EP1329527A2 - Superalliage à base de nickel à haute résistance mécanique, résistant à la corrosion et à l'oxidation à chaud, solidifié directionnellement et objets en ce superalliage - Google Patents

Superalliage à base de nickel à haute résistance mécanique, résistant à la corrosion et à l'oxidation à chaud, solidifié directionnellement et objets en ce superalliage Download PDF

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Publication number
EP1329527A2
EP1329527A2 EP02258710A EP02258710A EP1329527A2 EP 1329527 A2 EP1329527 A2 EP 1329527A2 EP 02258710 A EP02258710 A EP 02258710A EP 02258710 A EP02258710 A EP 02258710A EP 1329527 A2 EP1329527 A2 EP 1329527A2
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article
articles
alloy
titanium
aluminum
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EP02258710A
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German (de)
English (en)
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EP1329527B1 (fr
EP1329527A3 (fr
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Alan D. Cetel
Dilip M. Shah
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RTX Corp
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United Technologies Corp
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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
    • 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 present invention relates to the field of nickel base superalloys for use in directionally solidified articles, and more particularly to such alloys providing articles having good mechanical properties at elevated temperatures, good resistance to hot corrosion, and good oxidation resistance.
  • U.S. Pat. No. 3,619,182 describes a moderate strength superalloy, commercially known as IN 792, having purportedly superior corrosion resistance.
  • the alloy would have been cast to form an equiaxed (e.g., no indication of crystallographic orientation) article, e.g., for gas turbine engine components.
  • equiaxed e.g., no indication of crystallographic orientation
  • GTD-111 An alloy, commonly known as GTD-111 which has been cast in equiaxed and directionally solidified forms.
  • GTD-111 has a nominal composition, in weight percent, of: 14 Cr; 9.7 Co; 1.5 Mo; 3.8 W; 3 Ta; 3 Al; 0.10 C; 5 Ti; 0.02 B; 0.04 Zr, bal. Ni. See, e.g., Schiike, et el. "Advanced Materials Propel Progress in Land-Based Gas Turbines", Advanced Materials and Processes, April 1992; see also, U.K.
  • U.S. Pat. No. 3,615,376 is directed to an alloy with a claimed composition, in weight percent, of: 0.15 - 0.3 C (described as more than is required for de-oxidation and sufficient to form grain boundary carbides); 13 - 15.6 Cr; 5 - 15 Co; 2.5 - 5 Mo; 3 - 6 W; 4 - 6 Ti; 2 - 4 Al; 0.005 - 0.02 Zr; balance Ni and incidental impurities; and also requires that Ti/Al be 1:1 - 3:1; Ti + Al between 7.5 - 9; Mo + 0.5W between 5 - 7; with a substantial absence of sigma phase and a stress rupture life of at least 25 hours at 27.5 ksi (190 Pa) at 1800°F (982°C).
  • a directionally solidified version of this alloy may also include a significant, intentionally added amount of Hf, e.g. up to or over 0.5 wt. %. It has been our experience generally that when adapting an alloy for columnar grain use, significant amounts of Hf must be added to an alloy, whether the starting alloy is equiaxed or single crystal, in order to provide critical properties, such as acceptable transverse ductility and to prevent hot tearing during casting, required for uses such as gas turbine engine components.
  • alloy disclosed in commonly owned U.S. Pat. No. 4,597,809 arose from an investigation of the effects of the minor elements carbon, boron, zirconium and hafnium on the properties of certain commercial alloys in single crystal form (the major function of these minor elements appeared to involve grain boundary strengthening). It was previously determined that fabrication of alloy IN 792 (originally in equiaxed form) as altered in the '182 patent in single crystal form - but without grain boundary strengtheners - provided substantial and unexpected benefits in mechanical properties. The single crystal IN 792 articles evaluated had no intentional additions of carbon, boron, zirconium or hafnium. In the course of the investigation of the effects of the minor elements on IN 792, it was observed that adding small amounts of carbon, i.e.
  • 0.10 wt. % to IN 792 single crystals substantially improved the hot corrosion resistance but at the same time substantially reduced the mechanical properties of the material.
  • the improvement of the hot corrosion resistance was completely unexpected and was not understood.
  • additions of tantalum were made to the basic IN 792 composition in coordination with the added carbon and it was found that when the added tantalum and carbon contents were balanced (to tie up the carbon as tantalum carbide) a good combination of improved mechanical properties and improved corrosion resistance resulted.
  • Single crystal articles are in many cases more difficult and expensive to produce, relative to their columnar grain counterparts, especially as component size increases. Moreover, where relatively large articles are to be produced, e.g., for land based gas turbine applications, the difficulty and expense can increase substantially.
  • hafnium, carbon, boron and zirconium are typically added to the single crystal or equiaxed composition for the purpose of improving properties, such as transverse creep strength and/or ductility.
  • adding hafnium, even in small amounts such as 0.5 - 2 wt. % has several undesirable consequences including increased segregation banding, which can significantly reduce castability of the alloy.
  • hafnium promotes increased eutectic ⁇ / ⁇ ' formation.
  • Hafnium also lowers the incipient melting temperature of the alloy, thereby reducing the temperature range or window available for a solution heat treatment of the alloy. Since achieving good creep strength typically requires subjecting the part to a suitable solution heat treatment, the reduced window makes it more difficult - in some cases not possible - to provide a suitable solution heat treatment. This problem is exacerbated with larger articles, such as land based gas turbine components where segregation becomes worse. Adding hafnium also increases density of the alloy, increasing the weight of parts fabricated from the alloy, and also can reduce the microstructural stability of the alloy.
  • a directionally solidified article comprising a high strength, corrosion and oxidation resistant nickel base superalloy which comprises a matrix and from about 0.4 to 1.5 vol. % of a phase based on tantalum carbide, the alloy consisting substantially of, in weight percent, of: 10 - 13.5% chromium; 8 - 10% cobalt; 1.25 - 2.5% molybdenum; 3.25 - 4.25% tungsten; 4.5 - 6% tantalum; 3.25 - 4.5% aluminum; 3 - 4.75% titanium; 0.0025 - 0.025% boron; up to about 0.05% zirconium; 0.05 - 0.15% carbon; and having no intentional addition of niobium; no intentional addition of hafnium; and balance essentially nickel; wherein aluminum + titanium is between about 6.5 - 8%.
  • Alloys for columnar grain directionally solidified articles are disclosed which have at least comparable oxidation resistance relative to single crystal counterparts, and corrosion resistance at least comparable to such alloys. Moreover the inventive alloys have oxidation resistance at least equal to equiaxed counterparts, and at least equal corrosion resistance. In many instances, the alloys of the present invention provide articles in columnar grain directionally solidified form with superior oxidation resistance than comparable articles and alloys in equiaxed or single crystal form.
  • the inventive alloys comprise a matrix with a general composition, in weight percent, of 10 - 14.5% chromium; 8 - 10% cobalt; 1.25 - 2.5% molybdenum; 3.25 - 4.25% tungsten; 4.5 - 6% tantalum; 3.25 - 4.5% aluminum; 3 - 5% titanium; 0.0025 - 0.025% boron; up to about 0.02% zirconium (no intentional additions); 0.05 - 0.15% carbon; and having no intentional addition of niobium; no intentional addition of hafnium; and balance essentially nickel; wherein aluminum + titanium is between about 6.5 - 8%.
  • the alloy also includes roughly about 0.4 to 1.5 vol. % of a phase based on tantalum carbide.
  • the alloy exhibits oxidation resistance at 2000°F (1093°C) of at least roughly 2.5X, creep rupture life at 1400°F (760°C) of at least roughly 2.4X and at 1800°F (982°C) of at least roughly 1.5X compared to a similar article having a nominal composition of 14 Cr, 4.9 Ti, 1.5 Mo, 3.8 W, 2.8 Ta, 3 Al, 9.5 Co, 0.01 B, 0.02 Zr, 0.1 C, and balance Ni.
  • the invention composition may be cast in columnar grain, directionally-solidified (or single crystal) form according to the teachings of various prior patents as is known in the art.
  • the grains of the casting will have an orientation parallel to the principal stress axis of the component, e.g., ⁇ 100> although deviations may be tolerated.
  • the articles can include high angles boundaries of up to and in excess of 20°.
  • the present composition after being cast in directionally solidified form can be heat treated in order to improve the mechanical properties of the alloy by controlling the gamma prime particle size in accordance, e.g., with the teachings of U.S. Pat. No. 4,116,723 which is also expressly incorporated herein by reference.
  • such articles as cast may have adequate creep strength (depending upon their intended use) such that solution heat treatment is unnecessary.
  • the present invention is based on altering the chemistry originally adapted for use in single crystal articles, e.g., commonly owned U.S. Pat. No. 4,597,809, which is expressly incorporated by reference herein, into an alloy that is particularly useful in the production of columnar grain articles - although we believe that the alloy of the present invention may also be useful in the production of single crystal articles also.
  • cast articles in accordance with the present invention are characterized by good hot corrosion resistance, good oxidation resistance, and good longitudinal and transverse creep-rupture properties.
  • GTD-111 e.g., GB Pat. No.
  • 1,511,652 which is used in equiaxed and columnar grain forms, and has a nominal composition in weight percent of 14 Cr, 4.9 Ti, 1.5 Mo, 3.8 W, 2.8 Ta, 3 Al, 9.5 Co, 0.01 B, ⁇ 0.02 Zr, ⁇ 0.05 C, and balance Ni.
  • beneficial and different properties may be achieved, among other things, by altering the composition of the single crystal '809 alloy by significantly increasing the carbon and boron levels (and allowing a maximum amount of zirconium in the alloy) on one hand, or by altering the nominal content of the equiaxed/columnar grain -111 alloy by significantly increasing tantalum, aluminum, molybdenum and boron contents, and significantly decreasing the titanium and chromium contents on the other hand (e.g., the '562 patent teaches among other things high chromium (above 13.7 wt. %); relatively higher cobalt (over 9.5 wt. %); that more than 0.02% zirconium is acceptable; and that tantalum over 3 - 3.5 wt. % will cause unacceptable microstructural instability). This is particularly true in the case of columnar grain articles, together with close control of the overall composition.
  • the generally preferred composition of the present invention consists substantially of, in weight percent, about 10 - 14.5% (preferably 10 - 13.5%) chromium; 8 - 10% cobalt; 1.25 - 2.5% molybdenum; 3.25 - 4.25% tungsten; 4.5 - 6% tantalum; 3.25 - 4.5% aluminum; 3 - 5% (preferably 3 - 4.75%) titanium; 0.0025 - 0.025% boron; up to about 0.02% zirconium; 0.05 - 0.15% carbon; and having no intentional addition of niobium; no intentional addition of hafnium; and balance essentially nickel; wherein aluminum + titanium is between about 6.5 - 8%.
  • the alloy also includes roughly about 0.4 to 1.5 vol.
  • the alloy comprises about 11 - 13% chromium; 8.25 - 9.75% cobalt; 1.5 - 2.25% molybdenum; 3.4 - 4.3% tungsten; 4.7 - 5.5% tantalum; 3.3 - 4% aluminum; 3.75 - 4.3% titanium; 0.008 - 0.025% boron; up to about 0.02% zirconium; 0.08 - 0.13 carbon; wherein aluminum + titanium is between about 7 - 8%.
  • the alloy comprises about 12% chromium; 9% cobalt; 1.9% molybdenum; 3.8% tungsten; 5% tantalum; 3.6% aluminum; 4.1% titanium; 0.015% boron; less than 0.02% zirconium; 0.10% carbon; and having no intentional addition of zirconium (and in any event less than about 0.02 Zr) and no intentional addition of niobium; no intentional addition of hafnium; balance essentially nickel.
  • the inventive composition includes no intentional additions of zirconium, and whether or not it is practical to tolerate about up to about 0.02 wt. %, we prefer less.
  • Mod A number of modifications (“Mod") were prepared by investment casting columnar grain articles, and were evaluated as described below. Some of the compositions (all in wt. %) are outside of the preferred ranges invention, but are still encompassed by the invention. Overall, the composition of Mod 4 is the preferred composition of the six listed below, but the other Mods and other compositions within the inventive ranges are also useful. In each case, the balance of the composition comprises nickel and small amounts of incidental impurities. For example, we have optimized the alloy for castability, without debiting other properties, by increasing carbon to about 0.08 wt. % and increasing boron to about 0.015 wt. %. The optimization effport was brought about, in part, by siginificant hot tearing during casting of large parts.
  • FIG. 2 shows the relative hot corrosion resistance of the inventive alloy compared to other alloys, including the -111 alloy. Corrosion testing was performed at 1650°F (899°C) in a corrosion gaseous environment produced by combustion of Jet A fuel (30:1 air fuel ratio) with addition of 20 ppm of ASTM sea salt and sufficient sulfur dioxide to produce a sulfur content equivalent to a 1.3% S content in the fuel. The numbers presented are the hours of exposure required to produce 1 mil (25 ⁇ m) of corrosive attack. As seen in the FIG., the inventive alloy exhibits corrosion resistance comparable to GTD-111 and significantly better than single crystal alloys of similar compositions, see, commonly owned U.S. Pat. Nos. 4,209,348 and 4,719,080 both of which are expressly incorporated by reference herein.
  • FIG. 3 shows the relative uncoated, burner rig oxidation resistance of several Mods of the inventive alloy at 2000°F (1093°C) and several other alloys. While the oxidation resistance exceeds the oxidation resistance of GTD-111, Mod 4 is significantly higher (at least 2.5X) and similar to the oxidation resistance of the single crystal alloy of the '809 patent.
  • the increase in aluminum content and decrease in titanium content if the inventive alloy over GTD-111 is largely responsible for the inventive alloy's greater oxidation resistance.
  • Transverse creep rupture ductility was also tested for several Mods, as shown in FIG. 7. Minimum elongation at rupture (see FIG. 4) was at least about 5%. Such transverse ductility would be expected to provide a material that is more resistant to the formation of casting cracks.
  • the present invention is either based on a modification of a published composition for a prior art columnar grain article, or of a published composition for a prior art single crystal article.
  • the present invention includes among other things significantly increasing tantalum, aluminum and molybdenum contents, and significantly decreasing the titanium and chromium contents.
  • the present invention includes among other things discreet amounts of boron and carbon while controlling the presence of zirconium (each of which are explicitly kept out of the prior art alloy).
  • the inventive alloy and articles fabricated from the alloy exhibit a good combination of oxidation resistance, corrosion resistance and creep-rupture resistance at various temperatures.

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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)
  • Powder Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Coating By Spraying Or Casting (AREA)
EP02258710A 2001-12-18 2002-12-18 Superalliage à base de nickel à haute résistance mécanique, résistant à la corrosion et à l'oxidation à chaud, solidifié directionnellement et objets en ce superalliage Revoked EP1329527B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/023,565 US20030111138A1 (en) 2001-12-18 2001-12-18 High strength hot corrosion and oxidation resistant, directionally solidified nickel base superalloy and articles
US23565 2001-12-18

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EP1329527A2 true EP1329527A2 (fr) 2003-07-23
EP1329527A3 EP1329527A3 (fr) 2003-10-22
EP1329527B1 EP1329527B1 (fr) 2006-05-10

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EP02258710A Revoked EP1329527B1 (fr) 2001-12-18 2002-12-18 Superalliage à base de nickel à haute résistance mécanique, résistant à la corrosion et à l'oxidation à chaud, solidifié directionnellement et objets en ce superalliage

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US (1) US20030111138A1 (fr)
EP (1) EP1329527B1 (fr)
JP (1) JP4413492B2 (fr)
KR (1) KR100954683B1 (fr)
CN (1) CN1322157C (fr)
AT (1) ATE325901T1 (fr)
DE (1) DE60211297T2 (fr)
ES (1) ES2261604T3 (fr)
IL (1) IL153479A0 (fr)
RU (1) RU2295585C2 (fr)
UA (1) UA73989C2 (fr)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050069450A1 (en) * 2003-09-30 2005-03-31 Liang Jiang Nickel-containing alloys, method of manufacture thereof and articles derived thereform
US20060182649A1 (en) * 2005-02-16 2006-08-17 Siemens Westinghouse Power Corp. High strength oxidation resistant superalloy with enhanced coating compatibility
US9322089B2 (en) * 2006-06-02 2016-04-26 Alstom Technology Ltd Nickel-base alloy for gas turbine applications
CN100460543C (zh) * 2006-06-16 2009-02-11 中国科学院金属研究所 一种高强抗热腐蚀低偏析定向高温合金
US20110076179A1 (en) * 2009-03-24 2011-03-31 O'hara Kevin Swayne Super oxidation and cyclic damage resistant nickel-base superalloy and articles formed therefrom
US20100254822A1 (en) * 2009-03-24 2010-10-07 Brian Thomas Hazel Super oxidation and cyclic damage resistant nickel-base superalloy and articles formed therefrom
EP2248923A1 (fr) * 2009-04-27 2010-11-10 Siemens Aktiengesellschaft Superalliage de y/ý à base de nickel avec plusieurs éléments réactifs et utilisation de cet alliage dans des systèmes de matériau complexes
US20110076180A1 (en) * 2009-09-30 2011-03-31 General Electric Company Nickel-Based Superalloys and Articles
US20110076182A1 (en) * 2009-09-30 2011-03-31 General Electric Company Nickel-Based Superalloys and Articles
US20110076181A1 (en) * 2009-09-30 2011-03-31 General Electric Company Nickel-Based Superalloys and Articles
US9068251B2 (en) 2009-10-20 2015-06-30 Siemens Aktiengesellschaft Alloy for directional solidification and component made of stem-shaped crystals
EP2431489A1 (fr) * 2010-09-20 2012-03-21 Siemens Aktiengesellschaft Superalliages à base de nickel
CN102011195B (zh) * 2010-11-23 2012-06-06 北京科技大学 一种定向凝固高铌钛铝合金单晶的制备方法
US20130287566A1 (en) * 2011-01-19 2013-10-31 Ralf Bode Plain bearing for a turbomachine rotor and turbomachine having the plain bearing
US20120282086A1 (en) * 2011-05-04 2012-11-08 General Electric Company Nickel-base alloy
CN103114225B (zh) * 2011-11-16 2016-01-27 中国科学院金属研究所 一种高强抗热腐蚀镍基单晶高温合金
US9404388B2 (en) 2014-02-28 2016-08-02 General Electric Company Article and method for forming an article
ITUA20161551A1 (it) * 2016-03-10 2017-09-10 Nuovo Pignone Tecnologie Srl Lega avente elevata resistenza all’ossidazione ed applicazioni di turbine a gas che la impiegano
CN109234655B (zh) * 2018-09-27 2020-09-11 北京科技大学 一种提高gh4169高温合金松弛稳定性的方法
FR3094018B1 (fr) * 2019-03-20 2022-02-04 Safran Superalliage a proprietes optimisees et densite limitee
CN117660810B (zh) * 2024-01-31 2024-04-16 四川航大新材料有限公司 一种变循环燃气发动机涡轮叶片用高纯高温母合金及其制备方法和应用

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US3619182A (en) * 1968-05-31 1971-11-09 Int Nickel Co Cast nickel-base alloy
GB1409628A (en) * 1973-06-26 1975-10-08 Avco Corp Nickel base alloy containing hafnium
GB2033925A (en) * 1978-09-25 1980-05-29 Johnson Matthey Co Ltd Nickel based superalloys
US4597809A (en) * 1984-02-10 1986-07-01 United Technologies Corporation High strength hot corrosion resistant single crystals containing tantalum carbide
GB2268937A (en) * 1992-07-23 1994-01-26 Abb Research Ltd Precipitation-hardenable, nickel-based superalloy
EP0855449A1 (fr) * 1997-01-23 1998-07-29 Mitsubishi Materials Corporation Alliage à base de nickel résistant à la corrosion intergranulaire à des temperatures élevées ayant une structure de grains colonnaire, procédé de fabrication de cet alliage, pièce de grandes dimensions, et procédé de fabrication d'un pièce de grandes dimensions en cet alliage
WO1999067435A1 (fr) * 1998-06-23 1999-12-29 Siemens Aktiengesellschaft Alliage a solidification directionnelle a resistance transversale a la rupture amelioree

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US3619182A (en) * 1968-05-31 1971-11-09 Int Nickel Co Cast nickel-base alloy
GB1409628A (en) * 1973-06-26 1975-10-08 Avco Corp Nickel base alloy containing hafnium
GB2033925A (en) * 1978-09-25 1980-05-29 Johnson Matthey Co Ltd Nickel based superalloys
US4597809A (en) * 1984-02-10 1986-07-01 United Technologies Corporation High strength hot corrosion resistant single crystals containing tantalum carbide
GB2268937A (en) * 1992-07-23 1994-01-26 Abb Research Ltd Precipitation-hardenable, nickel-based superalloy
EP0855449A1 (fr) * 1997-01-23 1998-07-29 Mitsubishi Materials Corporation Alliage à base de nickel résistant à la corrosion intergranulaire à des temperatures élevées ayant une structure de grains colonnaire, procédé de fabrication de cet alliage, pièce de grandes dimensions, et procédé de fabrication d'un pièce de grandes dimensions en cet alliage
WO1999067435A1 (fr) * 1998-06-23 1999-12-29 Siemens Aktiengesellschaft Alliage a solidification directionnelle a resistance transversale a la rupture amelioree

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Publication number Publication date
EP1329527B1 (fr) 2006-05-10
CN1322157C (zh) 2007-06-20
JP2003231933A (ja) 2003-08-19
KR20030051386A (ko) 2003-06-25
KR100954683B1 (ko) 2010-04-27
UA73989C2 (en) 2005-10-17
DE60211297D1 (de) 2006-06-14
ATE325901T1 (de) 2006-06-15
ES2261604T3 (es) 2006-11-16
CN1432659A (zh) 2003-07-30
EP1329527A3 (fr) 2003-10-22
DE60211297T2 (de) 2007-04-26
US20030111138A1 (en) 2003-06-19
IL153479A0 (en) 2003-07-06
JP4413492B2 (ja) 2010-02-10
RU2295585C2 (ru) 2007-03-20

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