EP2491156A1 - Alloy for directional solidification and component made of stem-shaped crystals - Google Patents

Alloy for directional solidification and component made of stem-shaped crystals

Info

Publication number
EP2491156A1
EP2491156A1 EP09756148A EP09756148A EP2491156A1 EP 2491156 A1 EP2491156 A1 EP 2491156A1 EP 09756148 A EP09756148 A EP 09756148A EP 09756148 A EP09756148 A EP 09756148A EP 2491156 A1 EP2491156 A1 EP 2491156A1
Authority
EP
European Patent Office
Prior art keywords
superalloy according
weight
content
boron
iron
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.)
Granted
Application number
EP09756148A
Other languages
German (de)
French (fr)
Other versions
EP2491156B1 (en
Inventor
Winfried Esser
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
Howmet Corp
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
Application filed by Siemens AG filed Critical Siemens AG
Priority to EP18000230.5A priority Critical patent/EP3363923A1/en
Publication of EP2491156A1 publication Critical patent/EP2491156A1/en
Application granted granted Critical
Publication of EP2491156B1 publication Critical patent/EP2491156B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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 columnar grains it depends on the grain boundary strength and the grain boundary from ⁇ decisions or the presence of foreign elements (impurities) are deposited at the grain boundaries. These elements can have a significant influence on the mechanical behavior at high temperatures.
  • WO 00/44949 discloses a nickel-base superalloy having a high molybdenum content.
  • US 6,231,692 also discloses a nickel-based high molybdenum alloy.
  • EP 1 329 527 B1 discloses a nickel-based superalloy in which the elements zirconium and hafnium are deliberately added.
  • EP 0 855 449 B1 also discloses a minimal addition of zircon.
  • these alloys have a low Kornskynfes ⁇ ACTION, which as affecting the overall strength of a component ⁇ by negative, or are not sufficiently ductile by zirconium and hafnium. Lower additions of certain elements can have a negative impact on these properties of the alloy if exceeded.
  • Figure 2 is a combustion chamber
  • Figure 3 is a gas turbine.
  • FIG. 1 shows a perspective view of a rotor blade 120 or guide vane show ⁇ 130 of a turbomachine, which extends along a longitudinal axis of the 121st
  • 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, a fastening area 400, an adjacent blade platform 403 and an airfoil 406 and a blade tip 415.
  • the vane 130 having at its blade tip 415 have a further platform (not Darge ⁇ asserted).
  • 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, for example, as a hammerhead out staltet ⁇ . Other designs as fir tree or Schissebwschwanzfuß are possible.
  • the blade 120, 130 has for a medium which flows past the scene ⁇ felblatt 406 on a leading edge 409 and a trailing edge 412th
  • conventional blades 120, 130 in all regions 400, 403, 406 of the blade 120, 130, for example, massive metallic materials, in particular superalloys, are used.
  • 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 can hereby be manufactured by a casting process, also by directional solidification, by a forging process, by a milling process or combinations thereof.
  • 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.
  • 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 heat flow and form either a columnar grain structure (columnar, ie grains over the entire length run the workpiece and here, the general usage, referred to as directionally solidified) or a monocrystalline structure, ie the entire workpiece be ⁇ is made of a single crystal.
  • a columnar grain structure columnar, ie grains over the entire length run the workpiece and here, the general usage, referred to as directionally solidified
  • a monocrystalline structure ie the entire workpiece be ⁇ is made of a single crystal.
  • Structures are also called directionally solidified structures.
  • the blades 120, 130 may have coatings against corrosion or oxidation, e.g. B. (MCrAlX, M is at least one element of the group iron (Fe), cobalt (Co),
  • Nickel (Ni) 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 B1, EP 0 412 397 B1 or EP 1 306 454 A1.
  • the density is preferably 95% of the theoretical
  • 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 are also preferably used. 0.6Y-3Re or Ni-12Co-21Cr-IIAl-O, 4Y-2Re or Ni-25Co-17Cr-10A1-0, 4Y-1, 5Re.
  • thermal barrier coating which is preferably the outermost layer, and consists for example of Zr0 2 , Y2Ü3-Zr02, ie it is not, partially ⁇ or fully stabilized by yttria
  • the thermal barrier coating covers the entire MCrAlX layer.
  • Electron beam evaporation produces stalk-shaped grains in the thermal barrier coating.
  • the heat insulating layer can comprise porous, micro- or macro-cracked compatible grains for better thermal shock resistance.
  • the thermal barrier coating is therefore preferably more porous than the
  • 120, 130 may have to be freed from 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. Thereafter, a ⁇ As the coating of the component 120, 130, after which the component 120, the 130th
  • the blade 120, 130 may be hollow or solid. If the blade 120, 130 is to be cooled, it is hollow and also has, if necessary, film cooling holes 418 (indicated by dashed lines) on.
  • FIG. 2 shows a combustion chamber 110 of a gas turbine.
  • the combustion chamber 110 is configured, for example, as so-called an annular combustion chamber, in which are arranged a plurality of in the circumferential direction about an axis of rotation 102 Burners 107 open into a common combustion chamber space 154, the flames 156 produce.
  • 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 facing side with a formed from heat shield elements 155. liner.
  • 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 B1, EP 0 412 397 B1 or EP 1 306 454 A1.
  • a ceramic Wär ⁇ medämm Anlagen be present and consists for example of ZrÜ2, Y203 ⁇ Zr02, ie it is not, partially or fully ⁇ dig stabilized by yttrium and / or calcium oxide and / or magnesium oxide.
  • Electron beam evaporation produces stalk-shaped grains in the thermal barrier coating.
  • the heat- insulating layer may have porous, micro- or macro-cracked Kör ⁇ ner for better thermal shock resistance.
  • Refurbishment means that heat shield elements 155 may be replaced after use by heat shielding elements 155
  • Protective layers must be freed (for example by sandblasting). 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.
  • 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.
  • 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
  • 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.
  • annular annular hot gas channel 111 for example.
  • turbine stages 112 connected in series form the turbine 108.
  • Each turbine stage 112 is formed, for example, from two blade rings .
  • 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 moving blades 120 of a row 125 are attached to the rotor 103 by means of a turbine disk 133, for example.
  • air 135 is sucked by the compressor 105 through the intake housing and ver ⁇ seals.
  • the 105 ⁇ be compressed air provided at the turbine end of the compressor 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 on the rotor blades 120 in a pulse-transmitting manner, so that the rotor blades 120 drive the rotor 103 and drive the machine connected 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 highest 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 longitudinal grains (DS structure).
  • the components in particular for the turbine ⁇ blade 120, 130 and components of the combustion chamber 110 are For example, iron-, nickel- or cobalt-based superalloys used.
  • 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 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 EP 0 486 489 B1, EP 0 786 017 B1, EP 0 412 397 B1 or EP 1 306 454 A1.
  • MCrAlX may still be present a thermal barrier coating, and consists for example of Zr02, Y203-Zr02, ie it is not, partially or completely stabilized by Ytt ⁇ riumoxid and / or calcium oxide and / or magnesium oxide.
  • Electron beam evaporation produces stalk-shaped grains in the thermal barrier coating.
  • the guide blade 130 has a guide blade root facing the inner housing 138 of the turbine 108 (not shown here) and a guide blade foot opposite
  • the inventive alloy has the following contents in Ge ⁇ weight percent (wt%):
  • the superalloy comprises (in% by weight):
  • Zr Zircon
  • P phosphorus
  • S sulfur
  • Mn manganese
  • Silicon (Si) enhances oxidation resistance and causes deoxidation of the melt.
  • the proportion of iron (Fe) must not exceed 0.2% and may be at least 0.014Gew%.
  • Iron (Fe) is known as the ⁇ 'imager 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. lGew% with minimum values from 0.001Gew%.
  • the content of hafnium (Hf) is not RESIZE ⁇ SSER than 50ppm. This is in contrast to the known ones
  • 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 must not exceed a certain maximum value, since otherwise there will be a negative influence due to the melting point depressant.
  • the boron content is 150 ppm.
  • Ni niobium
  • Ni superalloys - The amount of niobium (Nb) - deliberately added in some Ni superalloys - may here be up to 75ppm with minimum values of 50ppm. Optimum carbide formation is achieved with 0.09% carbon (C).
  • grain boundary consolidators such as hafnium and zirconium is dispensed with.
  • Carbon content is higher than 0.08Gew%.
  • Impurities such as silicon (Si), manganese (Mn), iron (Fe) or copper (Cu).
  • 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%.
  • a higher purity of the alloy would be desirable, but hardly affordable and often not necessary.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

Known nickel-based super alloys for producing components made of stem-shaped single crystals do not provide sufficiently for grain boundary strength. The proposed nickel-based super alloy has a low molybdenum content and very accurately adjusted values for elements having grain boundary strength and elements that precipitate in grain boundaries.

Description

Legierung zur gerichteten Erstarrung und Bauteil aus  Alloy for directional solidification and component
stängelförmigen Kristallen  stem-shaped crystals
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 . Bei den Bauteilen mit den stängelförmigen Körnern kommt es auf die Korngrenzenfestigkeit an und auf die Korngrenzen-Aus¬ scheidungen bzw. das Vorhandensein von Fremdelementen (Verunreinigungen), die sich an den Korngrenzen abscheiden. Diese Elemente können einen erheblichen Einfluss auf das mechani- sehe Verhalten bei den hohen Temperaturen aufweisen. 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. The components with the columnar grains, it depends on the grain boundary strength and the grain boundary from ¬ decisions or the presence of foreign elements (impurities) are deposited at 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. Die US 6,231,692 offenbart ebenfalls eine nickelbasierte Legierung mit hohem Molybdängehalt. WO 00/44949 discloses a nickel-base superalloy having a high molybdenum content. US 6,231,692 also discloses a nickel-based high molybdenum alloy.
Die EP 1 329 527 Bl offenbart eine nickelbasierte Superlegie- rung bei dem die Elemente Zirkon und Hafnium bewusst hinzuge- geben werden. 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 Bl offenbart ebenfalls eine minimale Zugabe von Zirkon. Diese Legierungen weisen jedoch eine geringe Korngrenzenfes¬ tigkeit auf, die die gesamte Festigkeit eines Bauteils da¬ durch negativ beeinflussen, oder sind durch Zirkon und Hafnium zu wenig duktil. Geringere Zugaben von bestimmten Elementen können bei Überschreitung negative Auswirkungen auf diese Eigenschaften der Legierung haben. EP 0 855 449 B1 also discloses a minimal addition of zircon. However, these alloys have a low Korngrenzenfes ¬ ACTION, which as affecting the overall strength of a component ¬ by negative, or are not sufficiently ductile by zirconium and hafnium. Lower additions of certain elements can have a negative impact on these properties of the alloy if exceeded.
Allerdings stellt die Verringerung der Anteile solcher Ele¬ mente einen hohen Aufwand dar. Es ist also abzuwägen zwischen Kosten und Optimierung der Eigenschaften der Legierung. However, the reduction in the shares of such ele ¬ ments represent a high cost. So it is weighed against costs and optimize the properties of the alloy.
Es ist daher Aufgabe der Erfindung dieses Problem zu lösen. Die Aufgabe wird gelöst durch eine Legierung gemäß Anspruch 1 und einem Bauteil gemäß Anspruch 36. It is therefore an object of the invention to solve this problem. The object is achieved by an alloy according to claim 1 and a component according to claim 36.
In den Unteransprüchen sind weitere vorteilhafte Maßnahmen aufgelistet, die beliebig miteinander kombiniert werden kön¬ nen, um weiter Vorteile zu erzielen. In the dependent claims further advantageous measures are listed, which are combined with each other Kings ¬ nen to achieve benefits on.
Es zeigen Show it
Figur 1 perspektivisch eine Turbinenschaufel Figure 1 in perspective a turbine blade
Figur 2 eine Brennkammer Figure 2 is a combustion chamber
Figur 3 eine Gasturbine. Figure 3 is 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 Laufschau¬ fel 120 oder Leitschaufel 130 einer Strömungsmaschine, die sich entlang einer Längsachse 121 erstreckt. Die Strömungsmaschine kann eine Gasturbine eines Flugzeugs oder eines Kraftwerks zur Elektrizitätserzeugung, eine Dampfturbine oder ein Kompressor sein. 1 shows a perspective view of a rotor blade 120 or guide vane show ¬ 130 of a turbomachine, which extends along a longitudinal axis of the 121st 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 auf- einander 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 Schaufel¬ spitze 415 eine weitere Plattform aufweisen (nicht darge¬ stellt) . Im Befestigungsbereich 400 ist ein Schaufelfuß 183 gebildet, der zur Befestigung der Laufschaufeln 120, 130 an einer Welle oder einer Scheibe dient (nicht dargestellt) . The blade 120, 130 has, along the longitudinal axis 121, a fastening area 400, an adjacent blade platform 403 and an airfoil 406 and a blade tip 415. As a guide vane 130, the vane 130 having at its blade tip 415 have a further platform (not Darge ¬ asserted). 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).
Der Schaufelfuß 183 ist beispielsweise als Hammerkopf ausge¬ staltet. Andere Ausgestaltungen als Tannenbaum- oder Schwal- benschwanzfuß sind möglich. The blade root 183 is, for example, as a hammerhead out staltet ¬. Other designs as fir tree or Schwäbwschwanzfuß are possible.
Die Schaufel 120, 130 weist für ein Medium, das an dem Schau¬ felblatt 406 vorbeiströmt, eine Anströmkante 409 und eine Ab¬ strömkante 412 auf. Bei herkömmlichen Schaufeln 120, 130 werden in allen Bereichen 400, 403, 406 der Schaufel 120, 130 beispielsweise mas¬ sive metallische Werkstoffe, insbesondere Superlegierungen verwendet . The blade 120, 130 has for a medium which flows past the scene ¬ felblatt 406 on a leading edge 409 and a trailing edge 412th In conventional blades 120, 130, in all regions 400, 403, 406 of the blade 120, 130, for example, massive metallic materials, in particular superalloys, are used.
Solche Superlegierungen sind beispielsweise aus der EP 1 204 776 Bl, EP 1 306 454, EP 1 319 729 AI, WO 99/67435 oder WO 00/44949 bekannt.  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.
Die Schaufel 120, 130 kann hierbei durch ein Gussverfahren, auch mittels gerichteter Erstarrung, durch ein Schmiedeverfahren, durch ein Fräsverfahren oder Kombinationen daraus ge- fertigt sein.  The blade 120, 130 can hereby be manufactured 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 Belastun- gen ausgesetzt sind. 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.
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.  The production of 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.
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 be¬ steht 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 ausbil¬ den, welche die guten Eigenschaften des gerichtet erstarrten oder einkristallinen Bauteiles zunichte machen. Here, dendritic crystals are aligned along the heat flow and form either a columnar grain structure (columnar, ie grains over the entire length run the workpiece and here, the general usage, referred to as directionally solidified) or a monocrystalline structure, ie the entire workpiece be ¬ is made of a single crystal. In these methods, you have to avoid solidification transition to globular (polycrystalline), since non-directional growth inevitably forms transverse and longitudinal grain boundaries ¬ which make the good properties of the directionally solidified or single-crystal component naught.
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 Korn- grenzen aufweisen. Bei diesen zweitgenannten kristallinenIf the term generally refers to directionally solidified structures, it means both single crystals that have no grain boundaries or at most small-angle grain boundaries, and stem crystal structures that have grain boundaries running in the longitudinal direction but no transverse grain boundaries. In these second-mentioned crystalline
Strukturen spricht man auch von gerichtet erstarrten Gefügen (directionally solidified structures) . Structures are also called directionally solidified structures.
Solche Verfahren sind aus der US-PS 6,024,792 und der EP 0 892 090 AI bekannt.  Such methods are known from US Pat. No. 6,024,792 and EP 0 892 090 A1.
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) , Likewise, the blades 120, 130 may have coatings against corrosion or oxidation, e.g. B. (MCrAlX, M is at least one element of the group iron (Fe), cobalt (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 Bl, EP 0 786 017 Bl, EP 0 412 397 Bl oder EP 1 306 454 AI. 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 B1, EP 0 412 397 B1 or EP 1 306 454 A1.
Die Dichte liegt vorzugsweise bei 95% der theoretischen  The density is preferably 95% of the theoretical
Dichte. Density.
Auf der MCrAlX-Schicht (als Zwischenschicht oder als äußerste Schicht) bildet sich eine schützende Aluminiumoxidschicht (TGO = thermal grown oxide layer) . Vorzugsweise weist die SchichtZusammensetzung Co-30Ni-28Cr- 8A1-0, 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-llAl-0, 4Y-2Re oder Ni-25Co-17Cr- 10A1-0, 4Y-1, 5Re . 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). Preferably, the layer composition comprises Co-30Ni-28Cr-8A1-0, 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 are also preferably used. 0.6Y-3Re or Ni-12Co-21Cr-IIAl-O, 4Y-2Re or Ni-25Co-17Cr-10A1-0, 4Y-1, 5Re.
Auf der MCrAlX kann noch eine Wärmedämmschicht vorhanden sein, die vorzugsweise die äußerste Schicht ist, und besteht beispielsweise aus Zr02, Y2Ü3-Zr02, d.h. sie ist nicht, teil¬ weise oder vollständig stabilisiert durch Yttriumoxid On the MCrAlX may still be present a thermal barrier coating, which is preferably the outermost layer, and consists for example of Zr0 2 , Y2Ü3-Zr02, ie it is not, partially ¬ or fully stabilized by yttria
und/oder Kalziumoxid und/oder Magnesiumoxid. and / or calcium oxide and / or magnesium oxide.
Die Wärmedämmschicht bedeckt die gesamte MCrAlX-Schicht . The thermal barrier coating covers the entire MCrAlX layer.
Durch geeignete Beschichtungsverfahren wie z.B. Elektronen- strahlverdampfen (EB-PVD) werden stängelförmige Körner in der Wärmedämmschicht erzeugt. By suitable coating methods, e.g. Electron beam evaporation (EB-PVD) produces stalk-shaped grains in the thermal barrier coating.
Andere Beschichtungsverfahren sind denkbar, z.B. atmosphärisches Plasmaspritzen (APS), LPPS, VPS oder CVD. Die Wärme- dämmschicht kann poröse, mikro- oder makrorissbehaftete Kör¬ ner zur besseren Thermoschockbeständigkeit aufweisen. Die Wärmedämmschicht ist also vorzugsweise poröser als die Other coating methods are conceivable, for example atmospheric plasma spraying (APS), LPPS, VPS or CVD. The heat insulating layer can comprise porous, micro- or macro-cracked compatible grains for better thermal shock resistance. The thermal barrier coating is therefore preferably more porous than the
MCrAlX-Schicht . Wiederaufarbeitung (Refurbishment ) bedeutet, dass BauteileMCrAlX layer. Refurbishment means that components
120, 130 nach ihrem Einsatz gegebenenfalls von Schutzschichten befreit werden müssen (z.B. durch Sandstrahlen) . Danach erfolgt eine Entfernung der Korrosions- und/oder Oxidations- schichten 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. 120, 130 may have to be freed from 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. Thereafter, a ¬ As the coating of the component 120, 130, after which the component 120, the 130th
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 angedeu¬ tet) auf. The blade 120, 130 may be hollow or solid. If the blade 120, 130 is to be cooled, it is hollow and also has, if necessary, film cooling holes 418 (indicated by dashed lines) on.
Die Figur 2 zeigt eine Brennkammer 110 einer Gasturbine. FIG. 2 shows a combustion chamber 110 of a gas turbine.
Die Brennkammer 110 ist beispielsweise als so genannte Ring¬ brennkammer ausgestaltet, bei der eine Vielzahl von in Um- fangsrichtung 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 combustion chamber 110 is configured, for example, as so-called an annular combustion chamber, in which are arranged a plurality of in the circumferential direction about an axis of rotation 102 Burners 107 open into a common combustion chamber space 154, the flames 156 produce. 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 Betriebspa- rametern eine vergleichsweise lange Betriebsdauer zu ermög¬ lichen, ist die Brennkammerwand 153 auf ihrer dem Arbeitsme¬ dium M zugewandten Seite mit einer aus Hitzeschildelementen 155 gebildeten Innenauskleidung versehen. 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. To even under these unfavorable for the materials Betriebspa- rametern a comparatively long operating time to be made ¬ union, the combustion chamber wall 153 is provided on its side facing the working medium M facing side with a formed from heat shield elements 155. liner.
Jedes Hitzeschildelement 155 aus einer Legierung ist arbeits- mediumsseitig mit einer besonders hitzebeständigen Schutzschicht (MCrAlX-Schicht und/oder keramische Beschichtung) ausgestattet oder ist aus hochtemperaturbeständigem Material (massive keramische Steine) gefertigt.  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).
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 Bl, EP 0 786 017 Bl, EP 0 412 397 Bl oder EP 1 306 454 AI.  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 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 Wär¬ medämmschicht vorhanden sein und besteht beispielsweise aus ZrÜ2, Y203~Zr02, d.h. sie ist nicht, teilweise oder vollstän¬ dig stabilisiert durch Yttriumoxid und/oder Kalziumoxid und/oder Magnesiumoxid. On the MCrAlX, for example, a ceramic Wär ¬ medämmschicht be present and consists for example of ZrÜ2, Y203 ~ Zr02, ie it is not, partially or fully ¬ dig stabilized by yttrium and / or calcium oxide and / or magnesium oxide.
Durch geeignete Beschichtungsverfahren wie z.B. Elektronen- strahlverdampfen (EB-PVD) werden stängelförmige Körner in der Wärmedämmschicht erzeugt.  By suitable coating methods, e.g. Electron beam evaporation (EB-PVD) produces stalk-shaped grains in the thermal barrier coating.
Andere Beschichtungsverfahren sind denkbar, z.B. atmosphärisches Plasmaspritzen (APS), LPPS, VPS oder CVD. Die Wärme- dämmschicht kann poröse, mikro- oder makrorissbehaftete Kör¬ ner zur besseren Thermoschockbeständigkeit aufweisen. Other coating methods are conceivable, for example atmospheric plasma spraying (APS), LPPS, VPS or CVD. The heat- insulating layer may have porous, micro- or macro-cracked Kör ¬ ner for better thermal shock resistance.
Wiederaufarbeitung (Refurbishment ) bedeutet, dass Hitze- schildelemente 155 nach ihrem Einsatz gegebenenfalls vonRefurbishment means that heat shield elements 155 may be replaced after use by heat shielding elements 155
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. Protective layers must be freed (for example by sandblasting). 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.
Danach erfolgt eine Wiederbeschichtung der Hitzeschildele¬ mente 155 und ein erneuter Einsatz der Hitzeschildelemente 155. Then recoated and the Hitzeschildele ¬ elements 155, after use of the heat shield elements 155 is performed.
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 . 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 Rotations- achse 102 drehgelagerten Rotor 103 mit einer Welle 101 auf, der auch als Turbinenläufer bezeichnet wird.  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.
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.  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
Die Ringbrennkammer 110 kommuniziert mit einem beispielsweise ringförmigen Heißgaskanal 111. Dort bilden beispielsweise vier hintereinander geschaltete Turbinenstufen 112 die Tur- bine 108.  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.
Jede Turbinenstufe 112 ist beispielsweise aus zwei Schaufel¬ ringen gebildet. In Strömungsrichtung eines Arbeitsmediums 113 gesehen folgt im Heißgaskanal 111 einer Leitschaufelreihe 115 eine aus Laufschaufeln 120 gebildete Reihe 125. Each turbine stage 112 is formed, for example, from two blade rings . In the flow direction of a working medium As can be seen in the hot gas duct 111 of a guide blade row 115, a row 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. 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.
An dem Rotor 103 angekoppelt ist ein Generator oder eine Arbeitsmaschine (nicht dargestellt) .  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 ver¬ dichtet. Die am turbinenseitigen Ende des Verdichters 105 be¬ reitgestellte verdichtete Luft wird zu den Brennern 107 ge- führt 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 ent- spannt 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 100 104 air 135 is sucked by the compressor 105 through the intake housing and ver ¬ seals. The 105 ¬ be compressed air provided at the turbine end of the compressor 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. The working medium 113 expands on the rotor blades 120 in a pulse-transmitting manner, so that the rotor blades 120 drive the rotor 103 and drive the machine connected to it ,
Die dem heißen Arbeitsmedium 113 ausgesetzten Bauteile unter- liegen 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 be- lastet. 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 highest thermal stress in addition to the heat shield elements lining the annular combustion chamber 110.
Um den dort herrschenden Temperaturen standzuhalten, können diese mittels eines Kühlmittels gekühlt werden.  To withstand the prevailing temperatures, they can be cooled by means of a coolant.
Ebenso können Substrate der Bauteile eine gerichtete Struktur aufweisen, d.h. sie sind einkristallin ( SX-Struktur) oder weisen nur längsgerichtete Körner auf (DS-Struktur) . Likewise, substrates of the components may have a directional structure, i. they are monocrystalline (SX structure) or have only longitudinal grains (DS structure).
Als Material für die Bauteile, insbesondere für die Turbinen¬ schaufel 120, 130 und Bauteile der Brennkammer 110 werden beispielsweise eisen-, nickel- oder kobaltbasierte Superle- gierungen verwendet. As a material for the components, in particular for the turbine ¬ blade 120, 130 and components of the combustion chamber 110 are For example, iron-, nickel- or cobalt-based superalloys used.
Solche Superlegierungen sind beispielsweise aus der EP 1 204 776 Bl, EP 1 306 454, EP 1 319 729 AI, WO 99/67435 oder WO 00/44949 bekannt.  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.
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 Bl, EP 0 786 017 Bl, EP 0 412 397 Bl oder EP 1 306 454 AI. Auf der MCrAlX kann noch eine Wärmedämmschicht vorhanden sein, und besteht beispielsweise aus Zr02, Y203-Zr02, d.h. sie ist nicht, teilweise oder vollständig stabilisiert durch Ytt¬ riumoxid und/oder Kalziumoxid und/oder Magnesiumoxid. 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 EP 0 486 489 B1, EP 0 786 017 B1, EP 0 412 397 B1 or EP 1 306 454 A1. On the MCrAlX may still be present a thermal barrier coating, and consists for example of Zr02, Y203-Zr02, ie it is not, partially or completely stabilized by Ytt ¬ riumoxid and / or calcium oxide and / or magnesium oxide.
Durch geeignete Beschichtungsverfahren wie z.B. Elektronen- strahlverdampfen (EB-PVD) werden stängelförmige Körner in der Wärmedämmschicht erzeugt. By suitable coating methods, e.g. Electron beam evaporation (EB-PVD) produces stalk-shaped grains 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 gegenüberliegendenThe guide blade 130 has a guide blade root facing the inner housing 138 of the turbine 108 (not shown here) and a guide blade foot opposite
Leitschaufelkopf auf. Der Leitschaufelkopf ist dem Rotor 103 zugewandt und an einem Befestigungsring 140 des Stators 143 festgelegt . Die erfindungsgemäße Legierung weist folgende Gehalte in Ge¬ wichtsprozent (Gew%) auf: Guide vane head on. The vane head faces the rotor 103 and fixed to a mounting ring 140 of the stator 143. The inventive alloy has the following contents in Ge ¬ weight percent (wt%):
Chrom (Cr) 9, 0 bis 15, 0 Chromium (Cr) 9, 0 to 15, 0
insbesondere 9, 0 bis 15, 0 in particular 9, 0 to 15, 0
Titan (Ti) 2, 0 bis 6, 0  Titanium (Ti) 2, 0 to 6, 0
insbesondere 2, 0 bis 6, 0 in particular 2, 0 to 6, 0
Molybdän (Mo) 1, 0 bis 3, 0  Molybdenum (Mo) 1, 0 to 3, 0
Wolfram (W) 2, 0 bis 6, 0 Tantal (Ta) 3, 0 bis 7,0 Tungsten (W) 2, 0 to 6, 0 Tantalum (Ta) 3, 0 to 7.0
Aluminium (AI) 2,0 bis 6, 0  Aluminum (AI) 2.0 to 6.0
Kobalt (Co) 6, 0 bis 11,0  Cobalt (Co) 6, 0 to 11.0
Bor (B) 0, 0025 bis 0,05  Boron (B) 0.0025 to 0.05
Kohlenstoff (C) 0,01 bis 0,3  Carbon (C) 0.01 to 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. 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%) : Preferably, the superalloy comprises (in% by weight):
Chrom (Cr) 11,0 bis 13, 0 Chromium (Cr) 11.0 to 13, 0
insbesondere 11, 6 bis 12,7 in particular 11, 6 to 12.7
Titan (Ti) 3,5 bis 4,5  Titanium (Ti) 3.5 to 4.5
insbesondere 3, 9 bis 4,25 in particular 3, 9 to 4.25
Molybdän (Mo) 1, 65 bis 2,15  Molybdenum (Mo) 1, 65 to 2.15
Wolfram (W) 3,5 bis 4,1  Tungsten (W) 3.5 to 4.1
Tantal (Ta) 4,8 bis 5,2  Tantalum (Ta) 4.8 to 5.2
Aluminium (AI) 3,4 bis 3, 8  Aluminum (AI) 3,4 to 3, 8
Kobalt (Co) 8,5 bis 9,5  Cobalt (Co) 8.5 to 9.5
Bor (B) 0, 0125 bis 0,0175  Boron (B) 0, 0125 to 0.0175
Kohlenstoff (C) 0,08 bis 0,1  Carbon (C) 0.08 to 0.1
insbesondere 0,09. in particular 0.09.
Es können weitere Nebenelemente wie Silizium  There may be other minor elements such as silicon
(Fe) , Vanadium (V) , Niob (Nb) , Kupfer (Cu) , Rc' (Fe), vanadium (V), niobium (Nb), copper (Cu), Rc '
Zirkon (Zr) , Phosphor (P) , Schwefel (S) , und Mangan (Mn) vorhanden sein.  Zircon (Zr), phosphorus (P), sulfur (S), and manganese (Mn).
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%. 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%.
Silizium (Si) steigert die Oxidationsbeständigkeit und bewirkt die Deoxidierung der Schmelze. 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. Similarly, the proportion of iron (Fe) must not exceed 0.2% and may be at least 0.014Gew%.
Eisen (Fe) ist als γ' -Bildner und Nickelsubstituent bekannt. Silizium und Eisen verbessern auch die Gießbarkeit. Eine Reduzierung der Elemente wäre eher unerwünscht. Vorzugsweise ist der Gehalt an Vanadium (V) nicht größer als 75ppm und beträgt vorzugsweise mindestens 50ppm. Iron (Fe) is known as the γ 'imager and nickel substituent. Silicon and iron also improve castability. A reduction of the elements would be rather undesirable. 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. lGew% betragen bei Mindestwerten ab 0.001Gew%. The proportion of copper (Cu) may be up to 0. lGew% with minimum values from 0.001Gew%.
Ebenso vorzugsweise ist der Gehalt an Hafnium (Hf) nicht grö¬ ßer als 50ppm. Dies steht im Gegensatz zu den bekannten Also preferably, the content of hafnium (Hf) is not RESIZE ¬ SSER than 50ppm. This is in contrast to the known ones
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. 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. 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.
Ebenso darf der Borgehalt aber einen gewissen maximalen Wert nicht überschreiten, da es sonst zu einem negativen Einfluss aufgrund des Schmelzpunkterniedrigers kommt.  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. Eine optimale Karbidbildung wird mit 0,09% Kohlenstoff (C) erreicht . The amount of niobium (Nb) - deliberately added in some Ni superalloys - may here be up to 75ppm with minimum values of 50ppm. 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. In contrast to the known DS alloys, the higher addition of grain boundary consolidators such as hafnium and zirconium is dispensed with.
Dafür wird Bor (B) und Kohlenstoff (C) zugegeben. Der  For this, boron (B) and carbon (C) are added. Of the
Kohlenstoffgehalt liegt höher als 0.08Gew%. Durch die Minimierung der Korngrenzenfestiger Hafnium und Zirkon muss dafür genau auf die Einhaltung der Carbon content is higher than 0.08Gew%. By minimizing the grain boundary strength hafnium and zirconium must be precisely on the observance of
Verunreinigungen geachtet werden, wie Silizium (Si) , Mangan (Mn) , Eisen (Fe) oder Kupfer (Cu) . Impurities such as silicon (Si), manganese (Mn), iron (Fe) or copper (Cu).
Verunreinigungen der Legierungen haben vorzugsweise einen maximalen Wert von lOppm. 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. A higher purity of the alloy would be desirable, but hardly affordable and often not necessary.
Durch die Festlegung von zulässigen Bereichen von Nebenelementen können Bauteile 120, 130 günstig aber weiterhin mit bekannt guten Hochtemperatureigenschaften hergestellt werden. Vorzugsweise werden die Elemente Silizium (Si) , Eisen (Fe) , Phosphor (P) und Schwefel (S) akzeptiert.  By defining allowable ranges of minor elements, components 120, 130 may be manufactured inexpensively but with known good high temperature properties. 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 lOOppm, 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 50 ppm, in particular 100 ppm, improves the mechanical properties of the alloy because it promotes γ 'formation.

Claims

Patentansprüche claims
1. Nickelbasierte Superlegierung für die gerichtete Erstar- rung von Bauteilen mit stängelförmigen Körnern, 1. Nickel-based superalloy for the directional solidification of stalk-shaped components,
die aufweist (in Gew%) :  which has (in% by weight):
Chrom (Cr) 9, 0 bis 15  Chromium (Cr) 9, 0 to 15
insbesondere 9, 0 bis 15  in particular 9, 0 to 15
Titan (Ti) 2, 0 bis 6,  Titanium (Ti) 2, 0 to 6,
insbesondere 2, 0 bis 6,  especially 2, 0 to 6,
Molybdän (Mo) 1, 0 bis 3,  Molybdenum (Mo) 1, 0 to 3,
Wolfram (W) 2, 0 bis 6,  Tungsten (W) 2, 0 to 6,
Tantal (Ta) 3, 0 bis 7,  Tantalum (Ta) 3, 0 to 7,
Aluminium (AI) 2, 0 bis 6,  Aluminum (AI) 2, 0 to 6,
Kobalt (Co) 6, 0 bis 11  Cobalt (Co) 6, 0 to 11
Bor (B) 0, 0025 bis 0,  Boron (B) 0, 0025 to 0,
Kohlenstoff (C) 0, 01 bis 0,  Carbon (C) 0, 01 to 0,
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) .  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).
Superlegierung nach Anspruch 1, Superalloy according to claim 1,
bei der der maximale Siliziumgehalt (Si) 0,12Gew% beträgt, insbesondere maximal 0.06Gew%,  in which the maximum silicon content (Si) is 0.12% by weight, in particular not more than 0.06% by weight,
ganz insbesondere maximal 0.04Gew%.  in particular a maximum of 0.04Gew%.
3. Superlegierung nach Anspruch 1 oder 2, 3. Superalloy according to claim 1 or 2,
bei der der Siliziumgehalt (Si) mindestens 0,01Gew% beträgt,  in which the silicon content (Si) is at least 0.01% by weight,
insbesondere mindestens 0,02Gew%.  in particular at least 0.02% by weight.
4. Superlegierung nach Anspruch 1, 2 oder 3, 4. Superalloy according to claim 1, 2 or 3,
bei der der Eisengehalt (Fe) maximal 0,2Gew% beträgt, insbesondere maximal 0.1Gew%,  in which the iron content (Fe) is not more than 0.2% by weight, in particular not more than 0.1% by weight,
ganz insbesondere 0.06Gew%. Superlegierung nach Anspruch 1, 2, 3 oder 4, bei der der Eisengehalt (Fe) mindestens 0,014Gew in particular 0.06Gew%. A superalloy according to claim 1, 2, 3 or 4, wherein the iron content (Fe) is at least 0.014 wt
insbesondere mindestens 0,02Gew%.  in particular at least 0.02% by weight.
6. Superlegierung nach Anspruch 1, 2, 3, 4 oder 5, 6. Superalloy according to claim 1, 2, 3, 4 or 5,
bei der der Vanadiumgehalt (V) maximal 75ppm beträgt.  in which the vanadium content (V) is a maximum of 75ppm.
7. Superlegierung nach Anspruch 1, 2, 3, 4, 5 oder 6, 7. Superalloy according to claim 1, 2, 3, 4, 5 or 6,
bei der der Vanadiumgehalt (V) mindestens 50ppm beträgt.  in which the vanadium content (V) is at least 50 ppm.
8. Superlegierung nach Anspruch 1, 2, 3, 4, 5, 6 oder 7, bei der der maximale Niobgehalt (Nb) 75ppm beträgt A superalloy according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the maximum niobium content (Nb) is 75ppm
9. Superlegierung nach Anspruch 1, 2, 3, 4, 5, 6, 7 oder 8, bei der der Niobgehalt (Nb) mindestens 50ppm beträgt. A superalloy according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the niobium content (Nb) is at least 50 ppm.
10. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 10. Superalloy according to one or more of the preceding claims,
bei der der Kupfergehalt (Cu) maximal 0,lGew% beträgt, insbesondere maximal 0.05Gew%.  in which the copper content (Cu) is not more than 0.1% by weight, in particular not more than 0.05% by weight.
11. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 11. Superalloy according to one or more of the preceding claims,
bei der der Kupfergehalt (Cu) mindestens 0,001Gew% beträgt, insbesondere mindestens 0,01Gew%.  in which the copper content (Cu) is at least 0.001% by weight, in particular at least 0.01% by weight.
12. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, die maximal 75ppm Hafnium (Hf) enthält. 12. Superalloy according to one or more of the preceding claims, which contains a maximum of 75ppm hafnium (Hf).
13. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 13. Superalloy according to one or more of the preceding claims,
die mindestens lOppm Hafnium (Hf) enthält.  which contains at least 10 ppm hafnium (Hf).
14. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 14. Superalloy according to one or more of the preceding claims,
die maximal 25ppm Zirkon (Zr) enthält.  which contains a maximum of 25ppm zircon (Zr).
15. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 15. Superalloy according to one or more of the preceding claims,
die mindestens lOppm Zirkon (Zr) enthält.  which contains at least 10 ppm zirconium (Zr).
16. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 16. Superalloy according to one or more of the preceding claims,
bei der der maximale Mangangehalt (Mn) 0,12Gew% beträgt, insbesondere maximal 0.06Gew%.  in which the maximum manganese content (Mn) is 0.12 wt%, in particular a maximum of 0.06 wt%.
17. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 17. Superalloy according to one or more of the preceding claims,
bei der der Mangangehalt (Mn) mindestens 0,001Gew% beträgt, insbesondere mindestens 0.01Gew%.  in which the manganese content (Mn) is at least 0.001% by weight, in particular at least 0.01% by weight.
18. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 18. Superalloy according to one or more of the preceding claims,
bei der der Borgehalt (B) 150ppm beträgt.  where the boron content (B) is 150ppm.
19. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 19. Superalloy according to one or more of the preceding claims,
bei der der maximale Gehalt an Phosphor (P) 0,015Gew% be- trägt . in which the maximum content of phosphorus (P) is 0.015% by weight wearing .
20. Superlegierung nach einem oder mehreren der vorhergehen- den Ansprüche, 20. Superalloy according to one or more of the preceding claims,
bei der der minimale Gehalt an Phosphor (P) 0,003Gew%, insbesondere mindestens 0,004Gew% beträgt.  in which the minimum content of phosphorus (P) is 0.003% by weight, in particular at least 0.004% by weight.
21. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 21. Superalloy according to one or more of the preceding claims,
bei der der maximale Gehalt an Schwefel (S) 0,025Gew% be¬ trägt, at which the maximum content of sulfur (S) be ¬ carries 0,025Gew%,
insbesondere maximal 0.01Gew%.  in particular at most 0.01Gew%.
22. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 22. Superalloy according to one or more of the preceding claims,
bei der der minimale Gehalt an Schwefel (S) 0,0003Gew%, insbesondere 0,0004Gew% beträgt.  in which the minimum content of sulfur (S) is 0.0003% by weight, in particular 0.0004% by weight.
23. Superlegierung nach einem oder mehreren der vorhergehenden Ansprüche, 23. Superalloy according to one or more of the preceding claims,
die aufweist (in Gew%) :  which has (in% by weight):
Chrom (Cr) 11,0 bis 13, 0  Chromium (Cr) 11.0 to 13, 0
insbesondere 11, 6 bis 12,7  in particular 11, 6 to 12.7
Titan (Ti) 3,5 bis 4,5  Titanium (Ti) 3.5 to 4.5
insbesondere 3, 9 bis 4,25  in particular 3, 9 to 4.25
Molybdän (Mo) 1, 65 bis 2,15  Molybdenum (Mo) 1, 65 to 2.15
Wolfram (W) 3,5 bis 4,1  Tungsten (W) 3.5 to 4.1
Tantal (Ta) 4,8 bis 5,2  Tantalum (Ta) 4.8 to 5.2
Aluminium (AI) 3,4 bis 3, 8  Aluminum (AI) 3,4 to 3, 8
Kobalt (Co) 8,5 bis 9,5  Cobalt (Co) 8.5 to 9.5
Bor (B) 0, 0125 bis 0,0175  Boron (B) 0, 0125 to 0.0175
Kohlenstoff (C) 0,08 bis 0,1  Carbon (C) 0.08 to 0.1
insbesondere 0,09. in particular 0.09.
24. Superlegierung nach einem der vorhergehenden Ansprüche, die Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) aufweist und 24. Superalloy according to one of the preceding claims, the chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B), Having carbon (C) and
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) aufweist, insbesondere daraus besteht.  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), in particular consists thereof.
25. Superlegierung nach einem der vorhergehenden Ansprüche, die Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) aufweist und 25. Superalloy according to one of the preceding claims, the chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B), Having carbon (C) and
zumindest zwei Elemente der Gruppe Silizium (Si) , Eisen (Fe) , Vanadium (V) , Niob (Nb) , Kupfer (Cu) , Hafnium (Hf) , Zirkon (Zr) , Phosphor (P) , Schwefel (S) und Mangan (Mn) aufweist,  at least two elements of the group silicon (Si), iron (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S) and Has manganese (Mn),
insbesondere daraus besteht.  in particular.
26. Superlegierung nach einem der vorhergehenden Ansprüche, die Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) ,26. Superalloy according to one of the preceding claims, comprising chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W),
Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) aufweist und Tantalum (Ta), aluminum (AI), cobalt (Co), boron (B), carbon (C) and
zumindest drei Elemente der Gruppe Silizium (Si) , Eisen (Fe) , Vanadium (V) , Niob (Nb) , Kupfer (Cu) , Hafnium (Hf) , Zirkon (Zr) , Phosphor (P) , Schwefel (S) und Mangan (Mn) aufweist,  at least three elements of the group silicon (Si), iron (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S) and Has manganese (Mn),
insbesondere daraus besteht. in particular.
27. Superlegierung nach einem der vorhergehenden Ansprüche, die Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) aufweist und 27. Superalloy according to one of the preceding claims, comprising chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B), Having carbon (C) and
zumindest vier Elemente der Gruppe Silizium (Si) , Eisen at least four elements of the group silicon (Si), iron
(Fe) , Vanadium (V) , Niob (Nb) , Kupfer (Cu) , Hafnium (Hf) , Zirkon (Zr) , Phosphor (P) , Schwefel (S) und Mangan (Mn) aufweist, (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S) and manganese (Mn),
insbesondere daraus besteht.  in particular.
28. Superlegierung nach einem der vorhergehenden Ansprüche, die Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlen- Stoff (C) aufweist und A superalloy according to any one of the preceding claims comprising chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B), Has carbon (C) and
zumindest fünf Elemente der Gruppe Silizium (Si) , Eisen (Fe) , Vanadium (V) , Niob (Nb) , Kupfer (Cu) , Hafnium (Hf) , Zirkon (Zr) , Phosphor (P) , Schwefel (S) und Mangan (Mn) aufweist,  at least five elements of the group silicon (Si), iron (Fe), vanadium (V), niobium (Nb), copper (Cu), hafnium (Hf), zirconium (Zr), phosphorus (P), sulfur (S) and Has manganese (Mn),
insbesondere daraus besteht.  in particular.
29. Superlegierung nach einem der vorhergehenden Ansprüche, die Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) , Eisen (Fe) und Silizium (Si) aufweist, 29. Superalloy according to one of the preceding claims, comprising chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B), Having carbon (C), iron (Fe) and silicon (Si),
insbesondere daraus besteht.  in particular.
30. Superlegierung nach einem der vorhergehenden Ansprüche, die Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) , Eisen (Fe) und Phosphor (P) aufweist, A superalloy according to any one of the preceding claims comprising chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B), Having carbon (C), iron (Fe) and phosphorus (P),
insbesondere daraus besteht. in particular.
31. Superlegierung nach einem der vorhergehenden Ansprüche, die aus Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) , Silizium (Si) und Phosphor (P) aufweist, A superalloy according to any one of the preceding claims, which is selected from chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B). Having carbon (C), silicon (Si) and phosphorus (P),
insbesondere daraus besteht.  in particular.
32. Superlegierung nach einem der vorhergehenden Ansprüche, die aus Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) , Eisen (Fe), Silizium (Si) und Phosphor (P) aufweist, insbesondere daraus besteht. 32. Superalloy according to one of the preceding claims, consisting of chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B) , Carbon (C), iron (Fe), silicon (Si) and phosphorus (P), in particular consists thereof.
33. Superlegierung nach einem der vorhergehenden Ansprüche, die aus Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) , Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) und A superalloy according to any one of the preceding claims, which is selected from chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W), tantalum (Ta), aluminum (AI), cobalt (Co), boron (B). , Carbon (C) and
zumindest drei, insbesondere vier Elemente der Gruppe  at least three, in particular four elements of the group
Silizium (Si) , Phosphor (P) , Schwefel (S) und Eisen (Fe) aufweist, insbesondere daraus besteht.  Silicon (Si), phosphorus (P), sulfur (S) and iron (Fe), in particular consists thereof.
34. Superlegierung nach einem der vorhergehenden Ansprüche, die aus Chrom (Cr), Titan (Ti) , Molybdän (Mo), Wolfram (W) ,34. Superalloy according to one of the preceding claims, which consists of chromium (Cr), titanium (Ti), molybdenum (Mo), tungsten (W),
Tantal (Ta) , Aluminium (AI), Kobalt (Co), Bor (B) , Kohlenstoff (C) und Tantalum (Ta), aluminum (AI), cobalt (Co), boron (B), carbon (C) and
und zumindest ein, insbesondere zwei Elemente der Gruppe Silizium (Si) , Phosphor (P) , Schwefel (S) und Eisen (Fe) aufweist, insbesondere daraus besteht and at least one, in particular two elements of the group silicon (Si), phosphorus (P), sulfur (S) and iron (Fe), in particular consists thereof
35. Superlegierung nach einem oder mehreren der vorherigen Ansprüche, 35. Superalloy according to one or more of the preceding claims,
die 50ppm bis 2000 ppm,  the 50ppm to 2000ppm,
insbesondere bis 1000 ppm,  in particular up to 1000 ppm,
ganz insbesondere bis 500ppm,  especially up to 500ppm,
Zinn oder Zink,  Tin or zinc,
insbesondere Zinn (Sn) enthält.  in particular tin (Sn).
36. Bauteil, 36th component,
das stängelförmige Einkristalle aufweist und  has the stalk-shaped single crystals and
das eine Legierung gemäß einem oder mehreren der vorherigen that is an alloy according to one or more of the previous ones
Ansprüche 1 bis 35 aufweist. Claims 1 to 35 has.
EP09756148.4A 2009-10-20 2009-10-20 Alloy for directional solidification and columnar grained component Not-in-force EP2491156B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP18000230.5A EP3363923A1 (en) 2009-10-20 2009-10-20 Alloy for directional solidification and component made of stem-shaped crystals

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2009/063737 WO2011047714A1 (en) 2009-10-20 2009-10-20 Alloy for directional solidification and component made of stem-shaped crystals

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP18000230.5A Division EP3363923A1 (en) 2009-10-20 2009-10-20 Alloy for directional solidification and component made of stem-shaped crystals

Publications (2)

Publication Number Publication Date
EP2491156A1 true EP2491156A1 (en) 2012-08-29
EP2491156B1 EP2491156B1 (en) 2018-04-04

Family

ID=41571398

Family Applications (2)

Application Number Title Priority Date Filing Date
EP18000230.5A Withdrawn EP3363923A1 (en) 2009-10-20 2009-10-20 Alloy for directional solidification and component made of stem-shaped crystals
EP09756148.4A Not-in-force EP2491156B1 (en) 2009-10-20 2009-10-20 Alloy for directional solidification and columnar grained component

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP18000230.5A Withdrawn EP3363923A1 (en) 2009-10-20 2009-10-20 Alloy for directional solidification and component made of stem-shaped crystals

Country Status (3)

Country Link
US (1) US9068251B2 (en)
EP (2) EP3363923A1 (en)
WO (1) WO2011047714A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8921730B2 (en) * 2011-06-22 2014-12-30 General Electric Company Method of fabricating a component and a manufactured component
CH705327A1 (en) 2011-07-19 2013-01-31 Alstom Technology Ltd Lot for high-temperature soldering and method of repairing or manufacturing components using this solder.
CN105624472A (en) * 2015-12-28 2016-06-01 广东华科新材料研究院有限公司 Nickel-based high-temperature alloy powder for 3D printing and preparation method for nickel-based high-temperature alloy powder
US11123790B2 (en) 2017-10-16 2021-09-21 General Electric Company Apparatus for casting a mold
US11123791B2 (en) 2017-10-16 2021-09-21 General Electric Company Method for casting a mold

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3807993A (en) * 1971-10-15 1974-04-30 Avco Corp Nickel base alloy containing hafnium
DE2333775C3 (en) * 1973-06-27 1978-12-14 Avco Corp., Cincinnati, Ohio (V.St.A.) Process for the heat treatment of a nickel alloy
NL8201076A (en) 1982-03-15 1983-10-03 Administratie En Automatiserin DEVICE FOR ATTACHING A CLOSING WALL TO A PACKAGING.
DE3926479A1 (en) 1989-08-10 1991-02-14 Siemens Ag RHENIUM-PROTECTIVE COATING, WITH GREAT CORROSION AND / OR OXIDATION RESISTANCE
EP0486489B1 (en) 1989-08-10 1994-11-02 Siemens Aktiengesellschaft High-temperature-resistant, corrosion-resistant coating, in particular for components of gas turbines
KR100354411B1 (en) 1994-10-14 2002-11-18 지멘스 악티엔게젤샤프트 Protective layer for protecting parts against corrosion, oxidation and excessive thermal stresses, as well as process for producing the same
US6036791A (en) 1997-01-23 2000-03-14 Mitsubishi Materials Corporation Columnar crystalline Ni-based heat-resistant alloy having high resistance to intergranular corrosion at high temperature, method of producing the alloy, large-size article, and method of producing large-size article from the alloy
EP0892090B1 (en) 1997-02-24 2008-04-23 Sulzer Innotec Ag Method for manufacturing single crystal structures
EP0861927A1 (en) 1997-02-24 1998-09-02 Sulzer Innotec Ag Method for manufacturing single crystal structures
JP3722975B2 (en) * 1998-02-23 2005-11-30 三菱重工業株式会社 Method for recovering performance of Ni-base heat-resistant alloy
US20090107592A1 (en) * 1998-06-23 2009-04-30 Winfried Esser Heat treatment of alloys having elements for improving grain boundary strength
WO1999067435A1 (en) 1998-06-23 1999-12-29 Siemens Aktiengesellschaft Directionally solidified casting with improved transverse stress rupture strength
US6231692B1 (en) 1999-01-28 2001-05-15 Howmet Research Corporation Nickel base superalloy with improved machinability and method of making thereof
EP1204776B1 (en) 1999-07-29 2004-06-02 Siemens Aktiengesellschaft High-temperature part and method for producing the same
AU2001243302A1 (en) * 2000-02-29 2001-09-12 General Electric Company Nickel base superalloys and turbine components fabricated therefrom
DE50104022D1 (en) 2001-10-24 2004-11-11 Siemens Ag Protective layer containing rhenium to protect a component against corrosion and oxidation at high temperatures
DE50112339D1 (en) 2001-12-13 2007-05-24 Siemens Ag High-temperature resistant component made of monocrystalline or polycrystalline nickel-based superalloy
US20030111138A1 (en) 2001-12-18 2003-06-19 Cetel Alan D. High strength hot corrosion and oxidation resistant, directionally solidified nickel base superalloy and articles
CN100449031C (en) * 2002-10-23 2009-01-07 西门子公司 Heat treatment of alloy containing reinforced crystal boundary strength content
US20040200549A1 (en) * 2002-12-10 2004-10-14 Cetel Alan D. High strength, hot corrosion and oxidation resistant, equiaxed nickel base superalloy and articles and method of making
EP1536026A1 (en) * 2003-11-27 2005-06-01 Siemens Aktiengesellschaft High temperature resistant article
EP1820883A1 (en) * 2006-01-17 2007-08-22 Siemens Aktiengesellschaft Alloy, protective coating and component
US9322089B2 (en) * 2006-06-02 2016-04-26 Alstom Technology Ltd Nickel-base alloy for gas turbine applications
US20080260572A1 (en) * 2007-04-19 2008-10-23 Siemens Power Generation, Inc. Corrosion and oxidation resistant directionally solidified superalloy
US8262817B2 (en) * 2007-06-11 2012-09-11 Honeywell International Inc. First stage dual-alloy turbine wheel
EP2279817B1 (en) * 2008-05-09 2012-07-25 Siemens Aktiengesellschaft Directionally solidified elongated component with elongated grains of differing widths

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011047714A1 *

Also Published As

Publication number Publication date
US20120201713A1 (en) 2012-08-09
US9068251B2 (en) 2015-06-30
WO2011047714A1 (en) 2011-04-28
EP2491156B1 (en) 2018-04-04
EP3363923A1 (en) 2018-08-22

Similar Documents

Publication Publication Date Title
EP2701878A1 (en) Nickel-based alloy, use, and method
EP2382333B1 (en) Alloy, protective layer and component
EP1716965A1 (en) Solder comprising metallic elemental filler powder
EP1967312A1 (en) Method for repair soldering of a component under vacuum and a selected oxygen partial pressure
WO2008061813A2 (en) NiCoCrAl LAYER AND METAL LAYER SYSTEM
EP1816222A1 (en) Coating system with two-layered metallic protective coating
EP2491156B1 (en) Alloy for directional solidification and columnar grained component
EP1798299B1 (en) Alloy, protective coating and component
WO2010084036A1 (en) Component having varying structures and method for production
EP1790743A1 (en) Alloy, protective layer and component
EP2742171A1 (en) Ceramic double layer based on zirconium oxide
WO2008110454A1 (en) Solder alloys and method for the repair of a component
EP2637863A1 (en) Alloy, protective layer and component
WO2009141197A1 (en) Two-layer mcra1x coating having different contents of cobalt and nickel
EP2128285A1 (en) Two-layer MCrAIX coating with different cobalt and nickel contents
WO2012095221A1 (en) Cobalt-based alloy comprising germanium and method for soldering
WO2012107130A1 (en) Material having a pyrochlore structure with tantalum, use of the material, layer system and method for producing a layer system
WO2011127956A2 (en) Solder alloy, soldering method and component
WO2011127958A2 (en) Solder alloy, soldering method and component
EP2661370B1 (en) Alloy, protective layer and component
EP2611949B1 (en) Nickel base alloy, protective coating, and component
EP2558245B1 (en) Solder containing germanium, component with a solder and a soldering method
EP1970156A1 (en) Solder alloy and method for repairing a part
EP1790746B1 (en) Alloy, protective layer and component
WO2015071015A1 (en) Porous ceramic coating system

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120416

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SIEMENS AKTIENGESELLSCHAFT

RIN1 Information on inventor provided before grant (corrected)

Inventor name: PICKERT, URSULA

Inventor name: HANSLITS, CHRISTOPHER R.

Inventor name: GOLDSCHMIDT, DIRK

Inventor name: VOGT, RUSSEL G.

Inventor name: PAUL, UWE

Inventor name: OTT, MICHAEL

Inventor name: ESSER, WINFRIED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HOWMET CORPORATION

17Q First examination report despatched

Effective date: 20160623

17Q First examination report despatched

Effective date: 20160623

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HOWMET CORPORATION

Owner name: SIEMENS AKTIENGESELLSCHAFT

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HOWMET CORPORATION

Owner name: SIEMENS AKTIENGESELLSCHAFT

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20171213

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 985671

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180415

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502009014869

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180704

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180704

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180705

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180806

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20181005

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502009014869

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20181217

Year of fee payment: 10

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20181029

Year of fee payment: 10

Ref country code: GB

Payment date: 20181005

Year of fee payment: 10

Ref country code: FR

Payment date: 20181018

Year of fee payment: 10

26N No opposition filed

Effective date: 20190107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181020

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181020

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 985671

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502009014869

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20191101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180404

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20091020

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200501

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180804

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20191020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191020

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191020

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031