US20130288072A1 - Alloy, protective layer and component - Google Patents

Alloy, protective layer and component Download PDF

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Publication number
US20130288072A1
US20130288072A1 US13/977,747 US201113977747A US2013288072A1 US 20130288072 A1 US20130288072 A1 US 20130288072A1 US 201113977747 A US201113977747 A US 201113977747A US 2013288072 A1 US2013288072 A1 US 2013288072A1
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United States
Prior art keywords
alloy
protective layer
layer
component
nickel
Prior art date
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Abandoned
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US13/977,747
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English (en)
Inventor
Friedhelm Schmitz
Werner Stamm
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Siemens AG
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Siemens AG
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Filing date
Publication date
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Assigned to SIEMENS AKTIENGESELLSCHAFT reassignment SIEMENS AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHMITZ, FRIEDHELM, STAMM, WERNER
Publication of US20130288072A1 publication Critical patent/US20130288072A1/en
Abandoned legal-status Critical Current

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    • 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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • 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
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • 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
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • 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
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • 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 an alloy to a protective layer for protecting a component against corrosion and/or oxidation, in particular at high temperatures and to a component as claimed in the claims.
  • Typical coatings of this type are known from U.S. Pat. Nos. 4,005,989 and 4,034,142.
  • the addition of rhenium (Re) to NiCoCrAlY alloys is also known.
  • a protective layer must also have sufficiently good mechanical properties, not least in respect of the mechanical interaction between the protective layer and the base material.
  • the protective layer must be ductile enough to be able to accommodate possible deformations of the base material and not crack, since points of attack would thereby be provided for oxidation and corrosion.
  • the object is likewise achieved by an alloy and a protective layer and a component, in particular a component of a gas turbine or steam turbine, which comprises a protective layer of the type described above for protection against corrosion and oxidation at high temperatures as claimed in the independent claims.
  • the invention is based inter alia on the discovery that the protective layer may exhibit brittle rhenium precipitates in the layer and in the transition region between the protective layer and the base material.
  • These brittle phases which are formed increasingly over time and with the temperature during use, lead during operation to very pronounced longitudinal cracks in the layer as well as in the layer-base material interface, with subsequent shedding of the layer.
  • the brittleness of the rhenium precipitates is further increased by the interaction with carbon, which can diffuse into the layer from the base material or diffuses into the layer through the surface during a heat treatment in the furnace.
  • the impetus to cracking is further enhanced by oxidation of the rhenium phases.
  • FIG. 1 shows a layer system with a protective layer
  • FIG. 2 shows compositions of superalloys
  • FIG. 3 shows a gas turbine
  • FIG. 4 shows a turbine blade
  • FIG. 5 shows a combustion chamber
  • a protective layer 7 for protecting a component against corrosion and oxidation at a high temperature essentially comprises the following elements (proportions indicated in wt %):
  • Co cobalt
  • Al aluminum
  • Y yttrium
  • at least one equivalent metal from the group comprising scandium and the rare earth elements from 12% to 14% chromium (Cr), from 0.3% to 3% tantalum (Ta), nickel (Ni) (NiCoCrAlY).
  • An advantageous embodiment consists of the elements nickel, cobalt, chromium, aluminum, tantalum and yttrium.
  • the yttrium value is advantageously up to 0.7 wt %. Nevertheless, the yttrium content in the alloy should generally not be too high, since otherwise it leads to embrittlement.
  • the proportions of the individual elements are specially adapted with a view to their effects, which are to be seen particularly in connection with the element rhenium (not present). If the proportions are dimensioned in this way, the addition of rhenium (Re) can be dispensed with, so that, in addition, no rhenium precipitates are formed.
  • Advantageously no brittle phases are created during use of the protective layer so that the operating time performance is improved and extended.
  • the reduction of the mechanical stresses due to the selected nickel content improves the mechanical properties.
  • the protective layer has particularly good resistance against oxidation and is also distinguished by particularly good ductility properties, so that it is particularly qualified for use in a gas turbine 100 ( FIG. 3 ) with a further increase in the intake temperature.
  • the powders are for example applied by plasma spraying (APS, LPPS, VPS, etc.).
  • Other methods may likewise be envisaged (HVOF, PVD, CVD, cold gas spraying, etc.).
  • the described protective layer 7 also acts as a layer which improves adhesion to the superalloy.
  • a single protective layer 7 is used for the component, i.e. no duplex layer for the bondcoat.
  • thermo barrier layers 10 may be applied onto this protective layer 7 .
  • the protective layer 7 is advantageously applied onto a substrate 4 made of a nickel-based or cobalt-based superalloy.
  • composition in particular may be suitable as a substrate (data in wt %):
  • compositions of this type are known as casting alloys under the references GDT222, IN939, IN6203 and Udimet 500.
  • the thickness of the protective layer 7 on the component 1 is preferably dimensioned with a value of between about 100 ⁇ m and 300 ⁇ m.
  • the protective layer 7 is particularly suitable for protecting the component 1 , 120 , 130 , 155 against corrosion and oxidation while the component is being exposed to an exhaust gas at a material temperature of about 950° C., or even about 1100° C. in aircraft turbines.
  • the protective layer 7 according to the invention is therefore particularly qualified for protecting a component of a gas turbine 100 , in particular a guide vane 120 , rotor blade 130 or a heat shield element 155 , which is exposed to hot gas before or in the turbine of the gas turbine 100 or of the steam turbine.
  • the protective layer 7 may be used as an overlay (the protective layer is the outer layer) or as a bondcoat (the protective layer is an interlayer). It is preferably used as a single layer, i.e. there is no further metal layer.
  • FIG. 1 shows a layer system 1 as a component.
  • the layer system 1 consists of a substrate 4 .
  • the substrate 4 may be metallic and/or ceramic. Particularly in the case of turbine components, for example turbine rotor blades 120 ( FIG. 4 ) or guide vanes 130 ( FIGS. 3 , 4 ), heat shield elements 155 ( FIG. 5 ) or other housing parts of a steam or gas turbine 100 ( FIG. 3 ), the substrate 4 consists of a nickel-, cobalt- or iron-based superalloy. Nickel-based superalloys are preferably used.
  • the protective layer 7 is provided on the substrate 4 . It is preferably used as a single layer, i.e. there is no further metal layer.
  • This protective layer 7 is preferably applied by plasma spraying (VPS, LPPS, APS, etc.). It may be used as an outer layer (not shown) or interlayer ( FIG. 1 ). In the latter case, there will be a ceramic thermal barrier layer 10 on the protective layer 7 .
  • the protective layer 7 may be applied onto newly produced components and refurbished components.
  • Refurbishment means that components 1 are separated if need be from layers (thermal barrier layer) after their use and corrosion and oxidation products are removed, for example by an acid treatment (acid stripping). It may sometimes also be necessary to repair cracks. Such a component may subsequently be recoated, since the substrate 4 is very expensive.
  • FIG. 3 shows a gas turbine 100 by way of example in a partial longitudinal section.
  • the gas turbine 100 internally comprises a rotor 103 , which will also be referred to as the turbine rotor, mounted so as to rotate about a rotation axis 102 and having a shaft 101 .
  • a rotor 103 which will also be referred to as the turbine rotor, mounted so as to rotate about a rotation axis 102 and having a shaft 101 .
  • an intake manifold 104 there are an intake manifold 104 , a compressor 105 , an e.g. toroidal combustion chamber 110 , in particular a ring combustion chamber, having a plurality of burners 107 arranged coaxially, a turbine 108 and the exhaust manifold 109 .
  • the ring combustion chamber 110 communicates with an e.g. annular hot gas channel 111 .
  • Each turbine stage 112 is formed for example by two blade rings. As seen in the flow direction of a working medium 113 , a guide vane row 115 is followed in the hot gas channel 111 by a row 125 formed by rotor blades 120 .
  • the guide vanes 130 are fastened on an inner housing 138 of a stator 143 while the rotor blades 120 of a row 125 are fitted on the rotor 103 , for example by means of a turbine disk 133 . Coupled to the rotor 103 , there is a generator or a work engine (not shown).
  • air 135 is taken in and compressed by the compressor 105 through the intake manifold 104 .
  • the compressed air provided at the turbine-side end of the compressor 105 is delivered to the burners 107 and mixed there with a fuel.
  • the mixture is then burnt to form the working medium 113 in the combustion chamber 110 .
  • the working medium 113 flows along the hot gas channel 111 past the guide vanes 130 and the rotor blades 120 .
  • the working medium 113 expands by imparting momentum, so that the rotor blades 120 drive the rotor 103 and the work engine coupled to it.
  • the components exposed to the hot working medium 113 experience thermal loads during operation of the gas turbine 100 .
  • the guide vanes 130 and rotor blades 120 of the first turbine stage 112 are heated the most. In order to withstand the temperatures prevailing there, they may be cooled by means of a coolant.
  • the substrates may likewise comprise a directional structure, i.e. they are single-crystal (SX structure) or comprise only longitudinally directed grains (DS structure).
  • SX structure single-crystal
  • DS structure longitudinally directed grains
  • Iron-, nickel- or cobalt-based superalloys are for example used as the material for the components, in particular for the turbine blades 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 guide vanes 130 comprise a guide vane root (not shown here) facing the inner housing 138 of the turbine 108 , and a guide vane head lying opposite the guide vane root.
  • the guide vane head faces the rotor 103 and is fixed on a fastening ring 140 of the stator 143 .
  • FIG. 4 shows a perspective view of a rotor blade 120 or guide vane 130 of a turbomachine, which extends along a longitudinal axis 121 .
  • the turbomachine may be a gas turbine of an aircraft or of a power plant for electricity generation, a steam turbine or a compressor.
  • the blade 120 , 130 comprises, successively along the longitudinal axis 121 , a fastening zone 400 , a blade platform 403 adjacent thereto as well as a blade surface 406 and a blade tip 415 .
  • the vane 130 may have a further platform (not shown) at its vane tip 415 .
  • a blade root 183 which is used to fasten the rotor blades 120 , 130 on a shaft or a disk (not shown) is formed in the fastening zone 400 .
  • the blade root 183 is configured, for example, as a hammerhead. Other configurations as a firtree or dovetail root are possible.
  • the blade 120 , 130 comprises a leading edge 409 and a trailing edge 412 for a medium which flows past the blade surface 406 .
  • blades 120 , 130 for example solid metallic materials, in particular superalloys, are used in all regions 400 , 403 , 406 of the blade 120 , 130 .
  • 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 blade 120 , 130 may in this case be manufactured by a casting method, also by means of directional solidification, by a forging method, by a machining method or combinations thereof.
  • Workpieces with a single-crystal structure or single-crystal structures are used as components for machines which are exposed to heavy mechanical, thermal and/or chemical loads during operation.
  • Such single-crystal workpieces are manufactured, for example, by directional solidification from the melts. These are casting methods in which the liquid metal alloy is solidified to form a single-crystal structure, i.e. to form the single-crystal workpiece, or is directionally solidified.
  • Dendritic crystals are in this case aligned along the heat flux and form either a rod crystalline grain structure (columnar, i.e. grains which extend over the entire length of the workpiece and in this case, according to general terminology usage, are referred to as directionally solidified) or a single-crystal structure, i.e. the entire workpiece consists of a single crystal. It is necessary to avoid the transition to globulitic (polycrystalline) solidification in these methods, since nondirectional growth will necessarily form transverse and longitudinal grain boundaries which negate the beneficial properties of the directionally solidified or single-crystal component.
  • directionally solidified structures When directionally solidified structures are referred to in general, this is intended to mean both single crystals which have no grain boundaries or at most small-angle grain boundaries, and also rod crystal structures which, although they do have grain boundaries extending in the longitudinal direction, do not have any transverse grain boundaries. These latter crystalline structures are also referred to as directionally solidified structures. Such methods are known from U.S. Pat. No. 6,024,792 and EP 0 892 090 A1.
  • the blades 120 , 130 may also have layers 7 according to the invention protecting against corrosion or oxidation.
  • the density is preferably 95% of the theoretical density.
  • thermal barrier layer which is preferably the outermost layer and consists for example of ZrO 2 , Y 2 O 3 —ZrO 2 , i.e. it is not stabilized or is partially or fully stabilized by yttrium oxide and/or calcium oxide and/or magnesium oxide.
  • the thermal barrier layer covers the entire MCrAlX layer.
  • Rod-shaped grains are produced in the thermal barrier layer by suitable coating methods, for example electron beam deposition (EB-PVD).
  • the thermal barrier layer may comprise porous, micro- or macro-cracked grains for better thermal shock resistance.
  • the thermal barrier layer is thus preferably more porous than the MCrAlX layer.
  • the blade 120 , 130 may be designed to be hollow or solid. If the blade 120 , 130 is intended to be cooled, it will be hollow and optionally also comprise film cooling holes 418 (indicated by dashes).
  • FIG. 5 shows a combustion chamber 110 of the gas turbine 100 .
  • the combustion chamber 110 is designed for example as a so-called ring combustion chamber in which a multiplicity of burners 107 , which produce flames 156 and are arranged in the circumferential direction around a rotation axis 102 , open into a common combustion chamber space 154 .
  • the combustion chamber 110 as a whole is designed as an annular structure which is positioned around the rotation axis 102 .
  • the combustion chamber 110 is designed for a relatively high temperature of the working medium M, of about 1000° C. to 1600° C.
  • the combustion chamber wall 153 is provided with an inner lining formed by heat shield elements 155 on its side facing the working medium M.
  • a cooling system may also be provided for the heat shield elements 155 or for their retaining elements.
  • the heat shield elements 155 are then hollow, for example, and optionally also have cooling holes (not shown) opening into the combustion chamber space 154 .
  • Each heat shield element 155 made of an alloy is equipped with a particularly heat-resistant protective layer (MCrAlX layer and/or ceramic coating) on the working medium side, or is made of refractory material (solid ceramic blocks).
  • MrAlX layer and/or ceramic coating On the MCrAlX, there may furthermore be an e.g. ceramic thermal barrier layer which consists for example of ZrO 2 , Y 2 O 3 —ZrO 2 , i.e. it is not stabilized or is partially or fully stabilized by yttrium oxide and/or calcium oxide and/or magnesium oxide.
  • Rod-shaped grains are produced in the thermal barrier layer by suitable coating methods, for example electron beam deposition (EB-PVD). Other coating methods may be envisaged, for example atmospheric plasma spraying (APS), LPPS, VPS or CVD.
  • the thermal barrier layer may comprise porous, micro- or macro-cracked grains for better thermal shock resistance.
  • Refurbishment means that turbine blades 120 , 130 or heat shield elements 155 may need to be stripped of protective layers (for example by sandblasting) after their use. The corrosion and/or oxidation layers or products are then removed. Optionally, cracks in the turbine blade 120 , 130 or heat shield element 155 are also repaired. The turbine blades 120 , 130 or heat shield elements 155 are then recoated and the turbine blades 120 , 130 or heat shield elements 155 are used again.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Physical Vapour Deposition (AREA)
US13/977,747 2011-01-06 2011-11-22 Alloy, protective layer and component Abandoned US20130288072A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11150304.1 2011-01-06
EP11150304A EP2474414A1 (fr) 2011-01-06 2011-01-06 Alliage, couche de protection et composant
PCT/EP2011/070671 WO2012092997A1 (fr) 2011-01-06 2011-11-22 Alliage, couche protectrice et pièce

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Publication Number Publication Date
US20130288072A1 true US20130288072A1 (en) 2013-10-31

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US13/977,747 Abandoned US20130288072A1 (en) 2011-01-06 2011-11-22 Alloy, protective layer and component

Country Status (5)

Country Link
US (1) US20130288072A1 (fr)
EP (2) EP2474414A1 (fr)
CN (1) CN103282197A (fr)
ES (1) ES2640219T3 (fr)
WO (1) WO2012092997A1 (fr)

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US11092034B2 (en) 2011-08-09 2021-08-17 Siemens Energy Global Gmbh & Co, Kg Alloy, protective layer and component

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11092034B2 (en) 2011-08-09 2021-08-17 Siemens Energy Global Gmbh & Co, Kg Alloy, protective layer and component
CN106739261A (zh) * 2016-11-24 2017-05-31 苏州华意铭铄激光科技有限公司 一种低温塑性好的复合金属制品

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EP2474414A1 (fr) 2012-07-11
EP2661370B1 (fr) 2017-06-14

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