EP2076616B1 - Nickel-base superalloys - Google Patents

Nickel-base superalloys Download PDF

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Publication number
EP2076616B1
EP2076616B1 EP07803558.1A EP07803558A EP2076616B1 EP 2076616 B1 EP2076616 B1 EP 2076616B1 EP 07803558 A EP07803558 A EP 07803558A EP 2076616 B1 EP2076616 B1 EP 2076616B1
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Prior art keywords
nickel
base superalloy
amount
superalloy
alloy
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EP07803558.1A
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German (de)
French (fr)
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EP2076616A1 (en
Inventor
Magnus Hasselqvist
Gordon Mccolvin
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Siemens AG
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Siemens AG
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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
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%

Definitions

  • the invention relates to nickel-base superalloys and to components containing these alloys.
  • Nickel-base superalloys are used in applications where a combination of high strength and a strong resistance to chemical attacks at high temperatures is needed. They are employed for the production of components of gas turbines such as blades and vanes. These parts are arranged in the hot section of a turbine and thus have to withstand high temperatures and an aggressive atmosphere.
  • Nickel-base superalloys and components of the above mentioned kind are disclosed for example in US 6,818,077 , US 6,419,763 , US 6,177,046 , EP 0 789 087 and EP 0 637 474 .
  • Nickel-base superalloy which basically consists of 4.75 to 5.25% Co, 15.5 to 16.5% Cr, 0.8 to 1.2% Mo, 3.75 to 4.25% W, 3.75 to 4.25% A1, 1.75 to 2.25% Ti, 4.75 to 5.25% Ta, the remaining part being Nickel beside other constituents in traces.
  • Nickel-base superalloys are described in EP 0 560 296 A1 .
  • a composition containing 7.3 to 9% Cr, 4.7 to 5.5% A1, 5 to 6.3% W, 5 to 7.5% Ta, 0.5 to 1.8% Mo, 0.5 to 1.5% Co, 1.3 to 1.8% Nb, 1.3 to 1.65% Re, not more than 0.13% Hf and the balance Ni is proposed.
  • the nickel-base superalloy of the invention comprises in wt%: Co + Fe + Mn 0 - 20 Al 4 - 6, especially from 4.3 to 6 Cr >12 - 20 Ta >7.5 - 15 Ti 0 - ⁇ 0.45 V 0 - 1 Nb 0 - ⁇ 0.28 Mo 0 - 2.5 Mo + W + Re + Rh 2 - 8 Ru + Os + Ir + Pt + Pd 0 - 4 Hf 0 - 1.5 C + B + Zr 0 - 0.5 Ca + Mg + Cu 0 - 0.5 Y + La + Sc + Ce + Actinides + Lanthanides 0 - 0.5 Si 0 - 0.5 Ni balance and unavoidable impurities.
  • the superalloy consists of these elements. Especially one, several or all optionally listed elements are present in the alloy. "Present” means that the amount of this element is measurable higher than the known impurity level of this element in a nickel based super alloy. That means that the amount of this element is at least twice the impurity level of this element in a nickel powder based alloy.
  • the alloy contains significant levels of Al, Cr and Ta to provide a combination of high strength, high oxidation resistance and high corrosion resistance.
  • the amount of matrix strengthening elements Mo, W, Re and Rh is between 2 and 8 wt%.
  • Hf, C, B, Zr, Ca, Mg, Cu, Y, La, Sc, Ce, actinides and lanthanides, and Si can be present in the superalloy in order to adapt its properties to special needs such as grain boundary strengthening, oxide scale fortification, and compatibility with specific coating systems.
  • the content of Ti can be in the range (in wt%) of 0-0.40. Preferably it can be 0-0.35, more preferably 0-0.30 and most preferably 0-0.20.
  • the content of Nb (in wt%) can be in the range of 0-0.25, preferably 0-0.20, more preferably 0-0.15 and most preferably 0-0.10.
  • the content of C (in wt%) can be in the range of 0-0.15, preferably 0-0.08, more preferably 0.01-0.06 and most preferably 0.02-0.04.
  • the superalloy of the invention can also contain B in the range (in wt%) of 0-0.02, preferably 0-0.01, more preferably 0.001-0.008 and most preferably 0.003-0.007.
  • a conventional cast component, directionally solidified component and a single crystal component, which comprise the super alloy are provided.
  • a conventional cast or a single crystal component consisting of a superalloy which comprises in wt%: Co + Fe + Mn 0 - 20 Al 4 - 6 Cr >12 - 20 Ta >7.5 - 15 Ti 0 - 1.5 V 0 - 1 Ti + Nb + V 0-2 Mo 0 - 2.5 Mo + W + Re + Rh 2 - 8 Ru + Os + Ir + Pt + Pd 0-4 Hf 0 - 1.5 C + B + Zr 0 - 0.5 Ca + Mg + Cu 0 - 0.5 Y + La + Sc + Ce + Actinides + Lanthanides 0 - 0.5 Si 0 - 0.5 Ni balance and unavoidable impurities.
  • the components of the invention can especially be part of a gas turbine, for example a turbine blade or vane, or as filler material, for example for laser welding of gas turbine components.
  • the superalloy comprises the elements Ni, Co, Cr, Mo, W, Al, Ta, Hf, C and B and very especially consists only of these elements.
  • Ta supported by moderate levels of Mo and W is will also have a high strength, as Ta is a very potent strengthening element. Consequently it satisfies our requirements on high strength, high oxidation resistance, high corrosion resistance, microstructural stability and a large heat treatment window.
  • Table 2 shows a further preferred embodiment of the invention.
  • Table 2 Element wt% Ni balance Co 3 Cr 16 Mo 1.7 W 2.3 Al 4.5 Ta 10 Hf 0.1 Zr 0.02 C 0.06 B 0.01
  • the superalloy comprises the elements Ni, Co, Cr, Mo, W, Al, Ta, Hf, Zr, C and B and very especially consists only of these elements.
  • composition in Table 2 had an average content of sulphur (S) estimated to be ⁇ 30ppm, at which it should be severely detrimental, and the Al content is a comparatively moderate 4.5%.
  • the composition in Table 2 has a lower particle content than the composition in Table 1, about 45 vol% rather than about 60vol%, and should therefore have a larger heat treatment window, and be at least as stable.
  • the composition in Table 2 With 16%Cr and a low level of the detrimental element Mo it will also have a high corrosion resistance.

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

Description

  • The invention relates to nickel-base superalloys and to components containing these alloys.
  • Nickel-base superalloys are used in applications where a combination of high strength and a strong resistance to chemical attacks at high temperatures is needed. They are employed for the production of components of gas turbines such as blades and vanes. These parts are arranged in the hot section of a turbine and thus have to withstand high temperatures and an aggressive atmosphere.
  • Nickel-base superalloys and components of the above mentioned kind are disclosed for example in US 6,818,077 , US 6,419,763 , US 6,177,046 , EP 0 789 087 and EP 0 637 474 .
  • From US 2005/0194068 a Nickel-base superalloy is known, which basically consists of 4.75 to 5.25% Co, 15.5 to 16.5% Cr, 0.8 to 1.2% Mo, 3.75 to 4.25% W, 3.75 to 4.25% A1, 1.75 to 2.25% Ti, 4.75 to 5.25% Ta, the remaining part being Nickel beside other constituents in traces.
  • Further Nickel-base superalloys are described in EP 0 560 296 A1 . To achieve high temperature strength, high temperature ductility, hot corrosion and oxidation resistance, a composition containing 7.3 to 9% Cr, 4.7 to 5.5% A1, 5 to 6.3% W, 5 to 7.5% Ta, 0.5 to 1.8% Mo, 0.5 to 1.5% Co, 1.3 to 1.8% Nb, 1.3 to 1.65% Re, not more than 0.13% Hf and the balance Ni is proposed.
  • It is an object of the present invention to provide a nickel-base superalloy, which combines high strength, high oxidation resistance, high corrosion resistance, microstructural stability and a large heat treatment window. It is a further object of the present invention to provide components, which comprise such a superalloy.
  • These objects are solved by the superalloy of claim 1 and the components of claims 22 to 25.
  • The nickel-base superalloy of the invention comprises in wt%:
    Co + Fe + Mn 0 - 20
    Al 4 - 6, especially from 4.3 to 6
    Cr >12 - 20
    Ta >7.5 - 15
    Ti 0 - <0.45
    V 0 - 1
    Nb 0 - <0.28
    Mo 0 - 2.5
    Mo + W + Re + Rh 2 - 8
    Ru + Os + Ir + Pt + Pd 0 - 4
    Hf 0 - 1.5
    C + B + Zr 0 - 0.5
    Ca + Mg + Cu 0 - 0.5
    Y + La + Sc + Ce +
    Actinides + Lanthanides 0 - 0.5
    Si 0 - 0.5
    Ni balance
    and unavoidable impurities.
  • Especially the superalloy consists of these elements.
    Especially one, several or all optionally listed elements are present in the alloy. "Present" means that the amount of this element is measurable higher than the known impurity level of this element in a nickel based super alloy. That means that the amount of this element is at least twice the impurity level of this element in a nickel powder based alloy.
  • The alloy contains significant levels of Al, Cr and Ta to provide a combination of high strength, high oxidation resistance and high corrosion resistance.
  • Along Ta, other strengtheners of the gamma prime particles like Ti, Nb and V can be added to the superalloy, but since they are detrimental to the oxidation resistance, they should at most be added in limited quantities.
    The amount of Ti should not exceed 0.45, the amount of Nb should not exceed 0.28, and the amount of V should not exceed 1 wt% respectively.
  • The amount of matrix strengthening elements Mo, W, Re and Rh is between 2 and 8 wt%.
  • Other elements like Hf, C, B, Zr, Ca, Mg, Cu, Y, La, Sc, Ce, actinides and lanthanides, and Si can be present in the superalloy in order to adapt its properties to special needs such as grain boundary strengthening, oxide scale fortification, and compatibility with specific coating systems.
  • The content of Ti can be in the range (in wt%) of 0-0.40. Preferably it can be 0-0.35, more preferably 0-0.30 and most preferably 0-0.20.
  • It was also found that the content of Nb (in wt%) can be in the range of 0-0.25, preferably 0-0.20, more preferably 0-0.15 and most preferably 0-0.10.
  • According to another embodiment of the invention the content of C (in wt%) can be in the range of 0-0.15, preferably 0-0.08, more preferably 0.01-0.06 and most preferably 0.02-0.04.
  • The superalloy of the invention can also contain B in the range (in wt%) of 0-0.02, preferably 0-0.01, more preferably 0.001-0.008 and most preferably 0.003-0.007.
  • According to one aspect of the invention a conventional cast component, directionally solidified component and a single crystal component, which comprise the super alloy are provided.
  • According to another aspect of the invention, a conventional cast or a single crystal component consisting of a superalloy, which comprises in wt%:
    Co + Fe + Mn 0 - 20
    Al 4 - 6
    Cr >12 - 20
    Ta >7.5 - 15
    Ti 0 - 1.5
    V 0 - 1
    Ti + Nb + V 0-2
    Mo 0 - 2.5
    Mo + W + Re + Rh 2 - 8
    Ru + Os + Ir + Pt + Pd 0-4
    Hf 0 - 1.5
    C + B + Zr 0 - 0.5
    Ca + Mg + Cu 0 - 0.5
    Y + La + Sc + Ce + Actinides + Lanthanides 0 - 0.5
    Si 0 - 0.5
    Ni balance
    and unavoidable impurities.
  • Especially the superalloy consists of these elements.
  • The components of the invention can especially be part of a gas turbine, for example a turbine blade or vane, or as filler material, for example for laser welding of gas turbine components.
  • In the following one preferred embodiment of the invention is described. A superalloy was cast which has the composition given in table 1. Table 1
    Element wt%
    Co 4.12
    Cr 14.2
    Mo 0.96
    W 2.51
    Al 5.47
    Ta 10.1
    Hf 0.41
    C 0.04
    B 0.005
    Ni balance
  • Especially the superalloy comprises the elements Ni, Co, Cr, Mo, W, Al, Ta, Hf, C and B and very especially consists only of these elements.
  • In order to characterize the properties of the cast superalloy in Table 1 different experiments were conducted.
  • Solutioning experiments for 4h at 1220, 1250, 1260, 1270 and 1300°C followed by water quenching were done. At 1220°C residual particles were seen and at 1250, 1260, 1270 and 1300°C full solutioning without incipient melting was observed.
  • Further a heat treatment at 1250°C for 8h, 1100°C for 4h and 850°C for 24h was applied. SEM and TEM analysis showed a very regular microstructure with primary particles of ∼0.35 µm side length and a significant amount of secondary particles.
  • No trace of TCP phases was found. The particle content was measured to be ∼60 vol%.
    At this relatively high particle content it is usually difficult to obtain such a large heat treatment window, or, to include as much as 14%Cr without precipitation of brittle phases.
    Accordingly it was shown that this emphasis on Cr, Ta and Al with at most moderate levels of other alloy elements provides a large heat treatment window and a good microstructural stability. Since Al is regarded as highly beneficial, Cr and Ta as beneficial, Mo and W as mildly detrimental (and Ti, Nb and V as detrimental) to oxidation resistance the composition in Table 1 will have a high oxidation resistance. With 14%Cr and a low level of the detrimental element Mo it will also have a high corrosion resistance.
  • With as much as 10% Ta supported by moderate levels of Mo and W is will also have a high strength, as Ta is a very potent strengthening element. Consequently it satisfies our requirements on high strength, high oxidation resistance, high corrosion resistance, microstructural stability and a large heat treatment window.
  • Table 2 shows a further preferred embodiment of the invention. Table 2
    Element wt%
    Ni balance
    Co 3
    Cr 16
    Mo 1.7
    W 2.3
    Al 4.5
    Ta 10
    Hf 0.1
    Zr 0.02
    C 0.06
    B 0.01
  • Especially the superalloy comprises the elements Ni, Co, Cr, Mo, W, Al, Ta, Hf, Zr, C and B and very especially consists only of these elements.
  • Most highly oxidation resistant alloys like e.g. CMSX-4 contain >5% Al and are cast with production processes to obtain <5ppm S, and recently to levels as low as <0.5ppm S.
  • The composition in Table 2 had an average content of sulphur (S) estimated to be ∼30ppm, at which it should be severely detrimental, and the Al content is a comparatively moderate 4.5%.
  • Cyclic oxidation tests on the superalloy in Table 2 nevertheless showed a stable response for 300h under the severe test conditions of 1h cycle time and 1100C test temperature, which indicates an ability to form stable alumina, i.e. a high oxidation resistance. Accordingly it was shown that this emphasis on Cr, Ta and Al with at most moderate levels of other alloy elements provides a high oxidation resistance.
  • The composition in Table 2 has a lower particle content than the composition in Table 1, about 45 vol% rather than about 60vol%, and should therefore have a larger heat treatment window, and be at least as stable. With 16%Cr and a low level of the detrimental element Mo it will also have a high corrosion resistance.
    With as much as 10% Ta supported by moderate levels of Mo and W it will also have a high strength, as Ta is a very potent strengthening element.
    Consequently it satisfies our requirements on high strength, high oxidation resistance, high corrosion resistance, microstructural stability and a large heat treatment window.

Claims (26)

  1. A nickel-base superalloy comprising (in wt%): Co + Fe + Mn 0 - 20 Al 4 - 6, especially from 4.3 to 6, Cr >12 - 20 Ta >7.5 - 15 Ti 0 - <0.45 V 0 - 1 Nb 0 - <0.28 Mo 0 - 2.5 Mo + W + Re + Rh 2 - 8 Ru + Os + Ir + Pt + Pd 0 - 4 Hf 0 - 1.5 C + B + Zr 0 - 0.5 Ca + Mg + Cu 0 - 0.5 Y + La + Sc + Ce + Actinides + Lanthanides 0 - 0.5 Si 0 - 0.5 Ni balance
    and unavoidable impurities.
  2. The nickel-base superalloy as claimed in claim 1,
    wherein titanium (Ti) is in the range (in wt%) of 0 - 0.40, preferably 0 - 0.35,
    more preferably 0 - 0.30 and
    most preferably 0 - 0.20.
  3. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein niobium (Nb) is in the range (in wt%) of 0 - 0.25,
    preferably 0 - 0.20,
    more preferably 0 - 0.15 and
    most preferably 0 - 0.10.
  4. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein carbon (C) is in the range (in wt%) of 0 - 0.15,
    preferably 0 - 0.08,
    more preferably 0.01 - 0.06 and
    most preferably 0.02 - 0.04.
  5. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein boron (B) is in the range (in wt%) of 0 - 0.02,
    preferably 0 - 0.01,
    more preferably 0.001 - 0.008 and most preferably 0.003 - 0.007.
  6. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein molybdenum (Mo) is present in the alloy with 1.0wt% to 2.4 wt%,
    preferably 1.7wt% to Mo.
  7. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the element hafnium (Hf) is present in the alloy higher than 0.1wt%.
  8. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the maximum amount of Hf is 0.5wt%.
  9. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein Co is present in the alloy with 2wt% to 4wt%,
    preferably with 3wt%.
  10. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein cobalt (Co) and iron (Fe) are present in the alloy and
    wherein the amount of Fe is smaller than the amount of Co.
  11. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein cobalt (Co) and manganese (Mn) are present in the alloy and
    wherein the amount of Mn is smaller than the amount of Co.
  12. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein cobalt (Co), manganese (Mn) and iron (Fe) are present in the alloy and
    wherein the amount of Fe and Mn is smaller than the amount of Co.
  13. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the chromium (Cr) content is higher than 14wt%.
  14. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the chromium (Cr) content is higher than 16wt%.
  15. The nickel-base superalloy as claimed in any of the claims 1 to 13,
    wherein the amount of chromium (Cr) is between 14wt% to 18wt% Cr,
    preferably 16wt%.
  16. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the amount of tungsten (W) is between 1.7wt% and 2.8wt%,
    especially is 2.3wt%.
  17. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the amount of aluminium (Al) is equal or higher than 4.5wt%.
  18. The nickel-base superalloy as claimed in any of the claims 1 to 16,
    wherein the amount of aluminium (Al) is between 4.0wt% to 4.3wt%.
  19. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the amount of tantalum (Ta) is between 9wt% to 11wt%,
    preferably the amount of Ta is 10 wt%.
  20. The nickel-base superalloy as claimed in any of the claims 1 to 18,
    wherein the amount of tantalum (Ta) is higher than 10wt%.
  21. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the amount of zirconium (Zr) is higher or equal than 0.02 Zr,
    especially is 0.02 wt%.
  22. The nickel-base superalloy as claimed in any of the preceding claims,
    wherein the superalloy consists of
    Ni, Co, Cr, Mo, W, Al, Ta, Hf, Zr, C and B.
  23. A conventional cast component comprising a superalloy according to any of the claims 1 to 22.
  24. A directionally solidified component comprising a superalloy according to any of the claims 1 to 22.
  25. A single crystal component comprising a superalloy according to any of the claims 1 to 22.
  26. The component according to any of the claims 23 to 25, wherein the component is a part of a gas turbine.
EP07803558.1A 2006-10-17 2007-09-20 Nickel-base superalloys Active EP2076616B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07803558.1A EP2076616B1 (en) 2006-10-17 2007-09-20 Nickel-base superalloys

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06021724A EP1914327A1 (en) 2006-10-17 2006-10-17 Nickel-base superalloy
PCT/EP2007/059936 WO2008046708A1 (en) 2006-10-17 2007-09-20 Nickel-base superalloys
EP07803558.1A EP2076616B1 (en) 2006-10-17 2007-09-20 Nickel-base superalloys

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EP2076616A1 EP2076616A1 (en) 2009-07-08
EP2076616B1 true EP2076616B1 (en) 2015-10-28

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US (1) US20100296962A1 (en)
EP (2) EP1914327A1 (en)
JP (1) JP5124582B2 (en)
CN (1) CN101528959B (en)
WO (1) WO2008046708A1 (en)

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