EP2179068A2 - Corrosion resistant nickel alloy compositions with enhanced castability and mechanical properties - Google Patents
Corrosion resistant nickel alloy compositions with enhanced castability and mechanical propertiesInfo
- Publication number
- EP2179068A2 EP2179068A2 EP08794827A EP08794827A EP2179068A2 EP 2179068 A2 EP2179068 A2 EP 2179068A2 EP 08794827 A EP08794827 A EP 08794827A EP 08794827 A EP08794827 A EP 08794827A EP 2179068 A2 EP2179068 A2 EP 2179068A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- less
- alloy
- balance
- cast
- resistance
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000005260 corrosion Methods 0.000 title abstract description 10
- 230000007797 corrosion Effects 0.000 title abstract description 10
- 229910000990 Ni alloy Inorganic materials 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 70
- 239000000956 alloy Substances 0.000 claims abstract description 70
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 20
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 20
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 19
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 238000005050 thermomechanical fatigue Methods 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 17
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 17
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 16
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 16
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 229910000601 superalloy Inorganic materials 0.000 abstract description 3
- 238000007792 addition Methods 0.000 description 18
- 239000011651 chromium Substances 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910001011 CMSX-4 Inorganic materials 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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
- C22C19/056—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%
-
- 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%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
Definitions
- This invention relates in general to the field of nickel base superalloys possessing improved oxidation resistance, corrosion resistance, castability, and mechanical properties such as creep resistance and thermo-mechanical fatigue resistance.
- the present invention relates to alloys that may be cast as a single crystal or directionally solidified.
- Nickel base superalloys are alloys composed primarily of nickel with the addition of several other elements selected for their ability to survive an overall high temperature, high stress, and highly oxidative environment. Typically, this environment is that of a gas turbine engine.
- Fig. 1 illustrates comparative creep testing of embodiments of the present invention (called Alloys A and B) and a prior art alloy PWA 1483.
- Fig. 2 is a micrograph of Alloy A, after elevated temperature exposure to a thermally oxidized coal derived syngas test environment.
- Fig. 3 is a micrograph of Alloy B, after elevated temperature exposure to a thermally oxidized coal derived syngas test environment.
- Fig. 4 is a micrograph of the prior art alloy SieMet DS (PWA 1483 modified with grain boundary strengthening elements) after elevated temperature exposure to a thermally oxidized coal derived syngas test environment.
- Fig. 5 is a micrograph of another prior art alloy CM247LC after elevated temperature exposure to a thermally oxidized coal derived syngas test environment.
- the present invention provides an alloy composition that may be cast as a single crystal alloy or may be directionally solidified, and that has better castability than the prior art alloy available from Cannon-Muskegon Corporation under the registered trademark CMSX-4, has better corrosion resistance than alloy CM247LC available from that same source, and has better mechanical properties than the prior art alloy available through United Technologies Corporation under the trademark PWA 1483.
- Typical weight percent compositions of these prior art alloys are shown in Table 1.
- novel alloy compositions disclosed herein offer an improved set of properties that are particularly useful for application in Integrated Gasification Combined Cycle (IGCC) syngas fired gas turbines where relatively low quality fuels and high operating temperatures result in a highly corrosive environment.
- IGCC Integrated Gasification Combined Cycle
- Alloys of the present invention include Chromium (Cr) from 8-12 weight percent or about 10 weight percent to provide the compositions with a desired level of high temperature corrosion resistance.
- Alloys of the present invention may include Aluminum (Al) at a concentration that is lower than is generally observed in highly oxidation resistant alloys, for example as low as 2 weight percent or in the range of 2.0- 5.5 weight percent.
- Rare earth elements, Yttrium (Y), Silicon (Si), and Hafnium (Hf) are included to compensate for the reduction in Aluminum (Al) and to provide increased oxidation resistance.
- the alloy compositions disclosed herein have intentional additions of rare earth elements Lanthanum (La), Yttrium (Y), Gadolinium (Gd), Praseodymium (Pr), Dysprosium (Dy), Neodymium (Nd), and Erbium (Er) in combined amounts of up to 0.1 weight percent.
- These rare earth additions provide improved oxidation resistance of the inventive alloys and enhance the compatibility of the alloy compositions with various coatings.
- the rare earth additions also aid in increasing the life of any overlying protective ceramic coating.
- the increase in coating life through the addition of rare earth elements is attributed to their ability to form sulfides and oxi-sulfides that reduce the residual Sulfur (S) content and prevent the diffusion of sulfur atoms to the alumina scale that is formed at the boundary between the coating and the substrate alloy.
- Silicon (Si) is intentionally added to the present alloys to support the formation of a protective silicon dioxide surface oxide layer.
- the silicon dioxide provides enhanced oxidation resistance as the film is less susceptible to cracking compared with other protective oxide films. Excessive additions of silicon are detrimental to the performance of the alloy; consequently, an addition of less than 0.15 weight percent or in the range of 0.05-0.2 weight percent is preferred.
- Hafnium (Hf) at levels similar to those of Silicon or less than 0.5 weight percent serves to further enhance the oxidation resistance.
- An alloy composition consisting essentially of, by weight percent, 8- 12% Cr, 10-14% Co, 0.3-0.9% Mo, 3-7% W, 2-8% Ta, 2.0-5.5% Al, 1.5-5.0 % Ti, up to 2% Nb, less than 0.1% B, less than 0.1% Zr, 0.05-0.15% C, less than 0.5% Hf, 2-4% Re, 0.05-0.2% Si, up to 0.015% S (without intentional sulfur addition), up to 0.1% La, up to 0.1% Y, up to 0.1% Ce, up to 0.1% Nd, up to 0.1% Dy, up to 0.1% Pr, up to 0.1 % Gd, balance is Ni, and wherein (La+Y+Ce+Nd+Dy+Pr+Gd) is 0.001-0.1%, provides for an overall range of alloys that exhibit creep resistance, thermo-mechanical fatigue resistance, corrosion resistance, and the ability to be cast as a single crystal or directionally solidified alloy. All compositions herein are specified in weight percent values unless specified otherwise.
- compositions of this invention may be cast with processes known in the art.
- Fig. 1 is a comparison of the creep properties of two embodiments of the present invention with those of prior art PWA 1483. The test was conducted at a temperature of 850°C. Alloy A has increased refractory metal content and the addition of 3 weight percent Rhenium (Re), as shown in Table 2. Alloy A is an example of an embodiment of the alloy composition that is designed to be cast as a single crystal and have improved thermo-mechanical fatigue resistance at the expense of some creep resistance. Alloy B is an example of an embodiment of the alloy composition that is designed to be cast as a single crystal and have improved creep resistance at the expense of some thermo-mechanical fatigue resistance.
- CMSX-4 BaI 6.5 9.6 0.6 6.4 3 6.5 5.6 1 ⁇ 0.006 ...
- Figs. 2-5 are Scanning Electron Microscope (SEM) slides that show various alloys after exposure to the same thermally oxidized coal derived syngas environment at about 1 ,000 0 C. Both of the novel alloys (Figs 2-3) have survived the environment and Alloy B (Fig. 3) shows particularly good condition with little evidence of corrosive attack.
- the Siemet DS (PWA 1483 modified with grain boundary strengthening elements) shows sub-surface penetration as seen in Fig. 4 and the protective oxide has spalled on the CM247LC as seen in Fig. 5.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US95509207P | 2007-08-10 | 2007-08-10 | |
US12/173,983 US20090041615A1 (en) | 2007-08-10 | 2008-07-16 | Corrosion Resistant Alloy Compositions with Enhanced Castability and Mechanical Properties |
PCT/US2008/009137 WO2009023090A2 (en) | 2007-08-10 | 2008-07-29 | Corrosion resistant nickel alloy compositions with enhanced castability and mechanical properties |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2179068A2 true EP2179068A2 (en) | 2010-04-28 |
EP2179068B1 EP2179068B1 (en) | 2012-05-02 |
Family
ID=40346733
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08794827A Not-in-force EP2179068B1 (en) | 2007-08-10 | 2008-07-29 | Corrosion resistant nickel alloy compositions with enhanced castability and mechanical properties |
Country Status (4)
Country | Link |
---|---|
US (1) | US20090041615A1 (en) |
EP (1) | EP2179068B1 (en) |
AT (1) | ATE556154T1 (en) |
WO (1) | WO2009023090A2 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8708659B2 (en) | 2010-09-24 | 2014-04-29 | United Technologies Corporation | Turbine engine component having protective coating |
JP5146576B1 (en) | 2011-08-09 | 2013-02-20 | 新日鐵住金株式会社 | Ni-base heat-resistant alloy |
JP6016016B2 (en) * | 2012-08-09 | 2016-10-26 | 国立研究開発法人物質・材料研究機構 | Ni-based single crystal superalloy |
RU2530932C1 (en) * | 2013-10-29 | 2014-10-20 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Nickel-based cast heat resistant alloy and product made from it |
US9404388B2 (en) | 2014-02-28 | 2016-08-02 | General Electric Company | Article and method for forming an article |
CN103943297B (en) * | 2014-04-29 | 2016-06-01 | 黎明 | The preparation method of a kind of cobalt nickel base soft magnetic materials |
CN104476844A (en) * | 2014-12-23 | 2015-04-01 | 常熟市鑫吉利金属制品有限公司 | Anti-oxidation metal product |
GB2539959A (en) | 2015-07-03 | 2017-01-04 | Univ Oxford Innovation Ltd | A Nickel-based alloy |
JP6460336B2 (en) * | 2015-07-09 | 2019-01-30 | 三菱日立パワーシステムズ株式会社 | Ni-based high-strength heat-resistant alloy member, method for producing the same, and gas turbine blade |
RU2610577C1 (en) * | 2015-12-02 | 2017-02-13 | Федеральное государственное бюджетное учреждение науки Институт металлургии и материаловедения им. А.А. Байкова Российской академии наук (ИМЕТ РАН) | CASTING ALLOY BASED ON INTERMETALLIC COMPOUND Ni3Al, AND ARTICLE OUT OF IT |
US10967466B2 (en) * | 2017-04-20 | 2021-04-06 | Kennametal Inc. | Layered assemblies for superalloy article repair |
EP3839084A1 (en) * | 2019-12-20 | 2021-06-23 | David Jarvis | Metal alloy |
CN113913942A (en) * | 2021-01-13 | 2022-01-11 | 中国航发北京航空材料研究院 | Nickel-based single crystal alloy, use and heat treatment method |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE28681E (en) * | 1973-04-02 | 1976-01-13 | High temperature alloys | |
CA1212020A (en) * | 1981-09-14 | 1986-09-30 | David N. Duhl | Minor element additions to single crystals for improved oxidation resistance |
US5154884A (en) * | 1981-10-02 | 1992-10-13 | General Electric Company | Single crystal nickel-base superalloy article and method for making |
GB2235697B (en) * | 1986-12-30 | 1991-08-14 | Gen Electric | Improved and property-balanced nickel-base superalloys for producing single crystal articles. |
US4895201A (en) * | 1987-07-07 | 1990-01-23 | United Technologies Corporation | Oxidation resistant superalloys containing low sulfur levels |
US5240518A (en) * | 1990-09-05 | 1993-08-31 | General Electric Company | Single crystal, environmentally-resistant gas turbine shroud |
US5346563A (en) * | 1991-11-25 | 1994-09-13 | United Technologies Corporation | Method for removing sulfur from superalloy articles to improve their oxidation resistance |
US5395584A (en) * | 1992-06-17 | 1995-03-07 | Avco Corporation | Nickel-base superalloy compositions |
US7160400B2 (en) * | 1999-03-03 | 2007-01-09 | Daido Tokushuko Kabushiki Kaisha | Low thermal expansion Ni-base superalloy |
RU2215804C2 (en) * | 2001-10-08 | 2003-11-10 | Государственное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" | Nickel-base heat-resistant alloy and article made of thereof |
WO2003080882A1 (en) * | 2002-03-27 | 2003-10-02 | National Institute For Materials Science | Ni-BASE DIRECTIONALLY SOLIDIFIED SUPERALLOY AND Ni-BASE SINGLE CRYSTAL SUPERALLOY |
US20040042927A1 (en) * | 2002-08-27 | 2004-03-04 | O'hara Kevin Swayne | Reduced-tantalum superalloy composition of matter and article made therefrom, and method for selecting a reduced-tantalum superalloy |
CA2440573C (en) * | 2002-12-16 | 2013-06-18 | Howmet Research Corporation | Nickel base superalloy |
JP4449337B2 (en) * | 2003-05-09 | 2010-04-14 | 株式会社日立製作所 | High oxidation resistance Ni-base superalloy castings and gas turbine parts |
US20080008618A1 (en) * | 2003-12-26 | 2008-01-10 | Kawasaki Jukogyo Kabushiki Kaisha | Ni-Base Superalloy and Gas Turbine Component Using the Same |
-
2008
- 2008-07-16 US US12/173,983 patent/US20090041615A1/en not_active Abandoned
- 2008-07-29 EP EP08794827A patent/EP2179068B1/en not_active Not-in-force
- 2008-07-29 AT AT08794827T patent/ATE556154T1/en active
- 2008-07-29 WO PCT/US2008/009137 patent/WO2009023090A2/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2009023090A3 * |
Also Published As
Publication number | Publication date |
---|---|
EP2179068B1 (en) | 2012-05-02 |
WO2009023090A2 (en) | 2009-02-19 |
ATE556154T1 (en) | 2012-05-15 |
WO2009023090A3 (en) | 2009-07-16 |
US20090041615A1 (en) | 2009-02-12 |
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