WO2016071094A1 - Segmented thermal barrier layer made of fully stabilized zirconium oxide - Google Patents

Segmented thermal barrier layer made of fully stabilized zirconium oxide Download PDF

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Publication number
WO2016071094A1
WO2016071094A1 PCT/EP2015/073976 EP2015073976W WO2016071094A1 WO 2016071094 A1 WO2016071094 A1 WO 2016071094A1 EP 2015073976 W EP2015073976 W EP 2015073976W WO 2016071094 A1 WO2016071094 A1 WO 2016071094A1
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WO
WIPO (PCT)
Prior art keywords
layer
zirconium oxide
zirconia
thermal barrier
fully stabilized
Prior art date
Application number
PCT/EP2015/073976
Other languages
German (de)
French (fr)
Inventor
Arturo Flores Renteria
Original Assignee
Siemens Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO2016071094A1 publication Critical patent/WO2016071094A1/en

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288—Protective coatings for blades
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/20—Oxide or non-oxide ceramics
    • F05D2300/21—Oxide ceramics
    • F05D2300/2118—Zirconium oxides

Definitions

  • the invention relates to a thermal barrier coating system comprising a segmented ceramic layer of fully stabilized
  • CMAS impurities can lead to cleavage of ceramic thermal barrier coatings.
  • FIGURE shows schematically an inventive heat ⁇ dämm Anlagensystem.
  • the figure and the description represent only embodiments of the invention.
  • the figure shows a thermal barrier coating system 1 according to the invention.
  • the thermal barrier coating system 1 has a substrate 4.
  • the substrate 4 is preferably metallic and very preferably ⁇ a nickel or cobalt-based superalloy.
  • This may be a diffusion layer and / or a coating ⁇ coating.
  • the metallic bond ⁇ promoter layer the composition NiCoCrAlX, wherein X is yttrium (Y) and / or a rare earth, silicon (Si), rhenium (Re), tantalum (Ta) and / or iron (Fe) represents ,
  • an aluminum oxide layer will form after coating of the metallic adhesion promoter layer 7 during coating of the ceramic layer 16 or at least during operation (not shown).
  • the inner zirconium oxide layer 10 preferably has platelet-shaped grains.
  • the inner zirconia layer 10 is partially stabilized and preferably has a porosity of at least 5 vol ⁇ 6, in particular at least 8 vol%.
  • the proportion of yttrium oxide (Y 2 O 3 ) is preferably 8 mol%.
  • an outer and segmented zirconium oxide layer 13 of fully stabilized zirconium oxide is applied.
  • the proportion of yttrium oxide (Y 2 O 3 ) is preferably
  • the outer zirconium oxide layer 13 is at least twice as thick as the inner zirconium oxide layer 10.
  • the outer zirconium oxide layer 13 is preferably the outer layer of the layer system.
  • the stabilizers for the zirconia inner layer 10 and the outer layer 13 may be the same but may be different.
  • the segments 15 ', 15'',15''' of the outer segmented zirconium oxide layer 13 preferably extend up to the held ⁇ ren zirconium 10th
  • Segmented ceramic coatings are prior Tech ⁇ technology and may be prepared by various methods are known from the prior art, is achieved.
  • Such layers have sufficient fracture toughness and stress tolerance as well as low thermal conductivity.
  • yttrium here preferably also the reactivity and the reaction stock is increased with CMAS, so that gene ⁇ rell the life of a ceramic thermal barrier coating is increased.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

A higher service life even in the presence of CMAS impurities is ensured by using a fully stabilized zirconium oxide layer and thus a higher yttrium content and the segmentation.

Description

Segmentierte Wärmedämmschicht aus vollstabilisiertem  Segmented thermal insulation layer of fully stabilized
Zirkonoxid  zirconia
Die Erfindung betrifft ein Wärmedämmschichtsystem, das eine segmentierte keramische Schicht aus vollstabilisiertem The invention relates to a thermal barrier coating system comprising a segmented ceramic layer of fully stabilized
Zirkonoxid aufweist. Having zirconia.
Es ist bekannt, dass sogenannte CMAS-Verunreinigungen zur Ab- Spaltung von keramischen Wärmedämmschichten führen können. It is known that so-called CMAS impurities can lead to cleavage of ceramic thermal barrier coatings.
Vielfach werden andere, zusätzliche Materialen verwendet, die das Eindringen von CMAS verhindern sollen. Dies ist jedoch aufwändig. In many cases, other, additional materials are used to prevent the penetration of CMAS. However, this is expensive.
Es ist daher Aufgabe der Erfindung oben genanntes Problem zu lösen . Die Aufgabe wird gelöst durch ein Wärmedämmschichtsystem nach Anspruch 1. It is therefore an object of the invention to solve the above-mentioned problem. The object is achieved by a thermal barrier coating system according to claim 1.
In den Unteransprüchen sind weitere vorteilhafte Maßnahmen aufgelistet, die beliebig miteinander kombiniert werden kön- nen, um weitere Vorteile zu erzielen. The subclaims list further advantageous measures which can be combined with one another as desired in order to achieve further advantages.
Es zeigt die Figur schematisch ein erfindungsgemäßes Wärme¬ dämmschichtsystem. Die Figur und die Beschreibung stellen nur Ausführungsbeispiele der Erfindung dar. The FIGURE shows schematically an inventive heat ¬ dämmschichtsystem. The figure and the description represent only embodiments of the invention.
Die Figur zeigt ein erfindungsgemäßes Wärmedämmschichtsystem 1. The figure shows a thermal barrier coating system 1 according to the invention.
Das Wärmedämmschichtsystem 1 weist ein Substrat 4 auf. Das Substrat 4 ist vorzugsweise metallisch und ganz vorzugs¬ weise eine Nickel- oder Kobaltbasierte Superlegierung. The thermal barrier coating system 1 has a substrate 4. The substrate 4 is preferably metallic and very preferably ¬ a nickel or cobalt-based superalloy.
Auf dem Substrat 4 ist optional eine Haftvermittlerschicht 7, insbesondere eine metallische Haftvermittlerschicht 7 aufge¬ bracht . On the substrate 4 a bonding agent layer 7, in particular a metallic adhesion promoter layer is optional 7 ¬ be applied.
Das kann eine Diffusionsschicht sein und/oder eine Überzugs¬ beschichtung . This may be a diffusion layer and / or a coating ¬ coating.
Insbesondere bei Turbinenteilen weist die metallische Haft¬ vermittlerschicht 7 die Zusammensetzung NiCoCrAlX auf, wobei X Yttrium (Y) und/oder eine Seltene Erde, Silizium (Si) , Rhenium (Re) , Tantal (Ta) und/oder Eisen (Fe) darstellt. In particular, in turbine parts 7, the metallic bond ¬ promoter layer, the composition NiCoCrAlX, wherein X is yttrium (Y) and / or a rare earth, silicon (Si), rhenium (Re), tantalum (Ta) and / or iron (Fe) represents ,
Auf der Grenzfläche 19 zu der keramischen Wärmedämmschicht 16 wird sich nach dem Beschichten der metallischen Haftvermittlerschicht 7 beim Beschichten der keramischen Schicht 16 oder zumindest im Betrieb eine Aluminiumoxidschicht bilden (nicht dargestellt) . On the interface 19 to the ceramic thermal barrier coating 16, an aluminum oxide layer will form after coating of the metallic adhesion promoter layer 7 during coating of the ceramic layer 16 or at least during operation (not shown).
Auf diese Aluminiumoxidschicht oder auf der Haftvermittler¬ schicht 7 wird eine möglichst frei von vertikalen Rissen, innere Zirkonoxidschicht 10 aufgebracht. In this aluminum oxide layer, or the adhesion promoter layer 7 ¬ a free as possible from internal vertical cracks zirconium oxide layer 10 is applied.
Die innere Zirkonoxidschicht 10 weist vorzugsweise plättchen- förmige Körner auf. The inner zirconium oxide layer 10 preferably has platelet-shaped grains.
Die innere Zirkonoxidschicht 10 ist teilstabilisiert und weist vorzugweise eine Porosität von mindestens 5 vol~6 , ins besondere mindestens 8 vol% auf. The inner zirconia layer 10 is partially stabilized and preferably has a porosity of at least 5 vol ~ 6, in particular at least 8 vol%.
Der Anteil von Yttriumoxid (Y2O3) beträgt vorzugsweise 8mol%. The proportion of yttrium oxide (Y 2 O 3 ) is preferably 8 mol%.
Auf dieser teilstabilisierten Zirkonoxidschicht 10 ist eine äußere und segmentierte Zirkonoxidschicht 13 aus vollstabili- siertem Zirkonoxid aufgebracht. On this partially stabilized zirconium oxide layer 10, an outer and segmented zirconium oxide layer 13 of fully stabilized zirconium oxide is applied.
Der Anteil von Yttriumoxid (Y2O3) beträgt vorzugsweise The proportion of yttrium oxide (Y 2 O 3 ) is preferably
20mol%, um die Vollstabilisierung zu erreichen. Vorzugsweise können andere Gewichtsanteile oder in Kombina¬ tion mit anderen Seltenen Erden andere Gewichtsanteile verwendet werden, um die Vollstabilisierung zu erreichen. Die äußere Zirkonoxidschicht 13 ist mindestens zweimal so dick wie die innere Zirkonoxidschicht 10. 20mol% to achieve full stabilization. Preferably other parts by weight or in combina ¬ tion can be used with other rare earths other parts by weight, to achieve the full stabilization. The outer zirconium oxide layer 13 is at least twice as thick as the inner zirconium oxide layer 10.
Die äußere Zirkonoxidschicht 13 ist vorzugsweise die äußere Schicht des Schichtsystems. Die Stabilisatoren für die innere Zirkonoxidschicht 10 und die äußere Schicht 13 können die gleichen sein, aber auch verschieden .  The outer zirconium oxide layer 13 is preferably the outer layer of the layer system. The stabilizers for the zirconia inner layer 10 and the outer layer 13 may be the same but may be different.
Die Segmente 15' , 15' ' , 15' ' ' der äußeren, segmentierten Zir- konoxidschicht 13 erstrecken sich vorzugsweise bis zur inne¬ ren Zirkonoxidschicht 10. The segments 15 ', 15'',15''' of the outer segmented zirconium oxide layer 13 preferably extend up to the held ¬ ren zirconium 10th
Segmentierte keramische Schichten (DVC) sind Stand der Tech¬ nik und können durch verschiedene Verfahren, bekannt aus dem Stand der Technik, erzielt werden. Segmented ceramic coatings (DVC) are prior Tech ¬ technology and may be prepared by various methods are known from the prior art, is achieved.
Solche Schichten haben eine ausreichende Bruchzähigkeit und Stresstoleranz sowie eine geringe thermische Leitfähigkeit. Zusätzlich zu dem sehr deutlich höheren Anteil der Seltenen Erden, hier vorzugsweise Yttrium, wird auch das Reaktionsvermögen und der Reaktionsvorrat mit CMAS erhöht, so dass gene¬ rell die Lebensdauer einer keramischen Wärmedämmschicht erhöht wird. Such layers have sufficient fracture toughness and stress tolerance as well as low thermal conductivity. In addition to the very much higher proportion of the rare earths, yttrium here preferably also the reactivity and the reaction stock is increased with CMAS, so that gene ¬ rell the life of a ceramic thermal barrier coating is increased.

Claims

Patentansprüche claims
1. Keramisches Wärmedämmschichtsystem (1), 1. Ceramic thermal barrier coating system (1),
zumindest aufweisend  at least having
ein Substrat ( 4 ) ,  a substrate (4),
insbesondere ein metallisches Substrat (4),  in particular a metallic substrate (4),
optional eine metallische Haftvermittlerschicht (7) auf dem Substrat (4),  optionally a metallic adhesion promoter layer (7) on the substrate (4),
eine innere Zirkonoxidschicht (10) auf der metallischen Haftvermittlerschicht (7),  an inner zirconium oxide layer (10) on the metallic adhesion promoter layer (7),
wobei die innere Zirkonoxidschicht (10) teilstabilisiert ist und  wherein the inner zirconium oxide layer (10) is partially stabilized and
eine äußere Zirkonoxidschicht (13),  an outer zirconium oxide layer (13),
die zumindest teilweise vertikal segmentiert (15', 15'', 15"') und  the at least partially vertically segmented (15 ', 15' ', 15 "') and
vollstabilisiert ist.  fully stabilized.
2. Schichtsystem nach Anspruch 1, 2. Layer system according to claim 1,
bei dem die Dicke der äußeren Zirkonoxidschicht (13) min¬ destens zweimal so dick ist wie die Schichtdicke der inne¬ ren keramischen Zirkonoxidschicht (10). wherein the thickness of the outer zirconia layer (13) is min ¬ least twice as thick as the layer thickness of the inherent ¬ ren ceramic zirconium oxide layer (10).
3. Schichtsystem nach einem oder beiden der Ansprüche 1 oder 2, 3. Layer system according to one or both of claims 1 or 2,
bei dem Yttriumoxid (Y2O3) als Stabilisator für Zirkonoxid verwendet wird. in which yttria (Y 2 O 3 ) is used as a zirconia stabilizer.
4. Schichtsystem nach einem oder mehreren der Ansprüche 1, 2 oder 3, 4. Layer system according to one or more of claims 1, 2 or 3,
bei dem der Anteil an Yttriumoxid (Y2O3) in der vollstabi¬ lisierten Zirkonoxidschicht (10) mindestens 20mol% beträgt. wherein the proportion of yttrium oxide (Y 2 O 3) in the fully stabilized zirconium oxide ized ¬ (10) is at least 20 mol%.
5. Schichtsystem nach einem oder mehreren der Ansprüche 1, 2, 3 oder 4, 5. Layer system according to one or more of claims 1, 2, 3 or 4,
bei dem sich Segmente (15', 15'', 15''') in der vollstabi¬ lisierten, äußeren Zirkonoxidschicht (13) bis zur teilsta- bilisierten Zirkonoxidschicht (10) erstrecken. in which up to teilsta--stabilized zirconium oxide layer in the fully stable ¬ ized outer zirconia layer (13) (10) segments (15 '''15', 15 '') extend.
6. Schichtsystem nach einem oder mehreren der vorhergehenden Ansprüche, 6. Layer system according to one or more of the preceding claims,
bei dem die äußere Zirkonoxidschicht (13) die äußerste Schicht darstellt.  wherein the zirconia outer layer (13) is the outermost layer.
7. Schichtsystem nach einem oder mehreren der vorhergehen- den Ansprüche, 7. Layer system according to one or more of the preceding claims,
bei dem die innere Zirkonoxidschicht (10) nicht vertikal segmentiert ist.  wherein the inner zirconia layer (10) is not vertically segmented.
8. Schichtsystem nach einem oder mehreren der vorhergehenden Ansprüche, 8. Layer system according to one or more of the preceding claims,
bei dem die innere Zirkonoxidschicht (10) plättchenförmige Körner aufweist.  wherein the zirconia inner layer (10) has platelet-shaped grains.
PCT/EP2015/073976 2014-11-06 2015-10-16 Segmented thermal barrier layer made of fully stabilized zirconium oxide WO2016071094A1 (en)

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EP3453779B1 (en) 2017-09-08 2022-04-20 Raytheon Technologies Corporation Multi layer cmas resistant thermal barrier coating

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