EP2294235A1 - Couche de mcralx composée de deux strates présentant différentes teneurs en cobalt et en nickel - Google Patents

Couche de mcralx composée de deux strates présentant différentes teneurs en cobalt et en nickel

Info

Publication number
EP2294235A1
EP2294235A1 EP09749687A EP09749687A EP2294235A1 EP 2294235 A1 EP2294235 A1 EP 2294235A1 EP 09749687 A EP09749687 A EP 09749687A EP 09749687 A EP09749687 A EP 09749687A EP 2294235 A1 EP2294235 A1 EP 2294235A1
Authority
EP
European Patent Office
Prior art keywords
layer
mcralx
cobalt
nickel
content
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Withdrawn
Application number
EP09749687A
Other languages
German (de)
English (en)
Inventor
Friedhelm Schmitz
Werner Stamm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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
Priority claimed from EP08009324A external-priority patent/EP2128285A1/fr
Priority claimed from EP09000248A external-priority patent/EP2206806A1/fr
Application filed by Siemens AG filed Critical Siemens AG
Priority to EP09749687A priority Critical patent/EP2294235A1/fr
Publication of EP2294235A1 publication Critical patent/EP2294235A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other

Definitions

  • the invention relates to a two-layer MCrAlX layer in which the nickel and cobalt contents differ.
  • Ni and Co base materials are used in the hot gas path of gas turbines. However, because of their optimization to the highest possible strength, these materials often lack sufficient oxidation and high temperature corrosion resistance in the hot gas. The materials must therefore be protected with suitable protective coatings against hot gas attack.
  • a ceramic layer of zirconium oxide is additionally applied to thermal insulation on thermally highly stressed components. The underlying metallic layer serves as an adhesive layer for the ceramic thermal insulation layer and as an oxidation protection layer for the base material.
  • protective coatings are applied to the hottest components by means of thermal spraying or EB-PVD methods.
  • These usually consist of so-called MCrAlX coating layers which, in addition to Ni and / or Co, also contain chromium, aluminum, silicon, rhenium or rare earths such as yttrium.
  • MCrAlX coating layers which, in addition to Ni and / or Co, also contain chromium, aluminum, silicon, rhenium or rare earths such as yttrium.
  • MCrAlX coating layers which, in addition to Ni and / or Co, also contain chromium, aluminum, silicon, rhenium or rare earths such as yttrium.
  • the object of the invention is to solve the above-mentioned problem.
  • the object is achieved by a layer system according to claim 1 or 2.
  • Figure 3 shows a gas turbine
  • FIG. 4 is a perspective view of a turbine blade
  • FIG. 5 is a perspective view of a combustion chamber
  • FIG. 6 is a list of superalloys.
  • FIG. 1 shows a first example.
  • the component 1, 120, 130, 155 has a substrate 4.
  • the substrate 4 has a superalloy, in particular according to FIG.
  • a metallic protective layer 13 is present.
  • the metallic protective layer 13 comprises two different MCrAlX layers 7, 10, wherein the outer layer 10 has a higher cobalt content. 2008154 91
  • Higher cobalt content means at least a relative difference of 20% relative to the lower cobalt value.
  • the nickel content of the outer layer 10 is less than the nickel content of the underlying layer 7.
  • Higher nickel content means at least a relative difference of 20% based on the lower nickel content.
  • the metallic protective layer 13 preferably consists of two different MCrAlX layers 7, 10.
  • a metallic protective layer 13 which has a better oxidation resistance than the previously used MCrAlX layers compared with the layers used hitherto with simultaneously the same good thermomechanical behavior. This is achieved by using a duplex layer system which has different requirements with regard to an optimized diffusion interaction with the base material and, on the other hand, forms an optimized TGO layer at the phase boundary with the ceramic. A different chemical composition of the two MCrAlX alloys used achieves this goal.
  • the inner layer 7 close to the base material (substrate 4) preferably has the following basic composition (in wt%) in the chemical composition of the powder or ingot used: Ni about 38% to about 66.6% and Co from 8% to 22%.
  • This basic composition means that, despite a high Cr content of 21% to 29%, little or no ⁇ -Cr phases occur and a good ductility of the layer is maintained.
  • the relatively high Cr and / or Y content should act as a getter for sulfur in the base material and prevent a damaging effect on the TGO.
  • the relatively low Al content of 4% to 9% requires the ductility behavior of the layer 7, but also leads to a low interdiffusion with the base material.
  • On the other hand lies 2008154 91
  • the yttrium content of the inner layer 7 should preferably be from 0.4wt% to 0.9wt% and also be a gettering effect for sulfur.
  • the yttrium ( ⁇ ) should also be able to diffuse into the overlying outer layer 10.
  • the layer may also contain Re up to 1% to further delay interdiffusion.
  • the outer MCrAlX layer 10 located above has a thickness that is preferably the same as the first layer 7 within the scope of the manufacturing tolerances.
  • the outer layer (10) may be the same thickness or significantly thinner than the inner layer (7).
  • This basic composition in conjunction with a lowered Cr content of preferably around 20% by weight and an Al content of preferably 11.5% by weight, leads to excellent Al 2 C 3 cover formation, which is further enhanced by the low Y content of 0, 1% - 0.2% with regard to training and liability.
  • the low Y content prevents internal oxidation of the yttrium and does not form yttrium aluminate on the MCrAlX in the initial phase of the oxidation. This leads to a lower layer growth.
  • the layer 10 essentially has a phase composition of gamma, beta, is thermally stable and avoids the formation of brittle phases, which in turn leads to good ductility properties of the MCrAlX layer 10. 2008154 91
  • the protective layer 13 has two superimposed layers, preferably with the composition of inner layer 7 (in wt%):
  • Y is 0.05% -0.5%, preferably 0.1% -0.2%.
  • Nickel (in layer 7) or cobalt (in layer 10) preferably form the remainder, so that a final list is given.
  • Hf, Zr, P and other trace elements can be found in the outer protective layer 10 to a percentage of 0.3% positive properties by mutual exchange 2008154 91
  • FIG. 3 shows by way of example a gas turbine 100 in a longitudinal section.
  • the gas turbine 100 has inside a rotatably mounted about a rotation axis 102 rotor 103 with a shaft, which is also referred to as a turbine runner.
  • a compressor 105 for example, a toroidal combustion chamber 110, in particular annular combustion chamber with a plurality of coaxially arranged burners 107, a turbine 108 and the exhaust housing 109.
  • the annular combustion chamber 110 communicates with an example annular hot gas channel 111th
  • four turbine stages 112 connected in series form the turbine 108.
  • Each turbine stage 112 is formed, for example, from two blade rings. In flow direction of a working medium
  • a row 125 formed of rotor blades 120 follows.
  • the guide vanes 130 are fastened to an inner housing 138 of a stator 143, whereas the rotor blades 120 of a row 125 are attached to the rotor 103 by means of a turbine disk 133, for example.
  • air 105 is sucked in and compressed by the compressor 105 through the intake housing 104.
  • the compressed air provided at the turbine-side end of the compressor 105 is supplied to the burners 107 where it is mixed with a fuel.
  • the mixture is then burned to form the working fluid 113 in the combustion chamber 110. From there, the working medium 113 flows along the hot gas channel 111 past the guide vanes 2008154 91
  • the working medium 113 expands in a pulse-transmitting manner, so that the blades 120 drive the rotor 103 and this drives the machine coupled to it.
  • the components exposed to the hot working medium 113 are subject to thermal loads during the operation of the gas turbine 100.
  • the guide vanes 130 and rotor blades 120 of the first turbine stage 112, viewed in the direction of flow of the working medium 113, are subjected to the greatest thermal stress in addition to the heat shield elements lining the annular combustion chamber 110.
  • substrates of the components may have a directional structure, i. they are monocrystalline (SX structure) or have only slow grains (DS structure).
  • SX structure monocrystalline
  • DS structure slow grains
  • iron-, nickel- or cobalt-based superalloys are used as the material for the components, in particular for the turbine blade 120, 130 and components of the combustion chamber 110.
  • Such superalloys are known, for example, from EP 1 204 776 B1, EP 1 306 454, EP 1 319 729 A1, WO 99/67435 or WO 00/44949.
  • the vane 130 has a Leitschaufelfuß facing the réellegehause 138 of the turbine 108 (not shown here) and a Leitschaufelfuß the opposite vane head on.
  • the vane head faces the rotor 103 and fixed to a mounting ring 140 of the stator 143.
  • FIG. 4 shows a perspective view of a rotor blade 120 or guide blade 130 of a flow machine which extends along a longitudinal axis 121. 2008154 91
  • the flow machine may be a gas turbine of an aircraft or power plant for power generation, a steam turbine or a compressor.
  • the blade 120, 130 has along the longitudinal axis 121 in succession a fastening region 400, an adjacent blade platform 403 and an airfoil 406 and a blade tip 415.
  • the blade 130 may have at its blade tip 415 another platform (not shown).
  • a blade root 183 is formed, which serves for attachment of the blades 120, 130 to a shaft or a disc (not shown).
  • the blade root 183 is designed, for example, as a hammer head. Other designs as Christmas tree or Schwalbenschwanzfuß are possible.
  • the blade 120, 130 has a flow-on edge 409 and a downstream edge 412 for a medium that flows past the blade 406.
  • the blade 120, 130 can be made by a casting process, also by directional solidification, by a forging process, by a Fras vide or combinations thereof.
  • Such monocrystalline workpieces takes place e.g. by directed solidification from the melt.
  • These are casting processes in which the liquid metallic alloy is transformed into a monocrystalline structure, i. to the single-crystal workpiece, or directionally solidified.
  • dendritic crystals are aligned along the warm flow and form either a prismatic crystalline grain structure (columnar, i.e. grains extending throughout the length of the work piece and here, in common language use, referred to as directionally solidified) or a monocrystalline structure, i. the whole work consists of a single crystal.
  • a prismatic crystalline grain structure columnumnar, i.e. grains extending throughout the length of the work piece and here, in common language use, referred to as directionally solidified
  • a monocrystalline structure i. the whole work consists of a single crystal.
  • the blades 120, 130 may have coatings against corrosion or oxidation, e.g. M is at least one element of the group iron (Fe), cobalt (Co), nickel (Ni), X is an active element and stands for yttrium (Y) and / or silicon and / or at least one element of the rare ones Earth, or hafnium (Hf)).
  • M is at least one element of the group iron (Fe), cobalt (Co), nickel (Ni)
  • X is an active element and stands for yttrium (Y) and / or silicon and / or at least one element of the rare ones Earth, or hafnium (Hf)).
  • Such alloys are known from EP 0 486 489 B1, EP 0 786 017 B1, EP 0 412 397 B1 or EP 1 306 454 A1, which should be part of this disclosure with regard to the chemical composition of the alloy. 200815491
  • the density is preferably 95% of the theoretical density.
  • the layer composition comprises Co-30Ni-28Cr-8A1-0, 6Y-0, 7Si or Co-28Ni-24Cr-10Al-0, 6Y.
  • nickel-based protective layers such as Ni-10Cr-12Al-0.6Y-3Re or Ni-12Co-21Cr-IIAl-O, 4Y-2Re or Ni-25Co-17Cr-10A1-0, 4Y-1 are also preferably used , 5Re.
  • MCrAlX may still be a Warmedamm Mrs be present, which is preferably the outermost layer, and consists for example of ZrO 2 , Y 2 O 3 -ZrO 2 , ie it is not, partially or completely stabilized by yttria and / or calcium oxide and / or magnesium oxide.
  • the thermal insulation layer covers the entire MCrAlX layer. Suitable coating processes, such as electron beam evaporation (EB-PVD), are used to produce protuberant grains in the thermal insulation layer.
  • EB-PVD electron beam evaporation
  • the thermal barrier layer can have porous, micro- or macro-cracked grains for better thermal shock resistance.
  • the thermal insulation layer is therefore preferably more porous than the MCrAlX layer.
  • the blade 120, 130 may be hollow or solid. When the blade 120, 130 is to be cooled, it is hollow and possibly still has film cooling holes 418 (indicated by dashed lines).
  • FIG. 5 shows a combustion chamber 110 of the gas turbine 100.
  • the combustion chamber 110 is designed, for example, as a so-called annular combustion chamber, in which a large number of 200815491
  • the combustion chamber 110 is configured in its entirety as an annular structure, which is positioned around the axis of rotation 102 around.
  • the combustion chamber 110 is designed for a comparatively high temperature of the working medium M of about 1000 ° C. to 1600 ° C.
  • the combustion chamber wall 153 is provided on its side facing the working medium M side with an inner lining formed from heat shield elements 155.
  • a cooling system can additionally be provided for the heat shield elements 155 or for their holding elements.
  • the heat shield elements 155 are then, for example, hollow and possibly still have cooler holes (not shown) which still touch the combustion chamber space 154.
  • Each heat shield element 155 made of an alloy is equipped on the working fluid side with a particularly heat-resistant protective layer (MCrAlX layer and / or ceramic coating) or is made of high-temperature-resistant material (solid ceramic blocks).
  • M is at least one element of the group iron (Fe), cobalt (Co), nickel (Ni), X is an active element and stands for yttrium (Y) and / or silicon and / or at least one element of the rare earths, or hafnium (Hf).
  • MCrAlX means: M is at least one element of the group iron (Fe), cobalt (Co), nickel (Ni), X is an active element and stands for yttrium (Y) and / or silicon and / or at least one element of the rare earths, or hafnium (Hf).
  • Such alloys are known from EP 0 486 489 B1, EP 0 786 017 Bl, EP 0 412 397 B1 or EP 1 306 454 A1.
  • a ceramic thermal barrier layer may be present and consists for example of 200815491
  • Electron Beam Evaporation produces proton grains in the thermal insulation layer.
  • the thermal insulation layer may have porous, micro- or macro-cracked grains for better thermal shock resistance.
  • Refurbishment means that turbine blades 120, 130, heat shield elements 155 may need to be deprotected after use (e.g., by sandblasting). This is followed by removal of the corrosion and / or oxidation layers or products. Optionally, cracks in the turbine blade 120, 130 or the heat shield element 155 are also repaired. This is followed by a re-coating of the turbine blades 120, 130, heat shield elements 155 and a renewed use of the turbine blades 120, 130 or the heat shield elements 155.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L’invention se rapporte à une couche de MCrAlX composée de deux strates pour améliorer aussi bien la résistance à l’oxydation que la résistance thermomécanique : dans cette couche, on trouve des teneurs en nickel et en cobalt mais aussi en CR, en Al et en Z nettement différentes.
EP09749687A 2008-05-20 2009-04-16 Couche de mcralx composée de deux strates présentant différentes teneurs en cobalt et en nickel Withdrawn EP2294235A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09749687A EP2294235A1 (fr) 2008-05-20 2009-04-16 Couche de mcralx composée de deux strates présentant différentes teneurs en cobalt et en nickel

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08009324A EP2128285A1 (fr) 2008-05-20 2008-05-20 Couche de MCrAIX à double épaisseur ayant des teneurs en cobalt et nickel différentes
EP09000248A EP2206806A1 (fr) 2009-01-09 2009-01-09 Couche de MCrAIX à double épaisseur ayant des teneurs en cobalt et nickel différentes
EP09749687A EP2294235A1 (fr) 2008-05-20 2009-04-16 Couche de mcralx composée de deux strates présentant différentes teneurs en cobalt et en nickel
PCT/EP2009/054494 WO2009141197A1 (fr) 2008-05-20 2009-04-16 Couche de mcralx composée de deux strates présentant différentes teneurs en cobalt et en nickel

Publications (1)

Publication Number Publication Date
EP2294235A1 true EP2294235A1 (fr) 2011-03-16

Family

ID=40866660

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09749687A Withdrawn EP2294235A1 (fr) 2008-05-20 2009-04-16 Couche de mcralx composée de deux strates présentant différentes teneurs en cobalt et en nickel

Country Status (4)

Country Link
US (1) US20110189502A1 (fr)
EP (1) EP2294235A1 (fr)
CN (1) CN102037147A (fr)
WO (1) WO2009141197A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2354260A1 (fr) * 2010-01-12 2011-08-10 Siemens Aktiengesellschaft Alliage, couche de protection et composant
EP2345748A1 (fr) * 2010-01-14 2011-07-20 Siemens Aktiengesellschaft Alliage, couche de protection et composant
RU2597459C2 (ru) * 2011-09-12 2016-09-10 Сименс Акциенгезелльшафт СИСТЕМА СЛОЕВ С ДВОЙНЫМ МЕТАЛЛИЧЕСКИМ MCrAlY-ПОКРЫТИЕМ
EP2682488A1 (fr) * 2012-07-05 2014-01-08 Siemens Aktiengesellschaft Système de couche doté d'une couche de protection doble en NiCoCrAIY ayant une teneur en chrome variable et alliage
US20140186656A1 (en) * 2012-12-31 2014-07-03 United Technologies Corporation Spallation-Resistant Thermal Barrier Coating

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5499905A (en) * 1988-02-05 1996-03-19 Siemens Aktiengesellschaft Metallic component of a gas turbine installation having protective coatings
US5401307A (en) * 1990-08-10 1995-03-28 Siemens Aktiengesellschaft High temperature-resistant corrosion protection coating on a component, in particular a gas turbine component
EP0861927A1 (fr) * 1997-02-24 1998-09-02 Sulzer Innotec Ag Procédé de fabrication de structures monocristallines
US6610419B1 (en) * 1998-04-29 2003-08-26 Siemens Akteingesellschaft Product with an anticorrosion protective layer and a method for producing an anticorrosion protective
EP1295969A1 (fr) * 2001-09-22 2003-03-26 ALSTOM (Switzerland) Ltd Procédé pour la croissance d'un revêtement de MCrAlY ainsi qu'un objet revêtu de cet alliage
EP1380672A1 (fr) * 2002-07-09 2004-01-14 Siemens Aktiengesellschaft Composant à haute résistance contre l'oxydation
EP1783236A1 (fr) * 2005-11-04 2007-05-09 Siemens Aktiengesellschaft Alliage, couche protectrice pour proteger un élément structurel contre la corrosion et l'oxydation aux temperatures hautes et élément structurel
EP1798299B1 (fr) * 2005-12-14 2008-10-08 Siemens Aktiengesellschaft Alliage, couche de protection et élément de construction
EP1816222A1 (fr) * 2006-01-20 2007-08-08 Siemens Aktiengesellschaft Système de revêtements de couches métalliques protectrices à double couche
EP1845171B1 (fr) * 2006-04-10 2016-12-14 Siemens Aktiengesellschaft Utilisation de poudres métalliques ayant des particles de taille diverse pour fabriquer un système de couches

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009141197A1 *

Also Published As

Publication number Publication date
WO2009141197A1 (fr) 2009-11-26
CN102037147A (zh) 2011-04-27
US20110189502A1 (en) 2011-08-04

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