EP1362933A1 - Thermal barrier coating - Google Patents
Thermal barrier coating Download PDFInfo
- Publication number
- EP1362933A1 EP1362933A1 EP02010837A EP02010837A EP1362933A1 EP 1362933 A1 EP1362933 A1 EP 1362933A1 EP 02010837 A EP02010837 A EP 02010837A EP 02010837 A EP02010837 A EP 02010837A EP 1362933 A1 EP1362933 A1 EP 1362933A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- matrix material
- barrier coating
- insulation layer
- thermal insulation
- thermal barrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
Definitions
- the invention relates to a thermal barrier coating according to claim 1.
- Thermal insulation layers are applied to heat-stressed components, such as e.g. Turbine blades applied to a gas turbine Heat-sensitive, for example metallic substrate of these components protect from heat.
- the thermal insulation layer exists for example, made of zirconium oxide or partially stabilized zirconium oxide with yttrium oxide.
- EP 1 029 101 B1 shows a thermal barrier coating which has the composition LaAlO 3 , that is to say a perovskite.
- U.S. Patent 5,310,575 shows a material in which zirconia in is mixed into a matrix of a spinel.
- GB 745,257 discloses a thermal barrier coating, the Thermal insulation layer a spinel, a pyrochlore or zirconium oxide is.
- US 5,914,189 discloses a thermal barrier coating which is a mixture of a spinel and calcium zirconate (CaZrO 3 ).
- the object is achieved by a thermal barrier coating according to claim 1 solved.
- the thermal barrier coating according to the invention is a mixture of a matrix material such as zirconium oxide or aluminum oxide and at least one admixed material that has a reduced sintering potential at the operating temperatures of the thermal barrier coating.
- admixed materials are preferably ceramics from the systems of pyrochlores, such as, for example, La 2 Zr 2 O 7 , La 2 Hf 2 O 7 and perovskites, such as, for example, CaZrO 3 , LaAlO 3 and spinels, such as, for example, MgCr 2 O 4 , MgAl 2 O 4 , NiAl 2 O 4 with a volume fraction of 10% and 50%.
- the matrix material consists, for example, of zirconium oxide (ZrO 2 ) or partially stabilized zirconium oxide (ZrO 2 and 7% - 8% yttrium oxide (Y 2 O 3 ) or another ceramic.
- zirconium oxide enables the stretch tolerance to be set automatically in the high temperature range.
- the expansion coefficients of the admixture used are, for example, but not necessarily above or below the expansion coefficient of the zirconium oxide layer.
- cracks and voids are additionally created between the particles from the admixtures and the zirconium oxide during use at high temperatures, which compensate for the elongation tolerance lost in the zirconium oxide matrix, since the admixtures do not sinter, i.e. do not shrink or shrink to a lesser extent, even if the coefficient of thermal expansion is the same.
- the matrix material stretches more at high temperatures off than the admixture, brief compressive stresses arise, who relax, however. Through the onset of sintering in turn, porosities and cracks are created, the one create increasing porosity.
- the matrix material stretches less at high temperatures out as the admixture, so arise through the sintering the matrix additionally cracks and porosities between matrix and admixture, which compensates for lost ductility cause cracking or porosity.
- microporosity / microcracks in the thermal barrier coating will that is, by adding a reduced sintering potential and / or different expansion coefficients of matrix and admixture received.
- the microstructure can be created by a specifically selected mixture can be set so that one for the elongation tolerance of the Thermal insulation layer system necessary porosity and reduction the interlocking of the stem structures achieved with EBPVD layers becomes.
- the oxygen conductivity can be reduced so that oxidation of the MCrAlY layer is also reduced becomes.
Abstract
Description
Die Erfindung betrifft eine Wärmedämmschicht gemäß Anspruch 1.The invention relates to a thermal barrier coating according to claim 1.
Wärmedämmschichten werden auf wärmebelastete Bauteile, wie z.B. Turbinenschaufeln in Gasturbinen aufgebracht, um ein wärmeempfindliches, bspw. metallisches Substrat dieser Bauteile vor Wärme zu schützen. Die Wärmedämmschicht besteht bspw. dabei aus Zirkonoxid oder teilstabilisiertem Zirkonoxid mit Yttriumoxid.Thermal insulation layers are applied to heat-stressed components, such as e.g. Turbine blades applied to a gas turbine Heat-sensitive, for example metallic substrate of these components protect from heat. The thermal insulation layer exists For example, made of zirconium oxide or partially stabilized zirconium oxide with yttrium oxide.
Zwischen der Wärmedämmschicht und dem Substrat ist oft noch eine Haftvermittlerschicht MCrAlY oder Diffusionsschicht aufgebracht.There is often still between the thermal barrier coating and the substrate an adhesion promoter layer MCrAlY or diffusion layer applied.
Die EP 1 029 101 B1 zeigt eine Wärmedämmschicht, die die Zusammensetzung LaAlO3, also ein Perowskit, aufweist.EP 1 029 101 B1 shows a thermal barrier coating which has the composition LaAlO 3 , that is to say a perovskite.
Die US-PS 5,310,575 zeigt ein Material bei dem Zirkonoxid in einer Matrix aus einem Spinell beigemischt ist.U.S. Patent 5,310,575 shows a material in which zirconia in is mixed into a matrix of a spinel.
Die GB 745,257 offenbart eine Wärmedämmschicht, wobei die Wärmedämmschicht ein Spinell, ein Pyrochlor oder Zirkonoxid ist.GB 745,257 discloses a thermal barrier coating, the Thermal insulation layer a spinel, a pyrochlore or zirconium oxide is.
Die US 5,914,189 offenbart eine Wärmedämmschicht, die eine Mischung eines Spinells und Calciumzirkonat (CaZrO3) ist.US 5,914,189 discloses a thermal barrier coating which is a mixture of a spinel and calcium zirconate (CaZrO 3 ).
Aufgrund der unterschiedlichen Ausdehnungskoeffizienten von Wärmedämmschicht und Substrat während des Betriebes kommt es zu Spannungen, die jedoch nicht zum Versagen der Schicht führen, da eine gewisse Dehnungstoleranz durch eine gezielt eingestellte Mikroporosität der Wärmedämmschicht beim Plasmaspritzen gegeben ist. Bei PVD-Schichten (Physical vapour deposition) mittels Elektronenstrahlen (EB-PVD) gibt es eine dehnungstolerante Stängelstruktur. Jedoch verlieren diese Schichten aufgrund der Sinterung bei den hohen Einsatztemperaturen um bzw. über 1000°C ihre Dehnungstoleranz, wodurch die Gefahr des Versagens steigt.Due to the different expansion coefficients of Thermal insulation layer and substrate occur during operation to stresses that do not lead to failure of the layer, because a certain stretch tolerance through a specifically set Microporosity of the thermal barrier coating during plasma spraying given is. For PVD layers (physical vapor deposition) using electron beams (EB-PVD) there is one stretch-tolerant stem structure. However, they lose Layers due to sintering at high operating temperatures around or above 1000 ° C their elongation tolerance, whereby the risk of failure increases.
Es ist daher Aufgabe der Erfindung eine Wärmedämmschicht aufzuzeigen, die das oben genannte Problem überwindet.It is therefore an object of the invention to show a thermal barrier coating, that overcomes the above problem.
Die Aufgabe wird durch eine Wärmedämmschicht gemäß Anspruch 1 gelöst.The object is achieved by a thermal barrier coating according to claim 1 solved.
Weitere vorteilhafte Ausgestaltungen der Wärmedämmschicht sind in den Unteransprüchen aufgelistet.Further advantageous refinements of the thermal barrier coating are listed in the subclaims.
Die erfindungsgemäße Wärmedämmschicht ist eine Mischung aus
einem Matrixmaterial wie z.B. Zirkonoxid oder Aluminiumoxid
und zumindest einem beigemischten Material, dass ein reduziertes
Sinterpotential bei den Einsatztemperaturen der Wärmedämmschicht
aufweist.
Solche beigemischten Materialien sind vorzugsweise Keramiken
aus den Systemen der Pyrochlore, wie z.B. La2Zr2O7, La2Hf2O7
und Perowskite, wie z.B. CaZrO3, LaAlO3 sowie Spinelle, wie
z.B. MgCr2O4, MgAl2O4, NiAl2O4 mit einem Volumenanteil von 10%
und 50%.The thermal barrier coating according to the invention is a mixture of a matrix material such as zirconium oxide or aluminum oxide and at least one admixed material that has a reduced sintering potential at the operating temperatures of the thermal barrier coating.
Such admixed materials are preferably ceramics from the systems of pyrochlores, such as, for example, La 2 Zr 2 O 7 , La 2 Hf 2 O 7 and perovskites, such as, for example, CaZrO 3 , LaAlO 3 and spinels, such as, for example, MgCr 2 O 4 , MgAl 2 O 4 , NiAl 2 O 4 with a volume fraction of 10% and 50%.
Das Matrixmaterial besteht bspw. aus Zirkonoxid (ZrO2) oder
teilstabilisiertem Zirkonoxid (ZrO2 und 7% - 8% Yttriumoxid(Y2O3)
oder einer anderen Keramik.
Durch die Beimischung zu Zirkonoxid wird eine Selbsteinstellung
der Dehnungstoleranz im Hochtemperaturbereich erreicht.
Die Ausdehnungskoeffizienten der verwendeten Beimischung liegen
bspw. aber nicht notwendigerweise ober- oder unterhalb
des Ausdehnungskoeffizienten der Zirkonoxidschicht. Bei einer
Versinterung des Zirkonoxidmatrix, also einer Schrumpfung der
Matrix, reduziert sich lokal die Dehnungstoleranz im vorwiegend
aus Zirkonoxid bestehenden Teilbereich. Zwischen den
Teilchen aus den Beimischungen und dem Zirkonoxid werden während
des Einsatzes bei hohen Temperaturen jedoch zusätzlich
Risse und Hohlräume erzeugt, die die in der Zirkonoxidmatrix
verlorene Dehnungstoleranz kompensieren, da die Beimischungen
nicht versintern, also nicht oder nur in einem geringeren Maße
schrumpfen, auch wenn der thermischen Ausdehnungskoeffizient
gleich ist.The matrix material consists, for example, of zirconium oxide (ZrO 2 ) or partially stabilized zirconium oxide (ZrO 2 and 7% - 8% yttrium oxide (Y 2 O 3 ) or another ceramic.
The addition of zirconium oxide enables the stretch tolerance to be set automatically in the high temperature range. The expansion coefficients of the admixture used are, for example, but not necessarily above or below the expansion coefficient of the zirconium oxide layer. When the zirconium oxide matrix is sintered, that is to say when the matrix shrinks, the elongation tolerance is reduced locally in the partial area consisting predominantly of zirconium oxide. However, cracks and voids are additionally created between the particles from the admixtures and the zirconium oxide during use at high temperatures, which compensate for the elongation tolerance lost in the zirconium oxide matrix, since the admixtures do not sinter, i.e. do not shrink or shrink to a lesser extent, even if the coefficient of thermal expansion is the same.
Der Einfluss des thermischen Ausdehnungskoeffizients der beigemischten Materialien ist wie folgt:The influence of the thermal expansion coefficient of the admixed Materials is as follows:
Dehnt sich das Matrixmaterial bei hohen Temperaturen stärker aus als die Beimischung, so entstehen kurzzeitig Druckspannungen, die jedoch relaxieren. Durch die einsetzende Versinterung werden wiederum Porositäten und Risse erzeugt, die eine zunehmende Porosität erzeugen.The matrix material stretches more at high temperatures off than the admixture, brief compressive stresses arise, who relax, however. Through the onset of sintering in turn, porosities and cracks are created, the one create increasing porosity.
Dehnt sich das Matrixmaterial bei hohen Temperaturen geringer aus als die Beimischung, so entstehen durch die Versinterung der Matrix zusätzlich Risse und Porositäten zwischen Matrix und Beimischung, die eine Kompensation der verlorenen Duktilität durch Rissbildung oder Porosität bewirken.The matrix material stretches less at high temperatures out as the admixture, so arise through the sintering the matrix additionally cracks and porosities between matrix and admixture, which compensates for lost ductility cause cracking or porosity.
Die Mikroporosität/Mikrorisse in der Wärmedämmschicht wird also durch die Beimischung mit reduziertem Sinterpotential und/oder unterschiedliche Ausdehnungskoeffizienten von Matrix und Beimischung erhalten.The microporosity / microcracks in the thermal barrier coating will that is, by adding a reduced sintering potential and / or different expansion coefficients of matrix and admixture received.
Durch eine gezielt gewählte Mischung kann die Mikrostruktur so eingestellt werden, dass eine für die Dehnungstoleranz des Wärmedämmschichtsystems notwendige Porosität und Reduzierung der Verhakung der Stängelstrukturen bei EBPVD-Schichten erzielt wird.The microstructure can be created by a specifically selected mixture can be set so that one for the elongation tolerance of the Thermal insulation layer system necessary porosity and reduction the interlocking of the stem structures achieved with EBPVD layers becomes.
Außerdem kann die Sauerstoffleitfähigkeit reduziert werden, so dass auch eine Oxidation der MCrAlY-Schicht reduziert wird.In addition, the oxygen conductivity can be reduced so that oxidation of the MCrAlY layer is also reduced becomes.
Claims (12)
insbesondere für den Einsatz in einer Gasturbine,
dadurch gekennzeichnet, dass die Wärmedämmschicht ein Matrixmaterial aufweist, dass dem Matrixmaterial Materialien beigemischt sind, die gegenüber dem Matrixmaterial bei den Einsatztemperaturen ein reduziertes Sinterpotential aufweisen. 1. thermal insulation layer,
especially for use in a gas turbine,
characterized in that the thermal barrier coating has a matrix material that materials are mixed with the matrix material which have a reduced sintering potential compared to the matrix material at the operating temperatures.
dadurch gekennzeichnet, dass
dem Matrixmaterial ein Pyrochlor beigemischt ist. 2. Thermal insulation layer according to claim 1,
characterized in that
a pyrochlore is added to the matrix material.
dadurch gekennzeichnet, dass
das Pyrochlor die Zusammensetzung La2ZrO7 oder La2Hf2O7 aufweist. 3. Thermal insulation layer according to claim 2,
characterized in that
the pyrochlore has the composition La 2 ZrO 7 or La 2 Hf 2 O 7 .
dadurch gekennzeichnet, dass
dem Matrixmaterial ein Perowskit beigemischt ist. 4. Thermal insulation layer according to claim 1,
characterized in that
a perovskite is mixed into the matrix material.
dadurch gekennzeichnet, dass
das Perowskit die Zusammensetzung CaZrO3 oder LaAlO3 aufweist. 5. Thermal insulation layer according to claim 4,
characterized in that
the perovskite has the composition CaZrO 3 or LaAlO 3 .
dadurch gekennzeichnet, dass
dem Matrixmaterial ein Spinell beigemischt ist. 6. thermal barrier coating according to claim 1,
characterized in that
a spinel is mixed into the matrix material.
dadurch gekennzeichnet, dass
das Spinell die Zusammensetzung MgZr2O4 oder MgAl2O4 oder Ni-Al2O4 aufweist. 7. thermal barrier coating according to claim 6,
characterized in that
the spinel has the composition MgZr 2 O 4 or MgAl 2 O 4 or Ni-Al 2 O 4 .
dadurch gekennzeichnet, dass
die Beimischungen einen Volumenanteil von 10% - 50% aufweisen. 8. Thermal insulation layer according to claim 1,
characterized in that
the admixtures have a volume fraction of 10% - 50%.
dadurch gekennzeichnet, dass die Wärmedämmschicht ein Matrixmaterial aufweist,
dass dem Matrixmaterial Materialien beigemischt sind, die gegenüber dem Matrixmaterial bei den Einsatztemperaturen einen so unterschiedlichen thermischen Ausdehnungskoeffizienten aufweisen, dass Mikrorisse oder eine Mikroporosität gebildet werden. 10. thermal barrier coating, in particular according to claim 1, in particular for use in a gas turbine,
characterized in that the thermal barrier coating has a matrix material,
that materials are admixed to the matrix material which have a coefficient of thermal expansion which is so different from the matrix material at the application temperatures that microcracks or microporosity are formed.
dadurch gekennzeichnet, dass
das Matrixmaterial vollstabilisiertes oder teilstabilisiertes Zirkonoxid ist. 11. Thermal insulation layer according to claim 1 or 10,
characterized in that
the matrix material is fully stabilized or partially stabilized zirconium oxide.
dadurch gekennzeichnet, dass
das Matrixmaterial Aluminiumoxid ist. 12. Thermal insulation layer according to claim 1 or 10,
characterized in that
the matrix material is aluminum oxide.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02010837A EP1362933A1 (en) | 2002-05-15 | 2002-05-15 | Thermal barrier coating |
| JP2004505412A JP2005525472A (en) | 2002-05-15 | 2003-04-24 | Insulation layer |
| PCT/EP2003/004270 WO2003097901A1 (en) | 2002-05-15 | 2003-04-24 | Heat insulating layer |
| EP03752714A EP1511883A1 (en) | 2002-05-15 | 2003-04-24 | Heat insulating layer |
| US10/756,670 US20040146741A1 (en) | 2002-05-15 | 2004-01-13 | Thermal barrier coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02010837A EP1362933A1 (en) | 2002-05-15 | 2002-05-15 | Thermal barrier coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1362933A1 true EP1362933A1 (en) | 2003-11-19 |
Family
ID=29265933
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02010837A Withdrawn EP1362933A1 (en) | 2002-05-15 | 2002-05-15 | Thermal barrier coating |
| EP03752714A Withdrawn EP1511883A1 (en) | 2002-05-15 | 2003-04-24 | Heat insulating layer |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03752714A Withdrawn EP1511883A1 (en) | 2002-05-15 | 2003-04-24 | Heat insulating layer |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20040146741A1 (en) |
| EP (2) | EP1362933A1 (en) |
| JP (1) | JP2005525472A (en) |
| WO (1) | WO2003097901A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007080058A1 (en) * | 2006-01-09 | 2007-07-19 | Siemens Aktiengesellschaft | Ceramic solid component, ceramic layer having a high porosity, use of said layer, and a component comprising said layer |
| DE102007030602A1 (en) * | 2007-06-28 | 2009-01-02 | Siemens Ag | Component with a ceramic layer in which particles are incorporated, and method for its production |
| FR2925576A3 (en) * | 2007-12-21 | 2009-06-26 | Renault Sas | Oil temperature and pressure managing method for internal combustion engine of start and stop vehicle, involves regulating oil pressure by controlling pressure regulating unit, and regulating temperature and pressure based on cartography |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150274981A1 (en) * | 2010-09-22 | 2015-10-01 | Skyworks Solutions, Inc. | Dual function lanthanide coatings |
| CN107473739B (en) * | 2017-09-08 | 2020-08-07 | 中国人民解放军国防科技大学 | Lanthanum zirconate complex phase ceramic and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB745257A (en) * | 1952-08-08 | 1956-02-22 | Norton Grinding Wheel Co Ltd | Coating metals and other material with stable metal oxides |
| US5310575A (en) * | 1987-11-03 | 1994-05-10 | Robert Bosch Gmbh | Method of making a porous ceramic protective layer on an electrode of an electrochemical sensor for exposure to hot gas |
| WO1999042630A1 (en) * | 1998-02-20 | 1999-08-26 | Rainer Gadow | Thermal insulating material and method for producing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100463008B1 (en) * | 1995-06-26 | 2005-06-16 | 제너럴 일렉트릭 캄파니 | Protected Thermal Barrier Coating Composite With Multiple Coatings |
| EP1029115B1 (en) * | 1997-11-03 | 2001-09-19 | Siemens Aktiengesellschaft | Product,especially a gas turbine component, with a ceramic heat insulating layer |
| JP4218744B2 (en) * | 1998-09-10 | 2009-02-04 | 日鉄ハード株式会社 | Thermal spray material and member having coating formed by thermal spraying the same |
| EP1247941A1 (en) * | 2001-04-03 | 2002-10-09 | Siemens Aktiengesellschaft | Gas turbine blade |
-
2002
- 2002-05-15 EP EP02010837A patent/EP1362933A1/en not_active Withdrawn
-
2003
- 2003-04-24 WO PCT/EP2003/004270 patent/WO2003097901A1/en not_active Application Discontinuation
- 2003-04-24 EP EP03752714A patent/EP1511883A1/en not_active Withdrawn
- 2003-04-24 JP JP2004505412A patent/JP2005525472A/en not_active Abandoned
-
2004
- 2004-01-13 US US10/756,670 patent/US20040146741A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB745257A (en) * | 1952-08-08 | 1956-02-22 | Norton Grinding Wheel Co Ltd | Coating metals and other material with stable metal oxides |
| US5310575A (en) * | 1987-11-03 | 1994-05-10 | Robert Bosch Gmbh | Method of making a porous ceramic protective layer on an electrode of an electrochemical sensor for exposure to hot gas |
| WO1999042630A1 (en) * | 1998-02-20 | 1999-08-26 | Rainer Gadow | Thermal insulating material and method for producing same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007080058A1 (en) * | 2006-01-09 | 2007-07-19 | Siemens Aktiengesellschaft | Ceramic solid component, ceramic layer having a high porosity, use of said layer, and a component comprising said layer |
| DE102007030602A1 (en) * | 2007-06-28 | 2009-01-02 | Siemens Ag | Component with a ceramic layer in which particles are incorporated, and method for its production |
| US7763367B2 (en) | 2007-06-28 | 2010-07-27 | Siemens Aktiengesellschaft | Component with a ceramic coating, into which particles are embedded, and method for producing said component |
| FR2925576A3 (en) * | 2007-12-21 | 2009-06-26 | Renault Sas | Oil temperature and pressure managing method for internal combustion engine of start and stop vehicle, involves regulating oil pressure by controlling pressure regulating unit, and regulating temperature and pressure based on cartography |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003097901A1 (en) | 2003-11-27 |
| US20040146741A1 (en) | 2004-07-29 |
| JP2005525472A (en) | 2005-08-25 |
| EP1511883A1 (en) | 2005-03-09 |
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