EP2154258B1 - Auf Nickel basierende Superlegierung, zugehöriges Verfahren zur unidirektionalen Verfestigung und daraus gebildete Gussstücke - Google Patents

Auf Nickel basierende Superlegierung, zugehöriges Verfahren zur unidirektionalen Verfestigung und daraus gebildete Gussstücke Download PDF

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Publication number
EP2154258B1
EP2154258B1 EP09166869A EP09166869A EP2154258B1 EP 2154258 B1 EP2154258 B1 EP 2154258B1 EP 09166869 A EP09166869 A EP 09166869A EP 09166869 A EP09166869 A EP 09166869A EP 2154258 B1 EP2154258 B1 EP 2154258B1
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nickel
base superalloy
casting
alloy
superalloy according
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French (fr)
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EP2154258A1 (de
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Ganjiang Feng
Shyh-Chin Huang
Jian Zheng
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General Electric Co
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General Electric Co
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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
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B22D27/045—Directionally solidified castings

Definitions

  • the present invention generally relates to nickel-base superalloy compositions and processes for producing directionally-solidified castings therefrom. More particularly, the invention is directed to a nickel-base superalloy that is castable as single-crystal articles suitable for use as components of gas turbines and other high temperature applications.
  • Components of gas turbines such as blades (buckets), vanes (nozzles) and combustor components, are typically formed of nickel, cobalt or iron-base superalloys characterized by desirable mechanical properties at turbine operating temperatures. Because the efficiency of a gas turbine is dependent on its operating temperatures, there is an ongoing effort to develop components, and particularly turbine buckets, nozzles, and combustor components, that are capable of withstanding higher temperatures. As the material requirements for gas turbine components have increased, various processing methods and alloying constituents have been used to enhance the mechanical, physical and environmental properties of components formed from superalloys.
  • buckets, nozzles and other components employed in demanding applications are often cast by unidirectional casting techniques to have directionally-solidified (DS) or single-crystal (SX) microstructures, characterized by a crystal orientation or growth direction in a selected direction to produce columnar polycrystalline or single-crystal articles.
  • DS directionally-solidified
  • SX single-crystal
  • the nickel-base superalloy commercially known as René N5, disclosed in commonly-assigned U.S. Patent No. 6,074,602 has a composition of, by weight percent, about 5-10 chromium, about 5-10 cobalt, about 0-2 molybdenum, about 3-10 tungsten, about 3-8 tantalum, about 0-2 titanium, about 5-7 aluminum, about 0-6 rhenium, about 0-0.50 hafnium,about 0-0.07 carbon, about 0-0.015 boron, and about 0-0.075 yttrium, the balance being nickel and incidental impurities.
  • the composition of N5 is characterized by controlled concentrations of certain critical alloying elements to achieve a desired mix of properties.
  • properties include high temperature creep strength, oxidation and corrosion resistance, resistance to low and high cycle fatigue (LCF and HCF), and single-crystal castability.
  • N5 performs extremely well in applications within gas turbines, buckets and nozzles cast from N5 can exhibit external and internal freckle chains. Because excessive freckling can necessitate scrappage of a casting, there is a desire to reduce the incidence and level of freckling exhibited by the N5 alloy.
  • the present invention provides an alloy composition and method by which the incidence of freckling can be reduced in a unidirectionally-solidified casting having properties similar to unidirectionally-solidified castings produced from the N5 nickel-base superalloy.
  • a nickel-base superalloy that is particularly suitable for producing castings with unidirectional crystal structures.
  • the superalloy has a composition consisting of, by weight, 6% to 8% chromium, 6% to 9% cobalt, 0% to 2% molybdenum, 4% to 6% tungsten, 6.4% to 6.9% tantalum, 0% to 2% titanium, 5% to 7% aluminum, 2.7% to 3.0% rhenium, 0.3% to 0.7% hafnium, 0.04% to 0.08% carbon, 0.002% to 0.006% boron, 0% to 0.075% yttrium, 0.002% to 0.004% zirconium, the balance being nickel and incidental impurities.
  • a method for producing the nickel-base superalloy as a unidirectionally-solidified casting.
  • the method generally entails pouring a molten quantity of the composition into a heated zone of a preheated mold comprising a main cavity having the shape of the cast article, withdrawing the mold from the heated zone into a cooling tank to directionally solidify the molten metal, and then cooling the mold to produce the casting and a unidirectional crystal structure.
  • the unidirectional crystal structure of the casting is substantially free of freckle defects.
  • the characterization of a casting being substantially free of freckles is meant to indicate a total combined length of all freckles of not more than 0.5 inch (about 12 mm).
  • a significant advantage of this invention is that, though the composition of the casting contains the same alloying constituents as N5 and the alloying levels of these constituents are within or overlap the broadest ranges disclosed for N5, it has been determined that the employment of particular levels and relative proportions of these constituents are able to produce unexpected superior results as compared to the N5 alloy processed under identical conditions. In particular, the reduction in the incidence of freckling is greater than was expected for composition modifications alone, and the result is the absence of freckling that would otherwise be an expected property for N5 under the same processing conditions.
  • the unidirectional crystal structure of the casting is a single crystal with a preferred single crystal direction of ⁇ 001>, though crystalline structures having orientations other than ⁇ 001> are also within the scope of the invention.
  • the alloy composition and castings that can be produced in accordance with the invention are well suited for components of a gas turbine, such as buckets, nozzles, and other components of gas turbines.
  • FIG. 1 depicts a first stage bucket 10 for a land-based gas turbine, such as the H and FB class gas turbines used in the power-generating industry and manufactured by the assignee of the invention.
  • the bucket 10 has an airfoil 12 and shank 14, with a dovetail 16 formed on the shank 14 for anchoring the bucket 10 to a turbine disk (not shown).
  • the bucket 10 is preferably unidirectionally cast to have a columnar single crystal (SX) or columnar polycrystalline (DS) microstructure. While the advantages of this invention will be described with reference to components of a gas turbine, such as the bucket 10 shown in FIG. 1 , the teachings of this invention are generally applicable to other components that benefit from being cast from a high-temperature material such as N5.
  • freckles form in part as a result of molten metal convection in the casting mold which disrupts unidirectional solidification processes, producing irregularities seen on SX and DS casting surfaces as little chains of equiaxed, crystals.
  • Freckles can act as grain initiators during the solidification process that cause unacceptable off-axial grains, and may reduce fatigue life of the casting.
  • external and internal freckling can be inhibited and even eliminated in an alloy whose constituent levels fall within the ranges disclosed for N5 levels in US6,074,602 , the contents of which relating to composition of the N5 alloy are incorporated herein by reference.
  • the alloy can be used to produce large castings that are typically more prone to freckling, including the large turbine buckets of land-based gas turbines such as that of FIG. 1 , whose overall lengths are often in the range of about fifteen to about forty inches (about forty to about one hundred centimeters).
  • compositional modifications to the nickel-base N5 superalloy that achieve the reduction in freckling were initially based on data generated from a modeling technique, through which correlations were identified and analyzed regarding the overall effect of each element of the N5 alloy on freckle formation. Broad ranges disclosed in US6,074,602 for N5 are summarized in Table I below.
  • R c Freckle Susceptibility Index
  • the convection potency factor is a factor developed for use in the modeling technique, and takes into account several variables, including the slope of the liquidus line in the phase diagram, the segregation coefficient, solutal volume expansion coefficient, and thermal volume expansion coefficient. From the equation, it can be seen that elements with a negative convection potency factor (P i ) reduce the value of the Freckle Susceptibility Index, R e , and therefore are expected to reduce the risk of freckling, whereas elements with a positive P i value increase R c and are therefore expected to increase the risk of freckling.
  • P i convection potency factor
  • hafnium should have the strongest influence on freckle formation, and also the greatest beneficial effect on freckle prevention if present at sufficiently high levels. Tantalum and carbon also have beneficial effects, though not as pronounced as hafnium.
  • aluminum, tungsten, and rhenium are expected to have a moderate detrimental effect due to their moderate P i values in combination with their significant alloying levels in the N5 alloy.
  • the influence that any one element might have on the Freckle Susceptibility Index, R e can be predicted based on the product of its convection potency factor, P i , and its concentration tolerance ( ⁇ C i ) in the production specification for the N5 alloy.
  • P i convection potency factor
  • ⁇ C i concentration tolerance
  • tantalum (-3) and carbon (-5) should have moderate positive affects
  • rhenium (8), tungsten (6), and aluminum (2) should have moderate negative affects
  • cobalt, chromium, and molybdenum should have negligible affects (approximately 0), as will titanium, columbium, and zirconium if present as impurities.
  • the nickel-base alloy of the present invention nominally contains more hafnium, tantalum and carbon and less rhenium, tungsten, aluminum, and zirconium than the nominal N5 composition.
  • tantalum and aluminum are both gamma prime (Ni 3 X) formers, a lower level of aluminum can be offset by the higher level of tantalum to maintain the gamma prime content desired for N5.
  • rhenium and tungsten are both solid solution strengtheners, and as such attempts to offset reductions in both of these elements must be by increasing another solid solution strengthener in order to maintain the desirable properties of N5.
  • experiments conducted to verify the predictions of the modeling technique suggested that the influence of hafnium may be sufficiently strong to eliminate freckling if hafnium levels exceed the hafnium upper limit for N5 (0.50 weight percent).
  • the nickel-base alloy has the following broad, preferred, and nominal compositions, by weight.
  • TABLE III Constituent Broad Range Preferred Range Nominal Chromium 6 to 8 % 6.75 to 7.25 % 7 % Cobalt 6 to 9 % 7 to 8 % 7.5 % Molybdenum 0 to 2 % 1.3 to 1.7 % 1.5 % Tungsten 4 to 6 % 4.5 to 5.0 % 4.75 % Tantalum 6.4 to 6.9 % 6.5 to 6.8 % 6.7 % Titanium 0 to 2 % 0 to 0.05 % 0 to 0.02 % Aluminum 5 to 7 % 6.0 to 6.2 % 6.1 % Rhenium 2.7 to 3.0 % 2.75 to 2.9 % 2.8 % Carbon 0.04 to 0.08 % 0.05 to 0.07 % 0.06 % Hafnium 0.3 to 0.7 % 0.4 to 0.6 % 0.5 % Boron 0.002 to 0.006 % 0.003 to 0.005 %
  • the balance of the alloy is nickel and incidental impurities. Aside from freckling reduction, the alloy of this invention preferably has essentially the same properties as, and potentially superior properties to, the N5 alloy, and therefore provides an excellent alternative to N5.
  • Components of the alloy having SX or DS microstructures can be produced by generally conventional casting unidirectional casting techniques.
  • single-crystal castings are produced from a melt of the alloy, for example, prepared by known vacuum induction melting techniques.
  • heat transfer conditions during the solidification of the casting are controlled so that one section of the casting article does not cool faster than the rest of the casting to avoid the nucleation and formation of secondary grains from the melt in competition with the primary columnar single crystal.
  • Secondary and multi-grains are further controlled by adjusting the heat transfer conditions during the withdrawal of the mold into a cooling bath or radiation cooling zone to ensure that all parts of the casting cool at approximately the same rate.
  • FIG. 2 represents a shell mold 20 of a type suitable for producing a single-crystal casting of the alloy of this invention.
  • the mold 20 is preferably formed of a material such as alumina or silica, and has an internal cavity 22 corresponding to the desired shape of a casting 32, represented as a turbine bucket similar to that of FIG. 1 .
  • the cavity 22 is configured to produce the casting 32 with an airfoil portion 34, shank 36, and dovetail 38.
  • the mold 20 is shown secured to a chill plate 24 and placed in a heating zone 26 to heat the mold 20 to a temperature equal to or above the melting temperature of the alloy, and more particularly above the liquidus temperature of the alloy (about 1397°C).
  • the casting process is preferably carried out in a vacuum or an inert atmosphere.
  • the molten alloy is poured into the preheated mold 20, after which unidirectional solidification is initiated by withdrawing the base of the mold 20 and chill plate 24 downwardly at a fixed rate to a cooling zone (not shown), which may contain a liquid metal cooling bath or a vacuum or ambient or cooled air for radiation cooling.
  • the casting 32 grows epitaxially (for example, with the ⁇ 100> orientation) based on the crystalline structure and orientation of a small block of single-crystal seed material 28 at the base of the mold 20, from which a single crystal forms from a crystal selector 30.
  • the columnar single crystal becomes larger in the enlarged section of the cavity 22.
  • a bridge 40 connects protruding sections of the casting 32 with lower sections of the casting 32 so that a unidirectional columnar single crystal forms substantially throughout the casting 32.
  • the casting 32 is deemed to be a substantially columnar single crystal if more than 50% of the casting is single crystal.
  • a DS casting can be produced in a similar manner, though with modifications to the mold 20, such a growth zone at the base of the mold 20 that is open to the chill plate 24, and omission of the crystal selector 30.
  • Alloys A and B were substantially identical to the Baseline Alloy except for their levels of tungsten (which differed by only 0.15% from the Baseline), tantalum (which differed by only 0.24% or 0.25% from the Baseline), aluminum (which differed by only 0.15% from the Baseline), rhenium (which differed by only 0.11 % and 0.13% from the Baseline), hafnium (which differed by only 0.06% or 0.36% from the Baseline), and zirconium (which differed by only 0.004% from the Baseline). Nonetheless, it will be seen that these small changes in chemistry had a significant impact on the incidence of freckling in their respective alloys.
  • FIGS. 3 and 4 are scanned images showing external freckle chains in buckets formed of the Baseline Alloy and Alloy B, respectively.
  • FIG. 3 more than twenty freckle chains can be seen on the bucket root of the Baseline Alloy casting.
  • FIG. 5 is a graph plotting freckle length measurement data obtained from the buckets cast from all three alloys.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Claims (15)

  1. Superlegierung auf Nickelbasis, die eine Zusammensetzung aufweist, die, bezogen auf das Gewicht, besteht aus:
    6% bis 8% Chrom,
    6% bis 9% Kobalt,
    0% bis 2% Molybdän;
    4% bis 6% Wolfram,
    6,4% bis 6,9% Tantal,
    0% bis 2% Titan,
    5% bis 7% Aluminium,
    2,7% bis 3,0% Rhenium,
    0,3% bis 0,7% Hafnium,
    0,04% bis 0,08% Kohlenstoff,
    0,002% bis 0,006% Bor,
    0% bis 0,075% Yttrium,
    0,002% bis 0,004% Zirkonium,
    Rest Nickel und üblichen Verunreinigungen.
  2. Superlegierung auf Nickelbasis nach Anspruch 1, worin die Superlegierung auf Nickelbasis in der Form eines Gussstückes vorliegt.
  3. Superlegierung auf Nickelbasis nach Anspruch 2, worin das Gussstück im wesentlichen frei von Seigerungsfehlern ist.
  4. Superlegierung auf Nickelbasis nach Anspruch 2, worin das Gussstück eine unidirektionale Kristallstruktur aufweist.
  5. Superlegierung auf Nickelbasis nach Anspruch 4, worin die unidirektionale Kristallstruktur ein Einkristall ist.
  6. Superlegierung auf Nickelbasis nach Anspruch 4, worin das Gussstück eine Komponente für eine Gasturbine ist.
  7. Superlegierung auf Nickelbasis nach irgendeinem vorhergehenden Anspruch, worin die Zusammensetzung 6,5 bis 6,8 Gew.-% Tantal enthält.
  8. Superlegierung auf Nickelbasis nach irgendeinem vorhergehenden Anspruch, worin die Zusammensetzung 6 bis 6,2 Gew.-% Aluminium enthält.
  9. Superlegierung auf Nickelbasis nach irgendeinem vorhergehenden Anspruch, worin die Zusammensetzung 2,75 bis 2,9 Gew.-% Rhenium enthält.
  10. Superlegierung auf Nickelbasis nach irgendeinem vorhergehenden Anspruch, worin die Zusammensetzung 0,4 bis 0,6 Gew.-% Hafnium enthält.
  11. Superlegierung auf Nickelbasis nach irgendeinem vorhergehenden Anspruch, worin die Zusammensetzung 0,002 bis 0,003 Gew.-% Zirkonium enthält.
  12. Superlegierung auf Nickelbasis nach irgendeinem der Ansprüche 1 bis 6, worin die Zusammensetzung, bezogen auf das Gewicht, weniger als 4,90% Wolfram, mehr als 6,44% Tantal, weniger als 6,20% Aluminium und weniger als 2,91% Rhenium enthält.
  13. Verfahren zum Herstellen der Superlegierung auf Nickelbasis nach irgendeinem vorhergehenden Anspruch, wobei das Verfahren umfasst:
    Giessen einer geschmolzenen Menge der Zusammensetzung in eine erhitzte Zone einer vererhitzten Form, die einen Haupthohlraum umfasst,
    Herausziehen der Form aus der erhitzten Zone in eine Kühlzone zum gerichteten Erstarren des geschmolzenen Metalles und dann
    Abkühlen der Form zum Herstellen eines Gussstückes, das eine unidirektionale Kristallstruktur aufweist, die im wesentlichen frei von Seigerungsdefekten ist.
  14. Superlegierung auf Nickelbasis nach Anspruch 1, in der Form eines Gussstückes, das eine unidirektionale Kristallstruktur aufweist, die im wesentlichen frei von Seigerungsdefekten ist, wobei die Superlegierung eine Zusammensetzung aufweist, die, bezogen auf das Gewicht, besteht aus:
    6,75% bis 7,25% Chrom,
    7% bis 8% Kobalt,
    1,3% bis 1,7% Molybdän;
    4,5% bis 5,0% Wolfram,
    6,5% bis 6,8% Tantal,
    0% bis 0,05% Titan,
    6,0% bis 6,2% Aluminium,
    2,75% bis 2,90% Rhenium,
    0,4% bis 0,6% Hafnium,
    0,04% bis 0,08% Kohlenstoff,
    0,003% bis 0,005% Bor,
    0% bis 0,075% Yttrium,
    0,002% bis 0,003% Zirkonium,
    Rest Nickel und üblichen Verunreinigungen.
  15. Superlegierung auf Nickelbasis nach Anspruch 14, wobei die Zusammensetzung, bezogen auf das Gewicht, besteht aus:
    etwa 7% Chrom,
    etwa 7,5% Kobalt,
    etwa 1,5% Molybdän;
    etwa 4,75% Wolfram,
    etwa 6,7% Tantal,
    etwa 0% bis 0,02% Titan,
    etwa 6,1% Aluminium,
    etwa 2,8% Rhenium,
    etwa 0,5% Hafnium,
    etwa 0,06% Kohlenstoff,
    etwa 0,004% Bor,
    0% bis 0,03% Yttrium,
    etwa 0,0025% Zirkonium,
    Rest Nickel und üblichen Verunreinigungen.
EP09166869A 2008-08-06 2009-07-30 Auf Nickel basierende Superlegierung, zugehöriges Verfahren zur unidirektionalen Verfestigung und daraus gebildete Gussstücke Active EP2154258B1 (de)

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US12/187,049 US20100034692A1 (en) 2008-08-06 2008-08-06 Nickel-base superalloy, unidirectional-solidification process therefor, and castings formed therefrom

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WO2007122931A1 (ja) * 2006-03-31 2007-11-01 National Institute For Materials Science Ｎｉ基超合金とその製造方法
JP4773303B2 (ja) * 2006-08-22 2011-09-14 株式会社日立製作所 強度、耐食性、耐酸化特性に優れたニッケル基単結晶超合金及びその製造方法
RU2415190C2 (ru) * 2006-09-13 2011-03-27 Нэшнл Инститьют Фор Матириалз Сайенс МОНОКРИСТАЛЛИЧЕСКИЙ СУПЕРСПЛАВ НА ОСНОВЕ Ni
EP1914327A1 (de) * 2006-10-17 2008-04-23 Siemens Aktiengesellschaft Nickel-Basis-Superlegierung
US7704332B2 (en) * 2006-12-13 2010-04-27 United Technologies Corporation Moderate density, low density, and extremely low density single crystal alloys for high AN2 applications

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US20100034692A1 (en) 2010-02-11
JP2010037658A (ja) 2010-02-18
EP2154258A1 (de) 2010-02-17

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