US20030111138A1 - High strength hot corrosion and oxidation resistant, directionally solidified nickel base superalloy and articles - Google Patents

High strength hot corrosion and oxidation resistant, directionally solidified nickel base superalloy and articles Download PDF

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US20030111138A1
US20030111138A1 US10/023,565 US2356501A US2003111138A1 US 20030111138 A1 US20030111138 A1 US 20030111138A1 US 2356501 A US2356501 A US 2356501A US 2003111138 A1 US2003111138 A1 US 2003111138A1
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article
articles
alloy
titanium
aluminum
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US10/023,565
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Alan Cetel
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RTX Corp
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Priority to US10/023,565 priority Critical patent/US20030111138A1/en
Assigned to UNITED TECHNOLOGIES CORPORATION reassignment UNITED TECHNOLOGIES CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CETEL, ALAN D., SHAH, DILIP M.
Priority to IL15347902A priority patent/IL153479A0/xx
Priority to RU2002135012/02A priority patent/RU2295585C2/ru
Priority to UA20021210223A priority patent/UA73989C2/uk
Priority to KR1020020081052A priority patent/KR100954683B1/ko
Priority to ES02258710T priority patent/ES2261604T3/es
Priority to CNB021542112A priority patent/CN1322157C/zh
Priority to JP2002366323A priority patent/JP4413492B2/ja
Priority to AT02258710T priority patent/ATE325901T1/de
Priority to DE60211297T priority patent/DE60211297T2/de
Priority to EP02258710A priority patent/EP1329527B1/de
Publication of US20030111138A1 publication Critical patent/US20030111138A1/en
Abandoned legal-status Critical Current

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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.
  • the '182 patent is expressly incorporated herein by reference.
  • 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., Schilke, et el. “Advanced Materials Propel Progress in Land-Based Gas Turbines”, Advanced Materials and Processes, April 1992, page —— ; 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 at 1800° F.
  • 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.
  • 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.
  • 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. of at least roughly 2.5 ⁇ , creep rupture life at 1400° F. of at least roughly 2.4 ⁇ and at 1800° F. of at least roughly 1.5 ⁇ 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 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.
  • FIG. 1 is a graph illustrating preferred amounts of carbon and boron in accordance with the present invention.
  • FIG. 2 is a graph illustrating the relative hot corrosion resistance of the inventive alloy.
  • FIG. 3 is a graph illustrating the relative oxidation resistance of the inventive alloy.
  • FIGS. 4, 5 and 6 are graphs illustrating the creep rupture life of several variations of the inventive alloy.
  • FIG. 7 is a graph illustrating transverse creep ductility of the inventive alloy.
  • 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 composition of an alloy generally designated “GTD-111”, see, 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 essentially of, in weight percent, about 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; 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 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 (any 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.
  • the articles to be evaluated were investment cast, and then given similar heat treatments—a solution heat treat at about 2050° F. for 2 hours, followed by precipitation heat treat at 1975 F. for 4 hours, followed by stabilization heat treat at about 1550° F. for 24 hours. In some cases, articles were solution heat treated at 2150-2200° F. for less time, but showed no significant increase in properties.
  • 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. 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 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. and several other alloys. While the oxidation resistance exceeds the oxidation resistance of GTD-111, Mod 4 is significantly higher (at least 2.5 ⁇ ) 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)
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  • Powder Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
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US10/023,565 2001-12-18 2001-12-18 High strength hot corrosion and oxidation resistant, directionally solidified nickel base superalloy and articles Abandoned US20030111138A1 (en)

Priority Applications (11)

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
IL15347902A IL153479A0 (en) 2001-12-18 2002-12-16 High strength hot corrosion and oxidation resistant, directionally solidified nickel base superalloy and articles
RU2002135012/02A RU2295585C2 (ru) 2001-12-18 2002-12-16 Высокопрочный, стойкий к высокотемпературной коррозии и окислению суперсплав на основе никеля и направленно отвержденное изделие из этого суперсплава
UA20021210223A UA73989C2 (en) 2001-12-18 2002-12-17 High-strength, corrosion-resistant superalloy based on nickel and unidirectional article
EP02258710A EP1329527B1 (de) 2001-12-18 2002-12-18 Hochfeste heisskorrosions- und oxidationsbeständige, gerichtet erstarrte Superlegierung auf Nickelbasis und Gegenstände
DE60211297T DE60211297T2 (de) 2001-12-18 2002-12-18 Hochfeste heisskorrosions- und oxidationsbeständige, gerichtet erstarrte Superlegierung auf Nickelbasis und Gegenstände
ES02258710T ES2261604T3 (es) 2001-12-18 2002-12-18 Superaleaciones base niquel solidificadas direccionalmente, con elevada resistencia a la corrosion en caliente y resistentes a la oxidacion y articulos.
KR1020020081052A KR100954683B1 (ko) 2001-12-18 2002-12-18 고강도 내부식성 및 내산화성의 니켈계 초합금 및 이를 포함하는 방향성 고화 제품
CNB021542112A CN1322157C (zh) 2001-12-18 2002-12-18 高强度抗热腐蚀性和氧化性的定向凝固镍基超级合金及其制品
JP2002366323A JP4413492B2 (ja) 2001-12-18 2002-12-18 方向性凝固部品およびニッケル基超合金
AT02258710T ATE325901T1 (de) 2001-12-18 2002-12-18 Hochfeste heisskorrosions- und oxidationsbeständige, gerichtet erstarrte superlegierung auf nickelbasis und gegenstände

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

Cited By (11)

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US20060182649A1 (en) * 2005-02-16 2006-08-17 Siemens Westinghouse Power Corp. High strength oxidation resistant superalloy with enhanced coating compatibility
US20100080729A1 (en) * 2006-06-02 2010-04-01 Power Systems Manufacturing, Llc Nickel-base alloy for gas turbine applications
US20100254822A1 (en) * 2009-03-24 2010-10-07 Brian Thomas Hazel Super oxidation and cyclic damage resistant nickel-base superalloy and articles formed therefrom
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
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
US20110076180A1 (en) * 2009-09-30 2011-03-31 General Electric Company Nickel-Based Superalloys and Articles
US9404388B2 (en) 2014-02-28 2016-08-02 General Electric Company Article and method for forming an article
EP2520678A3 (de) * 2011-05-04 2016-12-14 General Electric Company Legierungen auf Nickelbasis
CN113584349A (zh) * 2016-03-10 2021-11-02 诺沃皮尼奥内技术股份有限公司 高抗氧化合金和使用所述合金的燃气涡轮机应用
US11821060B2 (en) 2019-03-20 2023-11-21 Safran Superalloy with optimized properties and a limited density

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US20050069450A1 (en) * 2003-09-30 2005-03-31 Liang Jiang Nickel-containing alloys, method of manufacture thereof and articles derived thereform
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
EP2248923A1 (de) * 2009-04-27 2010-11-10 Siemens Aktiengesellschaft y/ý-Superlegierung auf Nickelbasis mit mehreren reaktiven Elementen und Verwendung besagter Superlegierung in komplexen Materialsystemen
EP3363923A1 (de) 2009-10-20 2018-08-22 Siemens Aktiengesellschaft Legierung zur gerichteten erstarrung und bauteil aus stängelförmigen kristallen
EP2431489A1 (de) * 2010-09-20 2012-03-21 Siemens Aktiengesellschaft Superlegierung auf Nickelbasis
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
JP5745092B2 (ja) * 2011-01-19 2015-07-08 シーメンス アクティエンゲゼルシャフト ターボ機械ロータ用の平軸受、および平軸受を有するターボ機械
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
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
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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US5611670A (en) * 1993-08-06 1997-03-18 Hitachi, Ltd. Blade for gas turbine
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060182649A1 (en) * 2005-02-16 2006-08-17 Siemens Westinghouse Power Corp. High strength oxidation resistant superalloy with enhanced coating compatibility
US20100080729A1 (en) * 2006-06-02 2010-04-01 Power Systems Manufacturing, Llc Nickel-base alloy for gas turbine applications
US9322089B2 (en) 2006-06-02 2016-04-26 Alstom Technology Ltd Nickel-base alloy for gas turbine applications
EP2069546A4 (de) * 2006-07-25 2017-02-08 General Electric Technology GmbH Nickel-basen-legierung für gasturbinenanwendungen
US20100254822A1 (en) * 2009-03-24 2010-10-07 Brian Thomas Hazel Super oxidation and cyclic damage resistant nickel-base superalloy and articles formed therefrom
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
US20110076180A1 (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
US20110076182A1 (en) * 2009-09-30 2011-03-31 General Electric Company Nickel-Based Superalloys and Articles
EP2520678A3 (de) * 2011-05-04 2016-12-14 General Electric Company Legierungen auf Nickelbasis
US9404388B2 (en) 2014-02-28 2016-08-02 General Electric Company Article and method for forming an article
CN113584349A (zh) * 2016-03-10 2021-11-02 诺沃皮尼奥内技术股份有限公司 高抗氧化合金和使用所述合金的燃气涡轮机应用
US11821060B2 (en) 2019-03-20 2023-11-21 Safran Superalloy with optimized properties and a limited density

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KR100954683B1 (ko) 2010-04-27
EP1329527A3 (de) 2003-10-22
CN1432659A (zh) 2003-07-30
EP1329527B1 (de) 2006-05-10
ATE325901T1 (de) 2006-06-15
RU2295585C2 (ru) 2007-03-20
JP2003231933A (ja) 2003-08-19
EP1329527A2 (de) 2003-07-23
KR20030051386A (ko) 2003-06-25
JP4413492B2 (ja) 2010-02-10
CN1322157C (zh) 2007-06-20
IL153479A0 (en) 2003-07-06

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