Eine derartige Heisgasauskleidung in der Regel aus einer Anzahl von metallischen oder keramischen Hitzeschildelementen aufgebaut, mit denen die Brennkammerwand flächig ausgekleidet ist. Keramische Materialien bieten sich für den Aufbau einer Heisgasauskleidung im Vergleich zu metallischen Werkstoffen aufgrund ihrer hohen Temperaturbeständigkeit, Korrosionsbeständigkeit und niedrigen Wärmeleitfähigkeit idealerweise an. Ein keramischer Hitzeschild ist bspw. in
Die
Die
Weiterhin ist aus der
Eine weitere Lösung zur Realisierung Thermoschock-beständiger Hitzeschilde offenbart die
Einen weiteren Ansatz zur Anpassung der Materialeigenschaften an die unterschiedlichen Belastungen auf der Heißseite und der gegenüberliegenden Wandseite verfolgt die Ausführung aus der
Wegen materialtypischer Wärmedehnungseigenschaften und der im Rahmen des Betriebs typischerweise auftretenden Temperaturunterschiede - etwa zwischen der Umgebungstemperatur bei Stillstand der Gasturbinenanlage und der maximalen Temperatur bei Volllast - muss die Wärmebeweglichkeit insbesondere keramischer Hitzeschilde in Folge temperaturabhängiger Dehnung gewährleistet sein, damit keine den Hitzeschild zerstörenden Wärmespannungen durch Behinderung der temperaturabhängigen Dehnung auftreten. Zwischen den einzelnen Hitzeschildelementen sind daher Dehnspalte vorhanden, um die Wärmeausdehnung der Hitzeschildelemente zu ermöglichen. Aus Sicherheitsgründen sind die Dehnspalte so ausgelegt, dass die auch bei maximaler Temperatur des Heißgases nie völlig geschlossen sind. Es ist daher sicherzustellen, dass das Heißgas nicht über die Dehnspalte zur tragenden Wandstruktur der Brennkammer gelangt. Um die Dehnspalte gegen den Eintritt von Heißgas zu sperren, werden diese häufig mit einem in Richtung des Brennkammerinneren strömenden Sperrluftstrom gespült. Als Sperrluft findet in der Regel Luft Verwendung, die gleichzeitig als Kühlluft zum Kühlen von die Hitzeschildelemente haltenden Haltelementen dient, was u.a. zum Auftreten von Temperaturgradienten im Bereich der Kanten eines Hitzeschildelementes führt. Daher kommt es insbesondere bei keramischen Hitzeschildelementen auch ohne die Berührung benachbarter Hitzeschildelemente zu Spannungen auf der Heisseite, welche zu Rissbildungen führen und damit die Lebensdauer der Hitzeschildelemente negativ beeinflussen können.Due to material-typical thermal expansion properties and the temperature differences typically occurring during operation - such as between the ambient temperature at standstill of the gas turbine plant and the maximum temperature at full load - the thermal mobility particular ceramic heat shields must be guaranteed as a result of temperature-dependent expansion, so that no heat shield destructive thermal stresses by obstruction of temperature-dependent strain occur. Between the individual heat shield elements expansion gaps are therefore present to the thermal expansion to enable the heat shield elements. For safety reasons, the expansion gaps are designed so that they are never completely closed even at maximum temperature of the hot gas. It must therefore be ensured that the hot gas does not reach the load-bearing wall structure of the combustion chamber via the expansion gaps. In order to block the expansion gaps against the entry of hot gas, they are often flushed with a flowing in the direction of the combustion chamber interior air flow. As a rule, air is used as the sealing air, which at the same time serves as cooling air for cooling retaining elements holding the heat shield elements, which leads inter alia to the occurrence of temperature gradients in the region of the edges of a heat shield element. Therefore, in particular with ceramic heat shield elements, even without the contact of adjacent heat shield elements, stresses occur on the hot side, which can lead to cracking and thus adversely affect the life of the heat shield elements.
Um den Bedarf an Sperrluft zu verringern, wurde in
Alternative Vorgehensweisen bestehen darin, Hitzeschildelemente aus Metall zu verwenden. Metallische Hitzeschildelemente weisen zwar gegenüber Temperaturschwankungen und mechanischen Belastungen eine höhere Widerstandsfähigkeit als keramische Hitzeschildelemente auf, erfordern jedoch bspw. in Gasturbinenberennkammern eine aufwändige Kühlung des Hitzeschildes, da sie eine höhere Wärmeleitfähigkeit als keramische Hitzeschildelemente besitzen. Außerdem sind metallische Hitzeschildelemente korrosionsanfälliger und können aufgrund ihrer geringeren Temperaturstabilität nicht so hohen Temperaturen ausgesetzt werden wie keramische Hitzeschildelemente. Um Rissbildungen zu minimieren ist man daher in der Regel bemüht die thermische Belastung der Hitzeschildelemente eines Hitzeschildes möglichst gering zu halten.Alternative approaches are to use metal heat shield elements. Although metallic heat shield elements have a higher resistance to thermal fluctuations and mechanical loads than ceramic heat shield elements, however, for example in gas turbine combustion chambers, they require complex cooling of the heat shield, since they have a higher thermal conductivity than ceramic heat shield elements. In addition, metallic heat shield elements are more susceptible to corrosion and, due to their lower temperature stability, can not be subjected to temperatures as high as those of ceramic heat shield elements. In order to minimize the formation of cracks, it is therefore generally endeavored to minimize the thermal load on the heat shield elements of a heat shield.
Ein Hitzeschildelement weist eine einem heißen Medium zuzuwendende Heißseite, eine dem heißen Medium abzuwendende Kaltseite sowie die Heißseite mit der Kaltseite verbindende Umfangsflächen auf. Die Heißseite, die Kaltseite und die Umfangsflächen begrenzen das Materialvolumen des Hitzeschildelementes. Das vorteilhafte Hitzeschildelement zeichnet sich dadurch aus, dass das Materialvolumen mindestens zwei Materialbereiche umfasst, welche sich in ihren thermischen Ausdehnungskoeffizienten voneinander unterscheiden.A heat shield element has a hot side facing a hot medium, a cold side to be turned away from the hot medium, and circumferential surfaces connecting the hot side with the cold side. The hot side, the cold side and the peripheral surfaces limit the material volume of the heat shield element. The advantageous heat shield element is characterized in that the volume of material comprises at least two areas of material which differ from each other in their coefficients of thermal expansion.
Mit geeigneten thermischen Ausdehnungskoeffizienten lässt sich die thermische Ausdehnung der Materialbereiche gezielt beeinflussen. Insbesondere wenn Materialbereiche, die für relativ hohe Betriebstemperaturen vorgesehen sind, einen relativ niedrigen thermischen Ausdehnungskoeffizienten aufweisen und Materialbereiche, die für relativ niedrige Betriebstemperaturen vorgesehen sind, einen relativ hohen thermischen Ausdehnungskoeffizienten aufweisen, lassen sich die Spannungen innerhalb des Hitzeschildelementes beim Betrieb eines Hitzeschildes reduzieren.With suitable thermal expansion coefficients, the thermal expansion of the material regions can be influenced in a targeted manner. In particular, when material areas provided for relatively high operating temperatures have a relatively low coefficient of thermal expansion and material areas provided for relatively low operating temperatures have a relatively high coefficient of thermal expansion, the stresses within the heat shield element can be reduced during operation of a heat shield.
Das vorteilhafte Hitzeschildelement ist als keramisches Hitzeschildelement ausgestaltet.The advantageous heat shield element is designed as a ceramic heat shield element.
Die in Folge der verschiedenen thermischen Ausdehnungskoeffizienten verringerte Spannungsbildung beim Auftreten räumlicher Temperaturgradienten innerhalb des keramischen Hitzeschildelementes führt zu einer verringerten Rissbildungsneigung. Dadurch verringert sich in einem keramischen Hitzeschild das Risiko der Ausbildung von langen Rissen, die zu einem Austausch des Hitzeschildelementes führen würden. Zudem führt die verringerte Rissbildungsneigung zu einer höheren Lebensdauer der Hitzeschildelemente und somit zu einer Verringerung der Austauschraten von Hitzeschildelementen in Heisgasauskleidungen.The reduced voltage formation due to the different coefficients of thermal expansion when spatial temperature gradients occur within the ceramic heat shield element leads to a reduced tendency to crack. This reduces the risk in a ceramic heat shield of formation of long cracks, which would lead to an exchange of the heat shield element. In addition, the reduced cracking tendency leads to a longer life of the heat shield elements and thus to a reduction the replacement rates of heat shield elements in hot gas linings.
In einer Ausgestaltung des Hitzeschildelementes grenzt mindestens ein Materialbereich mit relativ niedrigem thermischen Ausdehnungskoeffizient an die Heißseite des Hitzeschildelementes an, wohingegen mindestens ein Materialbereich mit relativ hohem thermischen Ausdehnungskoeffizient an die Kaltseite des Hitzeschildelementes angrenzt. An der Heißseite treten beim Übergang von der Umgebungstemperatur (beispielsweise beim Stillstand einer Gasturbinenanlage) zu maximaler Betriebstemperatur (beispielsweise bei Volllast einer Gasturbinenanlage) größere Temperaturunterschiede auf als an der gekühlten Kaltseite des Hitzeschildelementes. Diese werden in der beschriebenen Ausgestaltung dadurch ausgeglichen, dass der thermische Ausdehnungskoeffizient des Hitzeschildelementes im Bereich der Heißseite geringer ist als im Bereich der Kaltseite. Bei geeigneter Wahl der thermischen Ausdehnungskoeffizienten lässt sich die Materialausdehnung im Bereich der Kaltseite an die Materialausdehnung im Bereich der Heißseite anpassen, wodurch Materialspannungen im Hitzeschildelement verringert werden können.In one embodiment of the heat shield element, at least one material region with a relatively low coefficient of thermal expansion adjoins the hot side of the heat shield element, whereas at least one material region with a relatively high coefficient of thermal expansion adjoins the cold side of the heat shield element. On the hot side occur at the transition from the ambient temperature (for example, when a gas turbine plant) to maximum operating temperature (for example, at full load of a gas turbine plant) greater temperature differences than on the cooled cold side of the heat shield element. These are compensated in the described embodiment in that the thermal expansion coefficient of the heat shield element in the region of the hot side is lower than in the region of the cold side. With a suitable choice of the coefficients of thermal expansion, the material expansion in the region of the cold side can be adapted to the material expansion in the region of the hot side, whereby material stresses in the heat shield element can be reduced.
Außerdem kann wenigstens ein Materialbereich mit relativ hohem thermischen Ausdehnungskoeffizienten an die Umfangsfläche des Hitzeschildelementes angrenzen und wenigstens ein Materialbereich mit relativ niedrigem thermischen Ausdehnungskoeffizienten von den Umfangsflächen aus gesehen im Inneren des Materialvolumens angeordnet sein. In dieser Ausgestaltung kann außerdem auch ein Materialbereich mit relativ niedrigem thermischem Ausdehnungskoeffizienten an die Heißseite und ein Materialbereich mit relativ hohem thermischem Ausdehnungskoeffizienten an die Kaltseite angrenzen. Da insbesondere im Bereich der Umfangsflächen eine Kühlung der Hitzeschildelemente eines Hitzeschildes aufgrund des Sperrluftstromes erfolgt, treten in Hitzeschildelementen mit homogenem thermischen Ausdehnungskoeffizienten im Bereich der Umfangsflächen hohe Spannungen auf, die aufgrund der gegenüber dem Rest des Hitzeschildelementes besonders niedrigen Betriebstemperaturen entstehen. Dadurch, dass der thermische Ausdehnungskoeffizient im Bereich der Umfangsflächen im Vergleich zum Inneren (von den Umfangsflächen aus gesehen) des Hitzeschildelementes erhöht ist, lassen sich die auftretenden Spannungen reduzieren.In addition, at least one material region with a relatively high coefficient of thermal expansion adjoins the peripheral surface of the heat shield element, and at least one material region with a relatively low coefficient of thermal expansion, viewed from the peripheral surfaces, can be arranged inside the material volume. In addition, in this embodiment, a material region with a relatively low coefficient of thermal expansion on the hot side and a material region with a relatively high coefficient of thermal expansion can also adjoin the cold side. Since, in particular in the area of the peripheral surfaces, the heat shield elements of a heat shield are cooled due to the blocking air flow, high temperature stresses occur in heat shield elements with a homogeneous coefficient of thermal expansion in the area of the peripheral surfaces Heat shield element particularly low operating temperatures arise. The fact that the coefficient of thermal expansion is increased in the region of the peripheral surfaces compared to the interior (seen from the peripheral surfaces) of the heat shield element, the voltages occurring can be reduced.
In einer Weiterbildung des Hitzeschildelementes sind einander benachbarte Materialbereiche mit unterschiedlichen thermischen Ausdehnungskoeffizienten derart ausgestaltet, dass in der Zone des Übergangs von dem einen Materialbereich zum anderen Materialbereich ein fließender Übergang von dem thermischen Ausdehnungskoeffizienten des einen Materialbereiches zu dem thermischen Ausdehnungskoeffizienten des anderen Materialbereiches stattfindet. Aufgrund des fließenden Übergangs des thermischen Ausdehnungskoeffizienten lässt sich die Gefahr einer Zerstörung des Hitzeschildes während des Herstellungsverfahrens, insbesondere während des Sinterprozesses, der bei erhöhter, etwa homogener Temperatur stattfindet, verringern.In a further development of the heat shield element, adjacent material regions with different coefficients of thermal expansion are configured in such a way that a smooth transition from the thermal expansion coefficient of one material region to the thermal expansion coefficient of the other material region takes place in the zone of the transition from one material region to the other material region. Due to the smooth transition of the thermal expansion coefficient, the risk of destruction of the heat shield during the manufacturing process, in particular during the sintering process, which takes place at elevated, approximately homogeneous temperature, can be reduced.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zum Herstellen von Hitzeschildelemente zur Verfügung zu stellen, bei denen die Materialeigenschaften an die jeweils unterschiedlichen Belastungen angepasst sind und hierbei die thermischen Spannungen innerhalb des Hitzeschildelements berücksichtigen.The object of the present invention is to provide a method for producing heat shield elements in which the material properties are adapted to the respective different loads and in this case take into account the thermal stresses within the heat shield element.
Die Aufgabe der Erfindung wird durch ein Verfahren nach Anspruch 1 gelöst. Der weitere Anspruch enthält eine vorteilhafte Weiterbildung der Erfindung.
Im erfindungsgemäßen Verfahren zum Herstellen eines keramischen Hitzeschildelementes erfolgt ein Pressen oder Gießen einer Grundmaterialmischung und ein anschließendes Sintern der gepressten bzw. gegossenen Grundmaterialmischung. Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, dass vor dem Sintern der gepressten bzw. gegossenen Grundmaterialmischung ein Einstellen der thermischen Ausdehnungskoeffizienten verschiedener Materialbereiche erfolgt. Durch das Einstellen der thermischen Ausdehnungskoeffizienten verschiedener Materialbereiche lässt sich die Widerstandsfähigkeit eines mittels des erfindungsgemäßen Verfahrens hergestellten Hitzeschildelementes gegenüber Temperaturgradienten innerhalb des Hitzeschildelementes erhöhen.The object of the invention is achieved by a method according to claim 1. The further claim contains an advantageous development of the invention.
In the method according to the invention for producing a ceramic heat shield element, pressing or casting of a base material mixture takes place and subsequent sintering of the pressed or cast base material mixture. The inventive method is characterized in that prior to sintering the pressed or cast base material mixture adjusting the thermal expansion coefficient different material areas. By adjusting the thermal expansion coefficients of different material regions, the resistance of a heat shield element produced by means of the method according to the invention to temperature gradients within the heat shield element can be increased.
Hierzu ist erfindungsgemäß vorgesehen, das Einstellen der thermischen Ausdehnungskoeffizienten vorzunehmen, indem nach dem Pressen oder Gießen der Grundmaterialmischung und vor dem Sintern ein Nachbehandeln mindestens eines Materialbereiches erfolgt, welcher nach dem Sintern einen gegenüber dem Rest der Grundmaterialmischung veränderten, bspw. einen relativ niedrigen thermischen Ausdehnungskoeffizient aufweisen soll.For this purpose, the invention provides to adjust the thermal expansion coefficients by aftertreatment of at least one material area after pressing or casting of the base material mixture and before sintering, which after sintering compared to the rest of the base material mixture changed, for example. A relatively low coefficient of thermal expansion should have.
Das Nachbehandeln kann beispielsweise erfolgen, indem der mindestens eine nachzubehandelnde Materialbereich mit einer Flüssigkeit getränkt wird. Diese Vorgehensweise erlaubt eine besonders gute Festlegung von Materialbereichen, die einen gegenüber dem Rest der Grundmaterialmischung veränderten thermischen Ausdehnungskoeffizienten aufweisen sollen.The aftertreatment can be carried out, for example, by impregnating the at least one material area to be post-treated with a liquid. This approach allows a particularly good definition of material areas, which should have a relation to the rest of the base material mixture modified thermal expansion coefficient.
Weitere Merkmale, Eigenschaften und Vorteile der vorliegenden Erfindung ergeben sich aus der nachfolgenden Beschreibung von Ausführungsbeispielen unter Bezugnahme auf die beiliegenden Figuren.
-
Figur 1 zeigt ein Hitzeschildelement in einer perspektivischen Ansicht. -
Figur 2a zeigt eine erste Ausführungsform des inFigur 1 dargestellten Hitzeschildelementes in einem Schnitt entlang der Linie A-A. -
Figur 2b zeigt eine Abwandlung des inFigur 2a dargestellten Hitzeschildelementes in einem Schnitt entlang der Linie B-B ausFigur 1 . -
zeigt eine zweite Ausführungsform des inFigur 3Figur 1 dargestellten Hitzeschildelementes in einem Schnitt entlang der Linie A-A. -
Figur 4 zeigt eine dritte Ausführungsform des inFigur 1 dargestellten Hitzeschildelementes in einem Schnitt entlang der Linie A-A. -
Figur 5a zeigt einen ersten Schritt eines Herstellungsverfahrens für ein Hitzeschildelement. -
Figur 5b zeigt einen zweiten Schritt des inFigur 5a gezeigten Verfahrens.
-
FIG. 1 shows a heat shield element in a perspective view. -
FIG. 2a shows a first embodiment of the inFIG. 1 shown heat shield element in a section along the line AA. -
FIG. 2b shows a modification of the inFIG. 2a illustrated heat shield element in a section along the line BBFIG. 1 , -
FIG. 3 shows a second embodiment of the inFIG. 1 shown heat shield element in a section along the line AA. -
FIG. 4 shows a third embodiment of the inFIG. 1 shown heat shield element in a section along the line AA. -
FIG. 5a shows a first step of a method of manufacturing a heat shield element. -
FIG. 5b shows a second step of the inFIG. 5a shown method.
Die
Die Heißseite 3, die Kaltseite 5, die ersten Umfangsflächen 7 und die zweiten Umfangsflächen 9 umschließen das Materialvolumen des Hitzeschildelementes, welches für die thermische Abschirmwirkung sorgt.The
Eine erste Ausführungsform des Hitzeschildelementes ist in
Beim Aufbau eines Hitzeschildes, beispielsweise für eine Gasturbinenbrennkammer, wird die tragende Struktur der Brennkammerwand mit einer Anzahl Hitzeschildelementen 10 flächendeckend ausgekleidet. Die Hitzeschildelemente 10 werden dabei derart an einander angrenzend angebracht, dass Dehnspalte zwischen benachbarten Hitzeschildelementen 10 verbleiben. Diese Dehnspalte dienen dazu, eine Ausdehnung der Hitzeschildelemente 10 beim Betrieb der Brennkammer aufgrund der hohen Betriebstemperaturen zu ermöglichen, ohne dass sich die Hitzeschildelemente 10 gegenseitig berühren.When constructing a heat shield, for example for a gas turbine combustor, the load-bearing structure of the combustion chamber wall is lined with a number of
Um einen Durchtritt des heißen Mediums, beispielsweise heißer Verbrennungsgase, durch die Dehnspalte zur tragenden Struktur der Brennkammerwand zu verhindern, werden die Dehnspalte mit Sperrluft gespült, die gleichzeitig zum Kühlen der die Hitzeschildelemente 10 haltenden Halteelemente dient. Aus diesem Grund herrschen an den sperrluftumströmten ersten Umfangsflächen 17 und den ebenfalls sperrluftumströmten zweiten Umfangsflächen (in
Im Hitzeschildelement 10 sind die Spannungen insbesondere in den kühlen Umfangsbereichen verringert, da die Materialbereiche 21 einen höheren thermischen Ausdehnungskoeffizient aufweisen als der zentrale Materialbereich 19. Die höhere Temperatur des zentralen Materialbereiches 19 wird also durch den größeren thermischen Ausdehnungsbereichkoeffizienten der Materialbereiche 21 im Bereich der Umfangsflächen 17 ausgeglichen.In the
Die thermischen Ausdehnungskoeffizienten der Materialbereiche 19 bzw. 21 sowie die Ausdehnung dieser Materialbereiche im Materialvolumen des Hitzeschildelementes 10 können numerisch derart optimiert werden, dass die Spannungen im Hitzeschildelement 10 minimiert werden. Beispielsweise kann die Ausdehnung der Materialbereiche 21 mit relativ hohen thermischen Ausdehnungskoeffizienten festgelegt werden, indem zunächst eine Berechnung des sich im angestrebten Betriebszustand bei entsprechenden Randbedingungen im Hitzeschildelement einstellenden Temperaturfeldes durchgeführt wird. Anschließend kann anhand dieses Ergebnisses die Größe der Bereiche 21 für den gewählten thermischen Ausdehnungskoeffizienten so eingestellt werden, dass hierdurch eine Minimierung der Spannungen im Hitzeschildelement 10 erfolgt. Selbstverständlich können auch die thermischen Ausdehnungskoeffizienten und die Ausdehnungen der Materialbereiche simultan optimiert werden. Es ist aber auch möglich, die Ausdehnung beispielsweise der umfänglichen Materialbereiche 21 vorzugeben und mittels einer Optimierung geeignete thermische Ausdehnungskoeffizienten zu finden.The thermal expansion coefficients of the
In
Eine zweite Ausführungsform des Hitzeschildelementes ist in
Das Hitzeschildelement 110 weist heißseitig einen Materialbereich 119 mit relativ niedrigem thermischen Ausdehnungskoeffizienten und relativ niedriger thermischer Leitfähigkeit auf. Kaltseitig weist es einen Materialbereich 121 mit einem gegenüber dem heißseitigen Materialbereich 119 erhöhten thermischen Ausdehnungskoeffizienten, einer erhöhten thermischen Leitfähigkeit und erhöhten mechanischen Belastbarkeit auf. Diese Ausgestaltung trägt dem Umstand Rechnung, dass die Heißseite 113 eines Hitzeschildelementes beim Betrieb einer Brennkammer einer höheren Temperatur ausgesetzt ist als die in der Regel gekühlte Kaltseite 115. Im Hitzeschildelement 110 bildet sich daher ein Temperaturgradient von der Heißseite 113 zur Kaltseite 115 hin aus. Die niedrigere Temperatur des kaltseitigen Materialbereiches 121 wird dann beim Betrieb der Brennkammer durch dessen im Vergleich zum heißseitigen Materialbereich 119 höheren thermischen Ausdehnungskoeffizienten ausgeglichen. Spannungen aufgrund des Temperaturgradienten können daher zuverlässig vermieden werden.The
Eine dritte Ausführungsform des Hitzeschildelementes ist in
Weitere Kombinationen von Materialbereichen mit voneinander verschiedenen thermischen und/oder mechanischen Eigenschaften sind möglich, bspw. eine Kombination aus allen in den zuvor beschriebenen Ausführungsbeispielen erwähnten Materialbereichen.Further combinations of material regions with mutually different thermal and / or mechanical properties are possible, for example a combination of all the material regions mentioned in the exemplary embodiments described above.
In allen drei hier dargestellten Ausführungsformen des Hitzeschildelementes liegen relativ abrupte Übergänge zwischen den verschiedenen Materialbereichen und damit relativ abrupte Übergänge zwischen verschiedenen thermischen Ausdehnungskoeffizienten vor. Die Bereiche mit unterschiedlichen Ausdehnungskoeffizienten sollten jedoch möglichst nicht in Form von scharfen Grenzen der Materialeigenschaften, sondern vielmehr in Form fließender Übergänge der Materialeigenschaften vorliegen, um der Gefahr einer Zerstörung des Hitzeschildes während des Herstellungsprozesses, insbesondere während des Sinterns, das bei erhöhter, weitgehend homogener Temperatur stattfindet, zu vermeiden.In all three embodiments of the heat shield element shown here, there are relatively abrupt transitions between the different material regions and thus relatively abrupt transitions between different thermal expansion coefficients. The areas with different coefficients of expansion should, if possible, not be in the form of sharp boundaries of the material properties, but rather in the form of smooth transitions of the material properties in order to avoid the risk of destruction of the heat shield during the manufacturing process, in particular during sintering. which occurs at elevated, largely homogeneous temperature, to avoid.
Es kann für den jeweiligen Anwendungsfall rechnerisch bestimmt und optimiert werden, wie die Variation des thermischen Ausdehnungskoeffizienten ausgeführt werden muss, damit weder eine Zerstörung des Hitzeschildelementes während des Sintervorgangs droht, gleichzeitig aber eine optimale Wirkung zum Vermeiden der Spannungsbildung im Betriebszustand erreicht wird. Hieraus kann beispielsweise eine optimale Guss- bzw. Pressform für die Herstellung eines Grünlings, das heißt einer Vorstufe des Hitzeschildelementes aus einem polymerkeramischen Material, in welchem eine Teilvernetzung des Polymers vorliegt, abgeleitet werden. Eventuelle Formänderungen des Hitzeschildelementes während des Sinterprozesses können so kompensiert werden.It can be computationally determined and optimized for the particular application, as the variation of the thermal expansion coefficient must be performed so that neither threatens destruction of the heat shield element during the sintering process, but at the same time an optimal effect to avoid the formation of stress is achieved in the operating condition. From this, for example, an optimum casting or pressing mold for the production of a green body, that is to say a precursor of the heat shield element made of a polymer-ceramic material in which a partial crosslinking of the polymer is present, can be derived. Any changes in shape of the heat shield element during the sintering process can be compensated.
Ein Herstellungsverfahren für Hitzeschildelemente wird nun mit Bezug auf die
Optional können auch die mit Nuten versehenen Umfangsflächen des Grünlings 410 (in
Beim Pressen des Hitzeschildelementes kann die Form liegend oder stehend gefüllt werden und das Einfüllen von Materialmischungen unter Verwendung von Schablonen erfolgen. Die Pressform kann dabei unter beliebigem Winkel aufgestellt bzw. gefüllt werden.When pressing the heat shield element, the mold can be filled horizontally or vertically and the filling of material mixtures using stencils done. The mold can be placed or filled at any angle.
Zwar ist beispielhaft das Herstellen eines Hitzeschildelementes, wie es in
Claims (2)
- Method for producing a ceramic heat shield element, wherein initially a basic composite material (419, 421) is press-moulded or cast and the press-moulded or cast basic composite material (419, 421) is then sintered,
characterised in that
in order to set the thermal expansion coefficients of different material regions, when the basic composite material (419) has been press-moulded or cast and prior to sintering, post-treating takes place of at least one material region (421) which, after sintering, is to have a thermal expansion coefficient that has been altered relative to the rest of the basic composite material (419). - Method according to claim 1,
characterised in that
the post-treatment consists in soaking the at least one material region (421) requiring to be post-treated in a liquid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP05811090.9A EP1817528B1 (en) | 2004-12-01 | 2005-11-22 | Method for the production of a thermal shield element |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP04028445A EP1666797A1 (en) | 2004-12-01 | 2004-12-01 | Heat shield element, method for manufacturing the same, heat shield and combustor |
PCT/EP2005/056127 WO2006058851A1 (en) | 2004-12-01 | 2005-11-22 | Thermal shield element, method for the production thereof, hot gas lining, and combustion chamber |
EP05811090.9A EP1817528B1 (en) | 2004-12-01 | 2005-11-22 | Method for the production of a thermal shield element |
Publications (2)
Publication Number | Publication Date |
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EP1817528A1 EP1817528A1 (en) | 2007-08-15 |
EP1817528B1 true EP1817528B1 (en) | 2016-10-19 |
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP04028445A Withdrawn EP1666797A1 (en) | 2004-12-01 | 2004-12-01 | Heat shield element, method for manufacturing the same, heat shield and combustor |
EP05811090.9A Not-in-force EP1817528B1 (en) | 2004-12-01 | 2005-11-22 | Method for the production of a thermal shield element |
Family Applications Before (1)
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EP04028445A Withdrawn EP1666797A1 (en) | 2004-12-01 | 2004-12-01 | Heat shield element, method for manufacturing the same, heat shield and combustor |
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US (1) | US20080104963A1 (en) |
EP (2) | EP1666797A1 (en) |
WO (1) | WO2006058851A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2428647B1 (en) * | 2010-09-08 | 2018-07-11 | Ansaldo Energia IP UK Limited | Transitional Region for a Combustion Chamber of a Gas Turbine |
DE102012201650A1 (en) | 2012-02-03 | 2013-08-08 | Sgl Carbon Se | Heat shield with outer fiber winding |
US9651258B2 (en) | 2013-03-15 | 2017-05-16 | Rolls-Royce Corporation | Shell and tiled liner arrangement for a combustor |
CN105324611A (en) * | 2013-05-21 | 2016-02-10 | 西门子股份公司 | Heat shield tile for a heat shield of a combustion chamber |
US10935236B2 (en) | 2016-11-10 | 2021-03-02 | Raytheon Technologies Corporation | Non-planar combustor liner panel for a gas turbine engine combustor |
US10830433B2 (en) | 2016-11-10 | 2020-11-10 | Raytheon Technologies Corporation | Axial non-linear interface for combustor liner panels in a gas turbine combustor |
US10655853B2 (en) | 2016-11-10 | 2020-05-19 | United Technologies Corporation | Combustor liner panel with non-linear circumferential edge for a gas turbine engine combustor |
US10935235B2 (en) | 2016-11-10 | 2021-03-02 | Raytheon Technologies Corporation | Non-planar combustor liner panel for a gas turbine engine combustor |
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EP1142852A2 (en) * | 2000-04-07 | 2001-10-10 | DLR Deutsches Zentrum für Luft- und Raumfahrt e.V. | Composite ceramic material having graded thermochemical protective coating |
WO2002033322A1 (en) * | 2000-10-16 | 2002-04-25 | Siemens Aktiengesellschaft | Thermal shield stone for covering the wall of a combustion chamber, combustion chamber and a gas turbine |
US20030207155A1 (en) * | 1998-03-27 | 2003-11-06 | Siemens Westinghouse Power Corporation | Hybrid ceramic material composed of insulating and structural ceramic layers |
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US3174444A (en) * | 1964-01-27 | 1965-03-23 | Harbison Walker Refractories | Suspended hot patch brick |
GB1272591A (en) * | 1968-03-28 | 1972-05-03 | Delaney Gallay Ltd | Improvements in and relating to heat shields |
US4485630A (en) * | 1982-12-08 | 1984-12-04 | General Electric Company | Combustor liner |
US4838030A (en) * | 1987-08-06 | 1989-06-13 | Avco Corporation | Combustion chamber liner having failure activated cooling and dectection system |
FR2664585B1 (en) * | 1990-07-13 | 1993-08-06 | Europ Propulsion | COOLED REFRACTORY STRUCTURES AND METHOD FOR THEIR MANUFACTURE. |
EP0558540B1 (en) * | 1990-11-29 | 1995-06-14 | Siemens Aktiengesellschaft | Ceramic heat shield on a bearing structure |
DE10046094C2 (en) * | 2000-09-18 | 2002-09-19 | Siemens Ag | Heat shield brick for lining a combustion chamber wall |
EP1191285A1 (en) * | 2000-09-22 | 2002-03-27 | Siemens Aktiengesellschaft | Heat shield panel, combustion chamber with inner lining and a gas turbine |
EP1302723A1 (en) * | 2001-10-15 | 2003-04-16 | Siemens Aktiengesellschaft | Lining for combustion chamber inside walls |
US7291407B2 (en) * | 2002-09-06 | 2007-11-06 | Siemens Power Generation, Inc. | Ceramic material having ceramic matrix composite backing and method of manufacturing |
US20060141237A1 (en) * | 2004-12-23 | 2006-06-29 | Katherine Leighton | Metal-ceramic materials |
-
2004
- 2004-12-01 EP EP04028445A patent/EP1666797A1/en not_active Withdrawn
-
2005
- 2005-11-22 US US11/792,130 patent/US20080104963A1/en not_active Abandoned
- 2005-11-22 WO PCT/EP2005/056127 patent/WO2006058851A1/en active Application Filing
- 2005-11-22 EP EP05811090.9A patent/EP1817528B1/en not_active Not-in-force
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US20030207155A1 (en) * | 1998-03-27 | 2003-11-06 | Siemens Westinghouse Power Corporation | Hybrid ceramic material composed of insulating and structural ceramic layers |
EP1142852A2 (en) * | 2000-04-07 | 2001-10-10 | DLR Deutsches Zentrum für Luft- und Raumfahrt e.V. | Composite ceramic material having graded thermochemical protective coating |
WO2002033322A1 (en) * | 2000-10-16 | 2002-04-25 | Siemens Aktiengesellschaft | Thermal shield stone for covering the wall of a combustion chamber, combustion chamber and a gas turbine |
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US20080104963A1 (en) | 2008-05-08 |
EP1666797A1 (en) | 2006-06-07 |
WO2006058851A1 (en) | 2006-06-08 |
EP1817528A1 (en) | 2007-08-15 |
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