EP2491156B1 - Alloy for directional solidification and columnar grained component - Google Patents

Alloy for directional solidification and columnar grained component Download PDF

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Publication number
EP2491156B1
EP2491156B1 EP09756148.4A EP09756148A EP2491156B1 EP 2491156 B1 EP2491156 B1 EP 2491156B1 EP 09756148 A EP09756148 A EP 09756148A EP 2491156 B1 EP2491156 B1 EP 2491156B1
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EP
European Patent Office
Prior art keywords
content
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iron
boron
phosphorus
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EP09756148.4A
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German (de)
French (fr)
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EP2491156A1 (en
Inventor
Winfried Esser
Dirk Goldschmidt
Christopher R. Hanslits
Michael Ott
Uwe Paul
Ursula Pickert
Russel G. Vogt
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Siemens AG
Howmet Corp
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Siemens AG
Howmet Corp
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Priority to EP18000230.5A priority Critical patent/EP3363923A1/en
Publication of EP2491156A1 publication Critical patent/EP2491156A1/en
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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
    • C22C19/051—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

Definitions

  • the invention relates to an alloy which serves for the production of directionally solidified components, and to a component which has stem-shaped crystals.
  • nickel-based superalloys are often used.
  • single crystals or components with stalk-shaped grains are used.
  • the components with the stem-shaped grains depend on the grain boundary strength and on the grain boundary precipitates or the presence of foreign elements (impurities) which deposit on the grain boundaries. These elements can have a significant influence on the mechanical behavior at high temperatures.
  • the WO 00/44949 discloses a nickel-base superalloy with a high molybdenum content.
  • the US 6,231,692 also discloses a nickel-based high molybdenum alloy.
  • the EP 1 329 527 B1 discloses a nickel-based superalloy in which the elements zirconium and hafnium are deliberately added.
  • the EP 0 855 449 B1 also discloses a minimal addition of zirconium.
  • FIG. 1 shows a perspective view of a 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 a power plant for power generation, a steam turbine or a compressor.
  • the blade 120, 130 has along the longitudinal axis 121 consecutively a fastening region 400, a blade platform 403 adjacent thereto 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 leading edge 409 and a trailing edge 412 for a medium flowing past the airfoil 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 for example from EP 1 204 776 B1 .
  • EP 1 306 454 .
  • the blade 120, 130 can be made by a casting process, also by directional solidification, by a forging process, by a milling process or combinations thereof.
  • 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 the EP 0 486 489 B1 .
  • EP 0 412 397 B1 or EP 1 306 454 A1 The density is preferably 95% of the theoretical density.
  • the layer composition comprises Co-30Ni-28Cr-8Al-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-11Al-0.4Y-2Re or Ni-25Co-17Cr-10Al-0.4Y-1 are also preferably used , 5RE.
  • thermal barrier coating 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 barrier coating covers the entire MCrAlX layer.
  • suitable coating processes such as electron beam evaporation (EB-PVD)
  • stalk-shaped grains are produced in the thermal barrier coating.
  • Other coating methods are conceivable, for example atmospheric plasma spraying (APS), LPPS, VPS or CVD.
  • the thermal barrier coating may have porous, micro- or macro-cracked grains for better thermal shock resistance.
  • the thermal barrier coating is therefore preferably more porous than the MCrAlX layer.
  • Refurbishment means that components 120, 130 may have to be freed of protective layers after use (eg by sandblasting). This is followed by removal of the corrosion and / or oxidation layers or products. Optionally, even cracks in the component 120, 130 are repaired. Then there is a like the coating of the component 120, 130 and a renewed use of the component 120, 130.
  • the blade 120, 130 may be hollow or solid. If the blade 120, 130 is to be cooled, it is hollow and may still film cooling holes 418 (indicated by dashed lines) on.
  • the FIG. 2 shows a combustion chamber 110 of a gas turbine.
  • the combustion chamber 110 is designed, for example, as a so-called annular combustion chamber, in which a plurality of burners 107 arranged around a rotation axis 102 in the circumferential direction open into a common combustion chamber space 154, which generate flames 156.
  • 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.
  • Each heat shield element 155 made of an alloy is equipped on the working medium 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 the EP 0 486 489 B1 .
  • EP 0 412 397 B1 or EP 1 306 454 A1 are known from the EP 0 486 489 B1 .
  • EP 0 412 397 B1 or EP 1 306 454 A1 is known from the EP 0 486 489 B1 .
  • a ceramic thermal barrier coating may be present 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.
  • suitable coating processes such as electron beam evaporation (EB-PVD)
  • stalk-shaped grains are produced in the thermal barrier coating.
  • APS atmospheric plasma spraying
  • LPPS LPPS
  • VPS vacuum plasma spraying
  • CVD chemical vaporation
  • the thermal barrier coating may have porous, micro- or macro-cracked grains for better thermal shock resistance.
  • Refurbishment means that heat shield elements 155 may need to be deprotected (e.g., by sandblasting) after use. This is followed by removal of the corrosion and / or oxidation layers or products. If necessary, cracks in the heat shield element 155 are also repaired. This is followed by a recoating of the heat shield elements 155 and a renewed use of the heat shield elements 155.
  • the heat shield elements 155 are then, for example, hollow and possibly still have cooling holes (not shown) which open into the combustion chamber space 154.
  • FIG. 3 shows by way of example a gas turbine 100 in a longitudinal partial section.
  • the gas turbine 100 has inside a rotatably mounted about a rotation axis 102 rotor 103 with a shaft 101, 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 109th
  • the annular combustion chamber 110 communicates with an annular annular hot gas channel 111, for example.
  • Each turbine stage 112 is formed, for example, from two blade rings.
  • a series 125 formed of rotor blades 120 follows.
  • the guide vanes 130 are fastened to an inner housing 138 of a stator 143, whereas the moving blades 120 of a row 125 are attached to the rotor 103 by means of a turbine disk 133, for example. Coupled to the rotor 103 is a generator or work machine (not shown).
  • 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.
  • 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 in a pulse-transmitting manner so that the rotor blades 120 drive the rotor 103 and drive the machine coupled to it.
  • the components exposed to the hot working medium 113 are subject to thermal loads during operation of the gas turbine 100.
  • the guide vanes 130 and rotor blades 120 of the first turbine stage 112, viewed in the flow direction 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. To withstand the prevailing temperatures, they can be cooled by means of a coolant.
  • substrates of the components can have a directional structure, ie they are monocrystalline (SX structure) or have only longitudinal grains (DS structure).
  • As the material for the components, in particular for the turbine blade 120, 130 and components of the combustion chamber 110 for example, iron-, nickel- or cobalt-based superalloys are used. Such superalloys are for example from EP 1 204 776 B1 .
  • EP 1 306 454 EP 1 319 729 A1 .
  • the blades 120, 130 may be anti-corrosion coatings (MCrAlX; M is at least one element of the group iron (Fe), cobalt (Co), nickel (Ni), X is an active element and is yttrium (Y) and / or silicon , Scandium (Sc) and / or at least one element of the rare earth or hafnium).
  • M is at least one element of the group iron (Fe), cobalt (Co), nickel (Ni)
  • X is an active element and is yttrium (Y) and / or silicon , Scandium (Sc) and / or at least one element of the rare earth or hafnium).
  • Such alloys are known from the EP 0 486 489 B1 .
  • EP 0 412 397 B1 or EP 1 306 454 A1 are known from the EP 0 486 489 B1 .
  • a thermal barrier coating On the MCrAlX may still be present a thermal barrier coating, 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.
  • suitable coating processes such as electron beam evaporation (EB-PVD), stalk-shaped grains are produced in the thermal barrier coating.
  • the vane 130 has a the inner casing 138 of the turbine 108 facing Leitschaufelfuß (not shown here ) and a vane head opposite the vane root.
  • the vane head faces the rotor 103 and fixed to a mounting ring 140 of the stator 143.
  • the alloy according to the invention has the following contents in percent by weight (% by weight): Chrome (Cr) 9.0 to 15.0 especially 9.0 to 15.0 Titanium (Ti) 2.0 to 6.0 especially 2.0 to 6.0 Molybdenum (Mo) 1.0 to 3.0 Tungsten (W) 2.0 to 6.0 Tantalum (Ta) 3.0 to 7.0 Aluminum (Al) 2.0 to 6.0 Cobalt (Co) 6.0 to 11.0 Boron (B) 0.0025 to 0.05 Carbon (C) 0.01 to 0.3 and at least one element of the group silicon (Si), iron (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S) , and manganese (Mn). This listing is not exhaustive.
  • the superalloy comprises (in% by weight): Chrome (Cr) 11.0 to 13.0 especially 11.6 to 12.7 Titanium (Ti) 3.5 to 4.5 especially 3.9 to 4.25 Molybdenum (Mo) 1.65 to 2.15 Tungsten (W) 3.5 to 4.1 Tantalum (Ta) 4.8 to 5.2 Aluminum (Al) 3.4 to 3.8 Cobalt (Co) 8.5 to 9.5 Boron (B) 0.0125 to 0.0175 Carbon (C) 0.08 to 0.1 especially 0.09.
  • Si silicon
  • iron Fe
  • vanadium V
  • niobium Nb
  • copper Cu
  • hafnium Hf
  • zirconium Zr
  • phosphorus P
  • sulfur S
  • manganese Mn
  • the proportion of iron (Fe) must not exceed 0.2% and may be at least 0.014Gew%.
  • Iron (Fe) is known as the ⁇ '-former and nickel-substituent.
  • Silicon and iron also improve castability. A reduction of the elements would be rather undesirable.
  • the content of vanadium (V) is not greater than 75 ppm and is preferably at least 50 ppm.
  • the proportion of copper (Cu) may be up to 0.1Gew% with minimum values from 0.001Gew%.
  • the content of hafnium (Hf) is not larger than 50ppm. This is in contrast to the known alloys for directional solidification with columnar grains, in which hafnium is deliberately added in larger proportions to stabilize the grain boundaries between the stem grains.
  • the boron content is 150 ppm.
  • Ni niobium
  • the amount of niobium (Nb) - deliberately added in some Ni superalloys - may here be up to 75ppm with minimum values of 50ppm.
  • grain boundary consolidators such as hafnium and zirconium
  • boron (B) and carbon (C) are added.
  • the carbon content is higher than 0.08Gew%.
  • Impurities of the alloys preferably have a maximum value of 10 ppm.
  • the proportion of sulfur (S) is at least 0.0003 wt% and at most 0.25 wt%.
  • the proportion of phosphorus (P) is at least 0.003 wt% and at most 0.025 wt%.
  • components 120, 130 may be manufactured inexpensively but with known good high temperature properties.
  • the elements silicon (Si), iron (Fe), phosphorus (P) and sulfur (S) are accepted.

Description

Die Erfindung betrifft eine Legierung, die zur Herstellung von gerichtet erstarrten Bauteilen dient, und ein Bauteil, dass stängelförmige Kristalle aufweist.The invention relates to an alloy which serves for the production of directionally solidified components, and to a component which has stem-shaped crystals.

Für den Einsatz im Hochtemperaturbereich, wie zum Beispiel bei Gasturbinen werden oft nickelbasierte Superlegierungen verwendet. Zur weiteren Steigerung der Festigkeit werden Einkristalle oder Bauteile mit stängelförmigen Körnern verwendet.For high temperature applications, such as gas turbines, nickel-based superalloys are often used. To further increase the strength, single crystals or components with stalk-shaped grains are used.

Bei den Bauteilen mit den stängelförmigen Körnern kommt es auf die Korngrenzenfestigkeit an und auf die Korngrenzen-Ausscheidungen bzw. das Vorhandensein von Fremdelementen (Verunreinigungen), die sich an den Korngrenzen abscheiden. Diese Elemente können einen erheblichen Einfluss auf das mechanische Verhalten bei den hohen Temperaturen aufweisen.The components with the stem-shaped grains depend on the grain boundary strength and on the grain boundary precipitates or the presence of foreign elements (impurities) which deposit on the grain boundaries. These elements can have a significant influence on the mechanical behavior at high temperatures.

Die WO 00/44949 offenbart eine Nickelbasis-Superlegierung mit einem hohen Molybdänanteil.The WO 00/44949 discloses a nickel-base superalloy with a high molybdenum content.

Die US 6,231,692 offenbart ebenfalls eine nickelbasierte Legierung mit hohem Molybdängehalt.The US 6,231,692 also discloses a nickel-based high molybdenum alloy.

Die EP 1 329 527 B1 offenbart eine nickelbasierte Superlegierung bei dem die Elemente Zirkon und Hafnium bewusst hinzugegeben werden.The EP 1 329 527 B1 discloses a nickel-based superalloy in which the elements zirconium and hafnium are deliberately added.

Die EP 0 855 449 B1 offenbart ebenfalls eine minimale Zugabe von Zirkon.The EP 0 855 449 B1 also discloses a minimal addition of zirconium.

Diese Legierungen weisen jedoch eine geringe Korngrenzenfestigkeit auf, die die gesamte Festigkeit eines Bauteils dadurch negativ beeinflussen, oder sind durch Zirkon und Hafnium zu wenig duktil.However, these alloys have a low grain boundary strength, which adversely affect the overall strength of a component, or are too ductile by zirconium and hafnium.

Geringere Zugaben von bestimmten Elementen können bei Überschreitung negative Auswirkungen auf diese Eigenschaften der Legierung haben.
Allerdings stellt die Verringerung der Anteile solcher Elemente einen hohen Aufwand dar. Es ist also abzuwägen zwischen Kosten und Optimierung der Eigenschaften der Legierung.Lower additions of certain elements can have a negative impact on these properties of the alloy if exceeded.
However, the reduction in the proportions of such elements is a high cost. It is therefore necessary to balance between costs and optimizing the properties of the alloy.

Es ist daher Aufgabe der Erfindung dieses Problem zu lösen. Die Aufgabe wird gelöst durch eine:
nickelbasierte Superlegierung für die gerichtete Erstarrung von Bauteilen mit stängelförmigen Körnern,
die besteht aus (in Gew.-%): Chrom (Cr) 9,0 bis 15,0 Titan (Ti) 2,0 bis 6,0 Molybdän (Mo) 1,0 bis 3,0 Wolfram (W) 2,0 bis 6,0 Tantal (Ta) 3,0 bis 7,0 Aluminium (Al) 2,0 bis 6,0 Kobalt (Co) 6,0 bis 11,0 Bor (B) 0,0025 bis 0,05 Kohlenstoff (C) 0,01 bis 0,3 Silizium (Si), wobei der der Siliziumgehalt (Si) mindestens 0,01% und maximal 0,12% beträgt,
Zirkon (Zr),
wobei die Legierung maximal 25ppm Zirkon (Zr) enthält, und zumindest ein Element der Gruppe
Eisen (Fe), Vanadium (V), Niob (Nb), Kupfer (Cu), Hafnium (Hf), Zirkon (Zr), Phosphor (P), Schwefel (S), und Mangan (Mn),
wobei gilt für diese Elemente, falls vorhanden,
bei der der Eisengehalt (Fe) maximal 0,2% beträgt, und/oder
bei der der Eisengehalt (Fe) mindestens 0,014% beträgt, insbesondere mindestens 0,02%,
bei der der Vanadiumgehalt (V) maximal 75ppm beträgt, und/oder bei der der Vanadiumgehalt (V) mindestens 50ppm beträgt,
bei der der maximale Niobgehalt (Nb) 75ppm beträgt, und/oder bei der der Niobgehalt (Nb) mindestens 50ppm beträgt,
bei der der Kupfergehalt (Cu) maximal 0,1% beträgt, und/oder
bei der der Kupfergehalt (Cu) mindestens 0,001% beträgt, bei der der Gehalt an Hafnium (Hf) maximal 75ppm beträgt, und/oder die mindestens 10ppm Hafnium (Hf) enthält, und/oder die mindestens 10ppm Zirkon (Zr) enthält,
bei der der maximale Mangangehalt (Mn) 0,12% beträgt, und/oder
bei der der Mangangehalt (Mn) mindestens 0,001% beträgt, bei der der maximale Gehalt an Phosphor (P) 0,015% beträgt, und/oder bei der der minimale Gehalt an Phosphor (P) 0,003%, bei der der maximale Gehalt an Schwefel (S) 0,025% beträgt, und/oder
bei der der minimale Gehalt an Schwefel (S) 0,0003%, optional:

  • bei der die Legierung 50ppm bis 2000 ppm,
  • Zinn oder Zink enthält.
It is therefore an object of the invention to solve this problem. The task is solved by a:
nickel-based superalloy for directional solidification of stalk-shaped components,
which consists of (in% by weight): Chrome (Cr) 9.0 to 15.0 Titanium (Ti) 2.0 to 6.0 Molybdenum (Mo) 1.0 to 3.0 Tungsten (W) 2.0 to 6.0 Tantalum (Ta) 3.0 to 7.0 Aluminum (Al) 2.0 to 6.0 Cobalt (Co) 6.0 to 11.0 Boron (B) 0.0025 to 0.05 Carbon (C) 0.01 to 0.3 Silicon (Si), wherein the silicon content (Si) is at least 0.01% and at most 0.12%,
Zircon (Zr),
wherein the alloy contains a maximum of 25ppm zirconium (Zr), and at least one element of the group
Iron (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S), and manganese (Mn),
where these elements apply, if any,
in which the iron content (Fe) is at most 0.2%, and / or
in which the iron content (Fe) is at least 0.014%, in particular at least 0.02%,
in which the vanadium content (V) is at most 75 ppm and / or in which the vanadium content (V) is at least 50 ppm,
where the maximum niobium content (Nb) is 75 ppm and / or where the niobium content (Nb) is at least 50 ppm,
in which the copper content (Cu) is at most 0.1%, and / or
in which the copper content (Cu) is at least 0.001%, in which the content of hafnium (Hf) is at most 75 ppm, and / or contains at least 10 ppm hafnium (Hf), and / or contains at least 10 ppm zirconium (Zr),
in which the maximum manganese content (Mn) is 0.12%, and / or
in which the manganese content (Mn) is at least 0.001%, where the maximum content of phosphorus (P) is 0.015%, and / or where the minimum content of phosphorus (P) is 0.003%, at which the maximum content of sulfur ( S) is 0.025%, and / or
where the minimum sulfur content (S) is 0.0003%, optional:
  • where the alloy is 50ppm to 2000ppm,
  • Contains tin or zinc.

In den Unteransprüchen sind weitere vorteilhafte Maßnahmen aufgelistet, die beliebig miteinander kombiniert werden können, um weitere Vorteile zu erzielen.In the dependent claims further advantageous measures are listed, which can be combined with each other in order to achieve further advantages.

Weitere Vorteile ergeben sich durch

  • einen Eisengehalt der maximal 0.1Gew% beträgt, insbesondere 0.06Gew%,
  • einen Kupfergehalt (Cu), der maximal 0.05Gew% beträgt,
  • einen Kupfergehalt (Cu), der mindestens 0,01Gew% beträgt,
  • maximal 25ppm Zirkon (Zr),
  • einen maximalen Mangangehalt (Mn) von 0.06Gew%,
  • einen Mangangehalt (Mn), der mindestens 0.01Gew% beträgt,
  • einen minimalen Gehalt an Phosphor (P), der mindestens 0,004Gew% beträgt,
  • einen maximalen Gehalt an Schwefel (S), der maximal 0.01Gew% beträgt,
  • einen minimalen Gehalt an Schwefel (S), der 0,0004Gew% beträgt,
  • eine Superlegierung, die Chrom (Cr), Titan (Ti), Molybdän (Mo), Wolfram (W), Tantal (Ta), Aluminium (Al), Kobalt (Co), Bor (B), Kohlenstoff (C), Eisen (Fe) und Silizium (Si) aufweist, insbesondere daraus besteht,
  • eine Superlegierung, die aus Chrom (Cr), Titan (Ti), Molybdän (Mo), Wolfram (W), Tantal (Ta), Aluminium (Al), Kobalt (Co), Bor (B), Kohlenstoff (C), Silizium (Si) und Phosphor (P) aufweist, insbesondere daraus besteht,
  • eine Superlegierung, die aus Chrom (Cr), Titan (Ti), Molybdän (Mo), Wolfram (W), Tantal (Ta), Aluminium (Al), Kobalt (Co), Bor (B), Kohlenstoff (C), Eisen (Fe), Silizium (Si) und Phosphor (P) aufweist, insbesondere daraus besteht,
  • eine Superlegierung, die bis 1000 ppm,
    insbesondere bis 500ppm,
    Zinn oder Zink,
    insbesondere Zinn (Sn) enthält.
Further advantages result from
  • an iron content of at most 0.1% by weight, in particular 0.06% by weight,
  • a copper content (Cu) which is a maximum of 0.05% by weight,
  • a copper content (Cu) which is at least 0.01% by weight,
  • maximum 25ppm zircon (Zr),
  • a maximum manganese content (Mn) of 0.06Gew%,
  • a manganese content (Mn) which is at least 0.01Gew%,
  • a minimum phosphorus (P) content of at least 0.004 wt%,
  • a maximum content of sulfur (S) which is a maximum of 0.01% by weight,
  • a minimum sulfur (S) content of 0.0004% by weight
  • a superalloy containing chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (Al), cobalt (Co), boron (B), carbon (C), iron (Fe) and silicon (Si), in particular consists of
  • a superalloy consisting of chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (Al), cobalt (Co), boron (B), carbon (C), Silicon (Si) and phosphorus (P), in particular consists of
  • a superalloy consisting of chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (Al), cobalt (Co), boron (B), carbon (C), Iron (Fe), silicon (Si) and phosphorus (P), in particular consists of
  • a superalloy that is up to 1000 ppm,
    especially up to 500ppm,
    Tin or zinc,
    in particular tin (Sn).

Die oben genannten Merkmale können beliebig miteinander kombiniert werden, um weitere Vorteile zu erzielen.The above features can be combined with each other to achieve further advantages.

Es zeigen

  • Figur 1 perspektivisch eine Turbinenschaufel
  • Figur 2 eine Brennkammer
  • Figur 3 eine Gasturbine.
Show it
  • FIG. 1 in perspective, a turbine blade
  • FIG. 2 a combustion chamber
  • FIG. 3 a gas turbine.

Die Beschreibung und die Figuren zeigen nur Ausführungsbeispiele der Erfindung.The description and the figures show only embodiments of the invention.

Die Figur 1 zeigt in perspektivischer Ansicht eine Laufschaufel 120 oder Leitschaufel 130 einer Strömungsmaschine, die sich entlang einer Längsachse 121 erstreckt.The FIG. 1 shows a perspective view of a blade 120 or guide vane 130 of a turbomachine, which extends along a longitudinal axis 121.

Die Strömungsmaschine kann eine Gasturbine eines Flugzeugs oder eines Kraftwerks zur Elektrizitätserzeugung, eine Dampfturbine oder ein Kompressor sein.The turbomachine may be a gas turbine of an aircraft or a power plant for power generation, a steam turbine or a compressor.

Die Schaufel 120, 130 weist entlang der Längsachse 121 aufeinander folgend einen Befestigungsbereich 400, eine daran angrenzende Schaufelplattform 403 sowie ein Schaufelblatt 406 und eine Schaufelspitze 415 auf.
Als Leitschaufel 130 kann die Schaufel 130 an ihrer Schaufelspitze 415 eine weitere Plattform aufweisen (nicht dargestellt).The blade 120, 130 has along the longitudinal axis 121 consecutively a fastening region 400, a blade platform 403 adjacent thereto and an airfoil 406 and a blade tip 415.
As a guide blade 130, the blade 130 may have at its blade tip 415 another platform (not shown).

Im Befestigungsbereich 400 ist ein Schaufelfuß 183 gebildet, der zur Befestigung der Laufschaufeln 120, 130 an einer Welle oder einer Scheibe dient (nicht dargestellt).
Der Schaufelfuß 183 ist beispielsweise als Hammerkopf ausgestaltet. Andere Ausgestaltungen als Tannenbaum- oder Schwalbenschwanzfuß sind möglich.In the mounting region 400, 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.

Die Schaufel 120, 130 weist für ein Medium, das an dem Schaufelblatt 406 vorbeiströmt, eine Anströmkante 409 und eine Abströmkante 412 auf.The blade 120, 130 has a leading edge 409 and a trailing edge 412 for a medium flowing past the airfoil 406.

Bei herkömmlichen Schaufeln 120, 130 werden in allen Bereichen 400, 403, 406 der Schaufel 120, 130 beispielsweise massive metallische Werkstoffe, insbesondere Superlegierungen verwendet.
Solche Superlegierungen sind beispielsweise aus der EP 1 204 776 B1 , EP 1 306 454 , EP 1 319 729 A1 , WO 99/67435 oder WO 00/44949 bekannt.
Die Schaufel 120, 130 kann hierbei durch ein Gussverfahren, auch mittels gerichteter Erstarrung, durch ein Schmiedeverfahren, durch ein Fräsverfahren oder Kombinationen daraus gefertigt sein.In conventional 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 for example from EP 1 204 776 B1 . EP 1 306 454 . EP 1 319 729 A1 . WO 99/67435 or WO 00/44949 known.
The blade 120, 130 can be made by a casting process, also by directional solidification, by a forging process, by a milling process or combinations thereof.

Werkstücke mit einkristalliner Struktur oder Strukturen werden als Bauteile für Maschinen eingesetzt, die im Betrieb hohen mechanischen, thermischen und/oder chemischen Belastungen ausgesetzt sind.
Die Fertigung von derartigen einkristallinen Werkstücken erfolgt z.B. durch gerichtetes Erstarren aus der Schmelze. Es handelt sich dabei um Gießverfahren, bei denen die flüssige metallische Legierung zur einkristallinen Struktur, d.h. zum einkristallinen Werkstück, oder gerichtet erstarrt.
Dabei werden dendritische Kristalle entlang dem Wärmefluss ausgerichtet und bilden entweder eine stängelkristalline Kornstruktur (kolumnar, d.h. Körner, die über die ganze Länge des Werkstückes verlaufen und hier, dem allgemeinen Sprachgebrauch nach, als gerichtet erstarrt bezeichnet werden) oder eine einkristalline Struktur, d.h. das ganze Werkstück besteht aus einem einzigen Kristall. In diesen Verfahren muss man den Übergang zur globulitischen (polykristallinen) Erstarrung meiden, da sich durch ungerichtetes Wachstum notwendigerweise transversale und longitudinale Korngrenzen ausbilden, welche die guten Eigenschaften des gerichtet erstarrten oder einkristallinen Bauteiles zunichte machen.
Ist allgemein von gerichtet erstarrten Gefügen die Rede, so sind damit sowohl Einkristalle gemeint, die keine Korngrenzen oder höchstens Kleinwinkelkorngrenzen aufweisen, als auch Stängelkristallstrukturen, die wohl in longitudinaler Richtung verlaufende Korngrenzen, aber keine transversalen Korngrenzen aufweisen. Bei diesen zweitgenannten kristallinen Strukturen spricht man auch von gerichtet erstarrten Gefügen (directionally solidified structures).
Solche Verfahren sind aus der US-PS 6,024,792 und der EP 0 892 090 A1 bekannt.Workpieces with a monocrystalline structure or structures are used as components for machines which are exposed to high mechanical, thermal and / or chemical stresses during operation.
The production of such monocrystalline workpieces, for example, by directed solidification from the melt. These are casting methods in which the liquid metallic alloy solidifies into a monocrystalline structure, ie a single-crystal workpiece, or directionally.
Here, dendritic crystals are aligned along the heat flow and form either a columnar grain structure (columnar, ie grains that run the entire length of the workpiece and here, in common parlance, referred to as directionally solidified) or a monocrystalline structure, ie the whole Workpiece consists of a single crystal. In these processes, it is necessary to avoid the transition to globulitic (polycrystalline) solidification, since non-directional growth necessarily forms transverse and longitudinal grain boundaries which negate the good properties of the directionally solidified or monocrystalline component.
The term generally refers to directionally solidified microstructures, which means both single crystals that have no grain boundaries or at most small angle grain boundaries, and stem crystal structures that have probably longitudinal grain boundaries but no transverse grain boundaries. These second-mentioned crystalline structures are also known as directionally solidified structures.
Such methods are known from U.S. Patent 6,024,792 and the EP 0 892 090 A1 known.

Ebenso können die Schaufeln 120, 130 Beschichtungen gegen Korrosion oder Oxidation aufweisen, z. B. (MCrAlX; M ist zumindest ein Element der Gruppe Eisen (Fe), Kobalt (Co), Nickel (Ni), X ist ein Aktivelement und steht für Yttrium (Y) und/oder Silizium und/oder zumindest ein Element der Seltenen Erden, bzw. Hafnium (Hf)). Solche Legierungen sind bekannt aus der EP 0 486 489 B1 , EP 0 786 017 B1 , EP 0 412 397 B1 oder EP 1 306 454 A1 .
Die Dichte liegt vorzugsweise bei 95% der theoretischen Dichte.
Auf der MCrAlX-Schicht (als Zwischenschicht oder als äußerste Schicht) bildet sich eine schützende Aluminiumoxidschicht (TGO = thermal grown oxide layer).Likewise, 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)). Such alloys are known from the EP 0 486 489 B1 . EP 0 786 017 B1 . EP 0 412 397 B1 or EP 1 306 454 A1 ,
The density is preferably 95% of the theoretical density.
A protective aluminum oxide layer (TGO = thermal grown oxide layer) is formed on the MCrAlX layer (as an intermediate layer or as the outermost layer).

Vorzugsweise weist die Schichtzusammensetzung Co-30Ni-28Cr-8Al-0,6Y-0,7Si oder Co-28Ni-24Cr-10Al-0,6Y auf. Neben diesen kobaltbasierten Schutzbeschichtungen werden auch vorzugsweise nickelbasierte Schutzschichten verwendet wie Ni-10Cr-12Al-0,6Y-3Re oder Ni-12Co-21Cr-11Al-0,4Y-2Re oder Ni-25Co-17Cr-10Al-0,4Y-1,5Re.Preferably, the layer composition comprises Co-30Ni-28Cr-8Al-0.6Y-0.7Si or Co-28Ni-24Cr-10Al-0.6Y. In addition to these cobalt-based protective coatings, nickel-based protective layers such as Ni-10Cr-12Al-0.6Y-3Re or Ni-12Co-21Cr-11Al-0.4Y-2Re or Ni-25Co-17Cr-10Al-0.4Y-1 are also preferably used , 5RE.

Auf der MCrAlX kann noch eine Wärmedämmschicht vorhanden sein, die vorzugsweise die äußerste Schicht ist, und besteht beispielsweise aus ZrO2, Y2O3-ZrO2, d.h. sie ist nicht, teilweise oder vollständig stabilisiert durch Yttriumoxid und/oder Kalziumoxid und/oder Magnesiumoxid.
Die Wärmedämmschicht bedeckt die gesamte MCrAlX-Schicht. Durch geeignete Beschichtungsverfahren wie z.B. Elektronenstrahlverdampfen (EB-PVD) werden stängelförmige Körner in der Wärmedämmschicht erzeugt.
Andere Beschichtungsverfahren sind denkbar, z.B. atmosphärisches Plasmaspritzen (APS), LPPS, VPS oder CVD. Die Wärmedämmschicht kann poröse, mikro- oder makrorissbehaftete Körner zur besseren Thermoschockbeständigkeit aufweisen. Die Wärmedämmschicht ist also vorzugsweise poröser als die MCrAlX-Schicht.On the MCrAlX may still be present a thermal barrier coating, 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 barrier coating covers the entire MCrAlX layer. By means of suitable coating processes, such as electron beam evaporation (EB-PVD), stalk-shaped grains are produced in the thermal barrier coating.
Other coating methods are conceivable, for example atmospheric plasma spraying (APS), LPPS, VPS or CVD. The thermal barrier coating may have porous, micro- or macro-cracked grains for better thermal shock resistance. The thermal barrier coating is therefore preferably more porous than the MCrAlX layer.

Wiederaufarbeitung (Refurbishment) bedeutet, dass Bauteile 120, 130 nach ihrem Einsatz gegebenenfalls von Schutzschichten befreit werden müssen (z.B. durch Sandstrahlen). Danach erfolgt eine Entfernung der Korrosions- und/oder Oxidationsschichten bzw. -produkte. Gegebenenfalls werden auch noch Risse im Bauteil 120, 130 repariert. Danach erfolgt eine Wie derbeschichtung des Bauteils 120, 130 und ein erneuter Einsatz des Bauteils 120, 130.Refurbishment means that components 120, 130 may have to be freed of protective layers after use (eg by sandblasting). This is followed by removal of the corrosion and / or oxidation layers or products. Optionally, even cracks in the component 120, 130 are repaired. Then there is a like the coating of the component 120, 130 and a renewed use of the component 120, 130.

Die Schaufel 120, 130 kann hohl oder massiv ausgeführt sein. Wenn die Schaufel 120, 130 gekühlt werden soll, ist sie hohl und weist ggf. noch Filmkühllöcher 418 (gestrichelt angedeutet) auf.The blade 120, 130 may be hollow or solid. If the blade 120, 130 is to be cooled, it is hollow and may still film cooling holes 418 (indicated by dashed lines) on.

Die Figur 2 zeigt eine Brennkammer 110 einer Gasturbine.
Die Brennkammer 110 ist beispielsweise als so genannte Ringbrennkammer ausgestaltet, bei der eine Vielzahl von in Umfangsrichtung um eine Rotationsachse 102 herum angeordneten Brennern 107 in einen gemeinsamen Brennkammerraum 154 münden, die Flammen 156 erzeugen. Dazu ist die Brennkammer 110 in ihrer Gesamtheit als ringförmige Struktur ausgestaltet, die um die Rotationsachse 102 herum positioniert ist.The FIG. 2 shows a combustion chamber 110 of a gas turbine.
The combustion chamber 110 is designed, for example, as a so-called annular combustion chamber, in which a plurality of burners 107 arranged around a rotation axis 102 in the circumferential direction open into a common combustion chamber space 154, which generate flames 156. For this purpose, the combustion chamber 110 is configured in its entirety as an annular structure, which is positioned around the axis of rotation 102 around.

Zur Erzielung eines vergleichsweise hohen Wirkungsgrades ist die Brennkammer 110 für eine vergleichsweise hohe Temperatur des Arbeitsmediums M von etwa 1000°C bis 1600°C ausgelegt. Um auch bei diesen, für die Materialien ungünstigen Betriebsparametern eine vergleichsweise lange Betriebsdauer zu ermöglichen, ist die Brennkammerwand 153 auf ihrer dem Arbeitsmedium M zugewandten Seite mit einer aus Hitzeschildelementen 155 gebildeten Innenauskleidung versehen.
Jedes Hitzeschildelement 155 aus einer Legierung ist arbeitsmediumsseitig mit einer besonders hitzebeständigen Schutzschicht (MCrAlX-Schicht und/oder keramische Beschichtung) ausgestattet oder ist aus hochtemperaturbeständigem Material (massive keramische Steine) gefertigt.
Diese Schutzschichten können ähnlich der Turbinenschaufeln sein, also bedeutet beispielsweise MCrAlX: M ist zumindest ein Element der Gruppe Eisen (Fe), Kobalt (Co), Nickel (Ni), X ist ein Aktivelement und steht für Yttrium (Y) und/oder Silizium und/oder zumindest ein Element der Seltenen Erden, bzw. Hafnium (Hf). Solche Legierungen sind bekannt aus der EP 0 486 489 B1 , EP 0 786 017 B1 , EP 0 412 397 B1 oder EP 1 306 454 A1 .To achieve a comparatively high efficiency, the combustion chamber 110 is designed for a comparatively high temperature of the working medium M of about 1000 ° C to 1600 ° C. In order to enable a comparatively long service life even with these, for the materials unfavorable operating parameters, 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.
Each heat shield element 155 made of an alloy is equipped on the working medium 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).
These protective layers may be similar to the turbine blades, so for example 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 the EP 0 486 489 B1 . EP 0 786 017 B1 . EP 0 412 397 B1 or EP 1 306 454 A1 ,

Auf der MCrAlX kann noch eine beispielsweise keramische Wärmedämmschicht vorhanden sein und besteht beispielsweise aus ZrO2, Y2O3-ZrO2, d.h. sie ist nicht, teilweise oder vollständig stabilisiert durch Yttriumoxid und/oder Kalziumoxid und/oder Magnesiumoxid.
Durch geeignete Beschichtungsverfahren wie z.B. Elektronenstrahlverdampfen (EB-PVD) werden stängelförmige Körner in der Wärmedämmschicht erzeugt.
Andere Beschichtungsverfahren sind denkbar, z.B. atmosphärisches Plasmaspritzen (APS), LPPS, VPS oder CVD. Die Wärmedämmschicht kann poröse, mikro- oder makrorissbehaftete Körner zur besseren Thermoschockbeständigkeit aufweisen.On the MCrAlX, for example, a ceramic thermal barrier coating may be present 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.
By means of suitable coating processes, such as electron beam evaporation (EB-PVD), stalk-shaped grains are produced in the thermal barrier coating.
Other coating methods are conceivable, for example atmospheric plasma spraying (APS), LPPS, VPS or CVD. The thermal barrier coating may have porous, micro- or macro-cracked grains for better thermal shock resistance.

Wiederaufarbeitung (Refurbishment) bedeutet, dass Hitzeschildelemente 155 nach ihrem Einsatz gegebenenfalls von Schutzschichten befreit werden müssen (z.B. durch Sandstrahlen). Danach erfolgt eine Entfernung der Korrosions- und/oder Oxidationsschichten bzw. -produkte. Gegebenenfalls werden auch noch Risse in dem Hitzeschildelement 155 repariert. Danach erfolgt eine Wiederbeschichtung der Hitzeschildelemente 155 und ein erneuter Einsatz der Hitzeschildelemente 155.Refurbishment means that heat shield elements 155 may need to be deprotected (e.g., by sandblasting) after use. This is followed by removal of the corrosion and / or oxidation layers or products. If necessary, cracks in the heat shield element 155 are also repaired. This is followed by a recoating of the heat shield elements 155 and a renewed use of the heat shield elements 155.

Aufgrund der hohen Temperaturen im Inneren der Brennkammer 110 kann zudem für die Hitzeschildelemente 155 bzw. für deren Halteelemente ein Kühlsystem vorgesehen sein. Die Hitzeschildelemente 155 sind dann beispielsweise hohl und weisen ggf. noch in den Brennkammerraum 154 mündende Kühllöcher (nicht dargestellt) auf.Due to the high temperatures inside the combustion chamber 110 may also be provided for the heat shield elements 155 and for their holding elements, a cooling system. The heat shield elements 155 are then, for example, hollow and possibly still have cooling holes (not shown) which open into the combustion chamber space 154.

Die Figur 3 zeigt beispielhaft eine Gasturbine 100 in einem Längsteilschnitt.The FIG. 3 shows by way of example a gas turbine 100 in a longitudinal partial section.

Die Gasturbine 100 weist im Inneren einen um eine Rotationsachse 102 drehgelagerten Rotor 103 mit einer Welle 101 auf, der auch als Turbinenläufer bezeichnet wird.
Entlang des Rotors 103 folgen aufeinander ein Ansauggehäuse 104, ein Verdichter 105, eine beispielsweise torusartige Brennkammer 110, insbesondere Ringbrennkammer, mit mehreren koaxial angeordneten Brennern 107, eine Turbine 108 und das Abgasgehäuse 109.
Die Ringbrennkammer 110 kommuniziert mit einem beispielsweise ringförmigen Heißgaskanal 111. Dort bilden beispielsweise vier hintereinander geschaltete Turbinenstufen 112 die Turbine 108.
Jede Turbinenstufe 112 ist beispielsweise aus zwei Schaufelringen gebildet. In Strömungsrichtung eines Arbeitsmediums 113 gesehen folgt im Heißgaskanal 111 einer Leitschaufelreihe 115 eine aus Laufschaufeln 120 gebildete Reihe 125.The gas turbine 100 has inside a rotatably mounted about a rotation axis 102 rotor 103 with a shaft 101, which is also referred to as a turbine runner.
Along the rotor 103 follow one another an intake housing 104, 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 109th
The annular combustion chamber 110 communicates with an annular annular hot gas channel 111, for example. There, for example, four turbine stages 112 connected in series form the turbine 108.
Each turbine stage 112 is formed, for example, from two blade rings. As seen in the direction of flow of a working medium 113, in the hot gas channel 111 of a row of guide vanes 115, a series 125 formed of rotor blades 120 follows.

Die Leitschaufeln 130 sind dabei an einem Innengehäuse 138 eines Stators 143 befestigt, wohingegen die Laufschaufeln 120 einer Reihe 125 beispielsweise mittels einer Turbinenscheibe 133 am Rotor 103 angebracht sind.
An dem Rotor 103 angekoppelt ist ein Generator oder eine Arbeitsmaschine (nicht dargestellt).The guide vanes 130 are fastened to an inner housing 138 of a stator 143, whereas the moving blades 120 of a row 125 are attached to the rotor 103 by means of a turbine disk 133, for example.
Coupled to the rotor 103 is a generator or work machine (not shown).

Während des Betriebes der Gasturbine 100 wird vom Verdichter 105 durch das Ansauggehäuse 104 Luft 135 angesaugt und verdichtet. Die am turbinenseitigen Ende des Verdichters 105 bereitgestellte verdichtete Luft wird zu den Brennern 107 geführt und dort mit einem Brennmittel vermischt. Das Gemisch wird dann unter Bildung des Arbeitsmediums 113 in der Brennkammer 110 verbrannt. Von dort aus strömt das Arbeitsmedium 113 entlang des Heißgaskanals 111 vorbei an den Leitschaufeln 130 und den Laufschaufeln 120. An den Laufschaufeln 120 entspannt sich das Arbeitsmedium 113 impulsübertragend, so dass die Laufschaufeln 120 den Rotor 103 antreiben und dieser die an ihn angekoppelte Arbeitsmaschine.During operation of the gas turbine 100, 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 130 and the rotor blades 120. On the rotor blades 120, the working medium 113 expands in a pulse-transmitting manner so that the rotor blades 120 drive the rotor 103 and drive the machine coupled to it.

Die dem heißen Arbeitsmedium 113 ausgesetzten Bauteile unterliegen während des Betriebes der Gasturbine 100 thermischen Belastungen. Die Leitschaufeln 130 und Laufschaufeln 120 der in Strömungsrichtung des Arbeitsmediums 113 gesehen ersten Turbinenstufe 112 werden neben den die Ringbrennkammer 110 auskleidenden Hitzeschildelementen am meisten thermisch belastet.
Um den dort herrschenden Temperaturen standzuhalten, können diese mittels eines Kühlmittels gekühlt werden.
Ebenso können Substrate der Bauteile eine gerichtete Struktur aufweisen, d.h. sie sind einkristallin (SX-Struktur) oder weisen nur längsgerichtete Körner auf (DS-Struktur).
Als Material für die Bauteile, insbesondere für die Turbinenschaufel 120, 130 und Bauteile der Brennkammer 110 werden beispielsweise eisen-, nickel- oder kobaltbasierte Superlegierungen verwendet.
Solche Superlegierungen sind beispielsweise aus der EP 1 204 776 B1 , EP 1 306 454 , EP 1 319 729 A1 , WO 99/67435 oder WO 00/44949 bekannt.The components exposed to the hot working medium 113 are subject to thermal loads during operation of the gas turbine 100. The guide vanes 130 and rotor blades 120 of the first turbine stage 112, viewed in the flow direction 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.
To withstand the prevailing temperatures, they can be cooled by means of a coolant.
Likewise, substrates of the components can have a directional structure, ie they are monocrystalline (SX structure) or have only longitudinal grains (DS structure).
As the material for the components, in particular for the turbine blade 120, 130 and components of the combustion chamber 110, for example, iron-, nickel- or cobalt-based superalloys are used.
Such superalloys are for example from EP 1 204 776 B1 . EP 1 306 454 . EP 1 319 729 A1 . WO 99/67435 or WO 00/44949 known.

Ebenso können die Schaufeln 120, 130 Beschichtungen gegen Korrosion (MCrAlX; M ist zumindest ein Element der Gruppe Eisen (Fe), Kobalt (Co), Nickel (Ni), X ist ein Aktivelement und steht für Yttrium (Y) und/oder Silizium, Scandium (Sc) und/oder zumindest ein Element der Seltenen Erden bzw. Hafnium). Solche Legierungen sind bekannt aus der EP 0 486 489 B1 , EP 0 786 017 B1 , EP 0 412 397 B1 oder EP 1 306 454 A1 .Also, the blades 120, 130 may be anti-corrosion coatings (MCrAlX; M is at least one element of the group iron (Fe), cobalt (Co), nickel (Ni), X is an active element and is yttrium (Y) and / or silicon , Scandium (Sc) and / or at least one element of the rare earth or hafnium). Such alloys are known from the EP 0 486 489 B1 . EP 0 786 017 B1 . EP 0 412 397 B1 or EP 1 306 454 A1 ,

Auf der MCrAlX kann noch eine Wärmedämmschicht vorhanden sein, und besteht beispielsweise aus ZrO2, Y2O3-ZrO2, d.h. sie ist nicht, teilweise oder vollständig stabilisiert durch Yttriumoxid und/oder Kalziumoxid und/oder Magnesiumoxid.
Durch geeignete Beschichtungsverfahren wie z.B. Elektronenstrahlverdampfen (EB-PVD) werden stängelförmige Körner in der Wärmedämmschicht erzeugt.On the MCrAlX may still be present a thermal barrier coating, 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.
By means of suitable coating processes, such as electron beam evaporation (EB-PVD), stalk-shaped grains are produced in the thermal barrier coating.

Die Leitschaufel 130 weist einen dem Innengehäuse 138 der Turbine 108 zugewandten Leitschaufelfuß (hier nicht darge stellt) und einen dem Leitschaufelfuß gegenüberliegenden Leitschaufelkopf auf. Der Leitschaufelkopf ist dem Rotor 103 zugewandt und an einem Befestigungsring 140 des Stators 143 festgelegt.The vane 130 has a the inner casing 138 of the turbine 108 facing Leitschaufelfuß (not shown here ) and a vane head opposite the vane root. The vane head faces the rotor 103 and fixed to a mounting ring 140 of the stator 143.

Die erfindungsgemäße Legierung weist folgende Gehalte in Gewichtsprozent (Gew%) auf: Chrom (Cr) 9,0 bis 15,0 insbesondere 9,0 bis 15,0 Titan (Ti) 2,0 bis 6,0 insbesondere 2,0 bis 6,0 Molybdän (Mo) 1,0 bis 3,0 Wolfram (W) 2,0 bis 6,0 Tantal (Ta) 3,0 bis 7,0 Aluminium (Al) 2,0 bis 6,0 Kobalt (Co) 6,0 bis 11,0 Bor (B) 0,0025 bis 0,05 Kohlenstoff (C) 0,01 bis 0,3 und zumindest ein Element der Gruppe Silizium (Si), Eisen (Fe), Vanadium (V), Niob (Nb), Kupfer (Cu), Hafnium (Hf), Zirkon (Zr), Phosphor (P), Schwefel (S), und Mangan (Mn). Diese Auflistung ist nicht abschließend.The alloy according to the invention has the following contents in percent by weight (% by weight): Chrome (Cr) 9.0 to 15.0 especially 9.0 to 15.0 Titanium (Ti) 2.0 to 6.0 especially 2.0 to 6.0 Molybdenum (Mo) 1.0 to 3.0 Tungsten (W) 2.0 to 6.0 Tantalum (Ta) 3.0 to 7.0 Aluminum (Al) 2.0 to 6.0 Cobalt (Co) 6.0 to 11.0 Boron (B) 0.0025 to 0.05 Carbon (C) 0.01 to 0.3 and at least one element of the group silicon (Si), iron (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S) , and manganese (Mn). This listing is not exhaustive.

Vorzugsweise weist die Superlegierung auf (in Gew%): Chrom (Cr) 11,0 bis 13,0 insbesondere 11,6 bis 12,7 Titan (Ti) 3,5 bis 4,5 insbesondere 3,9 bis 4,25 Molybdän (Mo) 1,65 bis 2,15 Wolfram (W) 3,5 bis 4,1 Tantal (Ta) 4,8 bis 5,2 Aluminium (Al) 3,4 bis 3,8 Kobalt (Co) 8,5 bis 9,5 Bor (B) 0,0125 bis 0,0175 Kohlenstoff (C) 0,08 bis 0,1 insbesondere 0,09. Preferably, the superalloy comprises (in% by weight): Chrome (Cr) 11.0 to 13.0 especially 11.6 to 12.7 Titanium (Ti) 3.5 to 4.5 especially 3.9 to 4.25 Molybdenum (Mo) 1.65 to 2.15 Tungsten (W) 3.5 to 4.1 Tantalum (Ta) 4.8 to 5.2 Aluminum (Al) 3.4 to 3.8 Cobalt (Co) 8.5 to 9.5 Boron (B) 0.0125 to 0.0175 Carbon (C) 0.08 to 0.1 especially 0.09.

Es können weitere Nebenelemente wie Silizium (Si), Eisen (Fe), Vanadium (V), Niob (Nb), Kupfer (Cu), Hafnium (Hf), Zirkon (Zr), Phosphor (P), Schwefel (S), und Mangan (Mn) vorhanden sein.Other minor elements such as silicon (Si), iron (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S), and manganese (Mn) may be present.

Es werden für weitere Elemente, die die Korngrenzenfestigkeit reduzieren, Obergrenzen festgelegt, aber auch Mindestwerte. Diese sind für Silizium min. 0,01Gew% und max. 0,12Gew%. Silizium (Si) steigert die Oxidationsbeständigkeit und bewirkt die Deoxidierung der Schmelze.Upper limits are set for other elements that reduce grain boundary strength, but also minimum values. These are for silicon min. 0.01% by weight and max. 0,12Gew%. Silicon (Si) enhances oxidation resistance and causes deoxidation of the melt.

Ebenso darf der Anteil an Eisen (Fe) 0,2% nicht überschreiten und kann mindestens 0.014Gew% betragen.
Eisen (Fe) ist als γ'-Bildner und Nickelsubstituent bekannt.Similarly, the proportion of iron (Fe) must not exceed 0.2% and may be at least 0.014Gew%.
Iron (Fe) is known as the γ '-former and nickel-substituent.

Silizium und Eisen verbessern auch die Gießbarkeit. Eine Reduzierung der Elemente wäre eher unerwünscht.Silicon and iron also improve castability. A reduction of the elements would be rather undesirable.

Vorzugsweise ist der Gehalt an Vanadium (V) nicht größer als 75ppm und beträgt vorzugsweise mindestens 50ppm.Preferably, the content of vanadium (V) is not greater than 75 ppm and is preferably at least 50 ppm.

Der Anteil an Kupfer (Cu) darf bis zu 0.1Gew% betragen bei Mindestwerten ab 0.001Gew%.The proportion of copper (Cu) may be up to 0.1Gew% with minimum values from 0.001Gew%.

Ebenso vorzugsweise ist der Gehalt an Hafnium (Hf) nicht größer als 50ppm. Dies steht im Gegensatz zu den bekannten Legierungen für Legierungen für die gerichtete Erstarrung mit stängelförmigen Körnern, bei denen Hafnium bewusst mit größeren Anteilen hinzugegeben wird, um die Korngrenzen zwischen den Stängelkörnern zu stabilisieren.Also, preferably, the content of hafnium (Hf) is not larger than 50ppm. This is in contrast to the known alloys for directional solidification with columnar grains, in which hafnium is deliberately added in larger proportions to stabilize the grain boundaries between the stem grains.

Es hat sich herausgestellt, dass der höhere Borgehalt (B) sich positiv auf die Korngrenzenfestigkeit auswirkt, obwohl Bor als Schmelzpunkterniedriger verwendet wird.
Ebenso darf der Borgehalt aber einen gewissen maximalen Wert nicht überschreiten, da es sonst zu einem negativen Einfluss aufgrund des Schmelzpunkterniedrigers kommt.It has been found that the higher boron content (B) has a positive effect on grain boundary strength, although boron is used as the melting point depressant.
Likewise, however, the boron content must not exceed a certain maximum value, since otherwise there will be a negative influence due to the melting point depressant.

Vorzugsweise beträgt der Borgehalt 150ppm.Preferably, the boron content is 150 ppm.

Der Anteil an Niob (Nb) - bei einigen Ni-Superlegierungen bewusst hinzugegeben - darf hier bis 75ppm betragen bei Mindestwerten von 50ppm.The amount of niobium (Nb) - deliberately added in some Ni superalloys - may here be up to 75ppm with minimum values of 50ppm.

Eine optimale Karbidbildung wird mit 0,09% Kohlenstoff (C) erreicht.Optimum carbide formation is achieved with 0.09% carbon (C).

Im Gegensatz zu den bekannten DS-Legierungen wird auf die höhere Zugabe von Korngrenzenfestigern wie Hafnium und Zirkon verzichtet.
Dafür wird Bor (B) und Kohlenstoff (C) zugegeben. Der Kohlenstoffgehalt liegt höher als 0.08Gew%.In contrast to the known DS alloys, the higher addition of grain boundary consolidators such as hafnium and zirconium is dispensed with.
For this, boron (B) and carbon (C) are added. The carbon content is higher than 0.08Gew%.

Durch die Minimierung der Korngrenzenfestiger Hafnium und Zirkon muss dafür genau auf die Einhaltung der Verunreinigungen geachtet werden, wie Silizium (Si), Mangan (Mn), Eisen (Fe) oder Kupfer (Cu).By minimizing the grain boundary strength of hafnium and zirconium, attention must be paid to compliance with the impurities, such as silicon (Si), manganese (Mn), iron (Fe) or copper (Cu).

Verunreinigungen der Legierungen haben vorzugsweise einen maximalen Wert von 10ppm.Impurities of the alloys preferably have a maximum value of 10 ppm.

Der Anteil von Schwefel (S) liegt bei mindestens 0.0003Gew% und maximal bis 0,25Gew%. Der Anteil an Phosphor (P) liegt mindestens bei 0,003Gew% und maximal bei 0,025Gew%.The proportion of sulfur (S) is at least 0.0003 wt% and at most 0.25 wt%. The proportion of phosphorus (P) is at least 0.003 wt% and at most 0.025 wt%.

Eine höhere Reinheit der Legierung wäre zwar wünschenswert, aber kaum bezahlbar und oft nicht notwendig.
Durch die Festlegung von zulässigen Bereichen von Nebenelementen können Bauteile 120, 130 günstig aber weiterhin mit bekannt guten Hochtemperatureigenschaften hergestellt werden.A higher purity of the alloy would be desirable, but hardly affordable and often not necessary.
By defining allowable ranges of minor elements, components 120, 130 may be manufactured inexpensively but with known good high temperature properties.

Vorzugsweise werden die Elemente Silizium (Si), Eisen (Fe), Phosphor (P) und Schwefel (S) akzeptiert.Preferably, the elements silicon (Si), iron (Fe), phosphorus (P) and sulfur (S) are accepted.

Die Zugabe von Zink oder Zinn, insbesondere von Zinn (Sn) im Bereich von 50ppm, insbesondere von 100ppm, verbessert die mechanischen Eigenschaften der Legierung, weil es die γ'-Bildung fördert.The addition of zinc or tin, especially tin (Sn) in the range of 50ppm, especially 100ppm, improves the mechanical properties of the alloy because it promotes gamma prime formation.

Claims (6)

  1. Nickel-based superalloy for the directional solidification of components having columnar grains,
    said superalloy consisting of(in % by weight): chromium (Cr) 9.0 to 15.0, titanium (Ti) 2.0 to 6.0, molybdenum (Mo) 1.0 to 3.0, tungsten (W) 2.0 to 6.0, tantalum (Ta) 3.0 to 7.0, aluminum (Al) 2.0 to 6.0, cobalt (Co) 6.0 to 11.0, boron (B) 0.0025 to 0.05, carbon (C) 0.01 to 0.3, silicon (Si) 0.01 to 0.12, zirconium (Zr),
    wherein the alloy contains at most 25 ppm zirconium (Zr), and at least one element selected from the group consisting of iron (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S) and manganese (Mn),
    wherein the following applies for said elements, if present,
    in which the iron content (Fe) is at most 0.2%,
    and/or
    in which the iron content (Fe) is at least 0.014%,
    in particular at least 0.02%,
    in which the vanadium content (V) is at most 75 ppm,
    and/or in which the vanadium content (V) is at least 50 ppm,
    in which the niobium content (Nb) is at most 75 ppm,
    and/or in which the niobium content (Nb) is at least 50 ppm,
    in which the copper content (Cu) is at most 0.1%,
    and/or
    in which the copper content (Cu) is at least 0.001%,
    in which the content of hafnium (Hf) is at most 75 ppm,
    and/or which contains at least 10 ppm hafnium (Hf),
    and/or which contains at least 10 ppm zirconium (Zr),
    in which the manganese content (Mn) is at most 0.12%,
    and/or
    in which the manganese content (Mn) is at least 0.001%,
    in which the phosphorus content (P) is at most 0.015%,
    and/or in which the phosphorus content (P) is at least 0.003%,
    in which the sulfur content (S) is at most 0.025%,
    and/or
    in which the sulfur content (S) is at least 0.0003%, optionally:
    tin (Sn) or zinc (Zn) 50 ppm to 2000 ppm, remainder nickel.
  2. Superalloy according to Claim 1,
    wherein the boron content (B) is 150 ppm.
  3. Superalloy according to Claim 1 or 2, which comprises chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (Al), cobalt (Co), boron (B), carbon (C), iron (Fe) and silicon (Si).
  4. Superalloy according to one or more of Claims 1, 2 to 3, which comprises chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (Al), cobalt (Co), boron (B), carbon (C), silicon (Si) and phosphorus (P) .
  5. Superalloy according to one of the preceding Claims 1 to 4, which comprises chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (Al), cobalt (Co), boron (B), carbon (C), iron (Fe), silicon (Si) and phosphorus (P).
  6. Component
    which has columnar single crystals and
    which comprises an alloy according to one or more of the preceding Claims 1 to 5.
EP09756148.4A 2009-10-20 2009-10-20 Alloy for directional solidification and columnar grained component Not-in-force EP2491156B1 (en)

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US9068251B2 (en) 2015-06-30

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