EP1329527B1 - 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 PDFInfo
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- EP1329527B1 EP1329527B1 EP02258710A EP02258710A EP1329527B1 EP 1329527 B1 EP1329527 B1 EP 1329527B1 EP 02258710 A EP02258710 A EP 02258710A EP 02258710 A EP02258710 A EP 02258710A EP 1329527 B1 EP1329527 B1 EP 1329527B1
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- single crystal
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000005260 corrosion Methods 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 9
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 66
- 239000000956 alloy Substances 0.000 claims abstract description 66
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910003468 tantalcarbide Inorganic materials 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 24
- 239000013078 crystal Substances 0.000 abstract description 23
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052735 hafnium Inorganic materials 0.000 abstract description 11
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 abstract description 11
- 229910052796 boron Inorganic materials 0.000 abstract description 9
- 238000007792 addition Methods 0.000 abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005495 investment casting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 101150110972 ME1 gene Proteins 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Images
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
-
- 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 an alloy 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 deoxidation 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 of, in weight percent: 11.94 Cr, 4.03 Ti, 1.84 Mo, 3.75 W, 5.15 Ta, 3.55 A1, 8.93 Co, 0.008 B, 0.02 Zr, 0.06 C and 0.01 Hf, balance nickel.
- the alloy for columnar grain directionally solidified articles has at least comparable oxidation resistance relative to single crystal counterparts, and corrosion resistance at least comparable to such alloys. Moreover the inventive alloy has oxidation resistance at least equal to equiaxed counterparts, and at least equal corrosion resistance.
- the alloy of the present invention provides articles in columnar grain directionally solidified form with superior oxidation resistance than comparable articles and alloys in equiaxed or single crystal form.
- 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.
- 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, 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 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 '652 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.
- Mod 4 A number of modifications (“Mod") were prepared by investment casting columnar grain articles, and were evaluated as described below. Overall the composition of Mod 4 is the claimed composition within the six listed below (all in wt.%) 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 effort 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.
- FIG. 3 shows the relative uncoated, burner rig oxidation resistance of Mod 4 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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Abstract
Description
- The present invention relates to the field of nickel base superalloys for use in directionally solidified articles, and more particularly to such an alloy providing articles having good mechanical properties at elevated temperatures, good resistance to hot corrosion, and good oxidation resistance.
- The increasing demands for efficiency in gas turbine engines have resulted in a demand for materials capable of withstanding more severe operating conditions. In particular, good strength is required for certain applications along with the resistance to hot corrosion, oxidation and creep.
- U.S. Pat. No. 3,619,182 describes a moderate strength superalloy, commercially known as IN 792, having purportedly superior corrosion resistance. The '182 patent describes an alloy having a composition, in weight percent, of: 9.5 - 14 Cr; 7 - 11 Co; 1 - 2.5 Mo; 3 - 4 W; 1 - 4 Ta; up to 1 Cb; 3 - 4 Al; 3 - 5 Ti; Al + Ti = 6.5 - 8; 0.005 - 0.05 B; 0.01 - 0.25 Zr; 0.02 - 0.25 C; bal. Ni. At the time the '182 application was filed, 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.
- An alloy, commonly known as GTD-111 which has been cast in equiaxed and directionally solidified forms. In equiaxed castings, 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. Patent GB 1,511,562 (13.7 - 14.3 Cr; 9 - 10 Co; 1 - 1.5 Mo; 4.8 - 5.5 Ti; 2.8 - 3.2 Al; 3.7 - 4.3 W; 1 - 1.5 Nb; 2.5 - 3 Ta; 2.8 - 3.2 Al; 0.08 - 0.2 C; 4.8 - 5.5 Ti; 0.01 - 0.02 B; 0.02 - 0.1 Zr; and either 1.5 - 3.5 mixture of Ta, Cb and Hf, or 2.5 - 3 Ta or 2 - 2.5 Hf or 1 - 1.5 Cb [or Ta + Cb + Hf = 1.5 - 3.5]; and consisting of a matrix and a monocarbide phase distributed through the matrix consisting of: Ti, Mo, W and/or Ta and/or Cb and/or Hf in proportions such that the total of Mo and W is less than 15 weight percent of the carbide phase). In directionally solidified castings, the nominal composition is similar except for slightly lower amounts of zirconium. See, G.K. Bouse, "Eta (η) and Platelet Phases in Investment Cast Superalloys", presented at Superalloys 1996, Seven Springs, PA.
- 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 deoxidation 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.
- The 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. % toIN 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. As a further step in the investigation, additions of tantalum were made to thebasic 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.
- As noted above, when adapting an alloy originally designed for use in single crystal articles for use in columnar grain directionally solidified applications, or adapting an alloy originally designed for use in equiaxed form for use as columnar grain directionally solidified applications, certain compositional changes are typically warranted to increase grain boundary strength and ductility. For example, 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. However, 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. In addition, hafnium promotes increased eutectic γ/γ' 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.
- It would be desirable to provide a material for the fabrication of columnar grain articles, and to provide such articles, which have adequate strength relative to comparable articles in single crystal form, and which also demonstrate at least comparable oxidation and corrosion resistance.
- It would also be desirable to provide the benefits of an alloy composition adapted for use as in columnar grain directionally-solidified parts while maintaining the benefits of the alloy as adapted for use in single crystal articles.
- It would likewise be desirable to provide such an alloy which provides oxidation resistance in columnar grain form at least comparable to that in single crystal form.
- It would be further desirable to provide such an alloy that provides adequate transverse ductility without the addition of hafnium.
- It would be yet further desirable to provide such an alloy which does not require a solution heat treatment in order to achieve adequate creep strength.
- It is known from WO-A-99/67435 to provide a directionally solidified columnar grain nickel base alloy casting having a composition in weight percent of : 12.00 Cr, 9.00 Co, 1.85 Mo, 3.70 W, 5.10 Ta, 3.60 Al, 4.00 Ti, 0.0125 B, 0.09 C, balance Ni.
- According to the present invention, there is provided 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 of, in weight percent: 11.94 Cr, 4.03 Ti, 1.84 Mo, 3.75 W, 5.15 Ta, 3.55 A1, 8.93 Co, 0.008 B, 0.02 Zr, 0.06 C and 0.01 Hf, balance nickel.
- The alloy for columnar grain directionally solidified articles has at least comparable oxidation resistance relative to single crystal counterparts, and corrosion resistance at least comparable to such alloys. Moreover the inventive alloy has oxidation resistance at least equal to equiaxed counterparts, and at least equal corrosion resistance. The alloy of the present invention provides articles in columnar grain directionally solidified form with superior oxidation resistance than comparable articles and alloys in equiaxed or single crystal form.
- In columnar grain form, 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. Typically 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. In the case of single crystal article, we believe that the articles can include high angles boundaries of up to and in excess of 20°. Where needed, 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. However, such articles as cast may have adequate creep strength (depending upon their intended use) such that solution heat treatment is unnecessary.
- The present invention will now be described in greater detail by way of example only and with reference to the accompanying drawings, in which:
- FIG. 1 is a graph illustrating the effect of carbon and boron on castability;
- FIG. 2 is a graph illustrating the relative hot corrosion resistance of an embodiment of the inventive alloy;
- FIG. 3 is a graph illustrating the relative oxidation resistance of an embodiment of the inventive alloy;
- FIGS. 4, 5 and 6 are graphs illustrating the creep rupture life of the inventive alloy; and
- FIG. 7 is a graph illustrating transverse creep ductility of an embodiment 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, 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. In columnar grain form, 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. We also considered the 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. We believe that 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 '652 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.
- We discovered that even small additions of zirconium detrimentally affected the castability of part, particularly large parts such as land based gas turbine engine blades. Articles having more than about 0.02 wt. % zirconium tended to tear after on investment casting, during cooling and solidification of the molten material. While not fully understood, the tearing problem was obviated where zirconium was present at a level of 0.02 wt. percent. In an effort to improve the tearing problem, we tried several compositions, including intentional additions of up to about 1.0 weight % hafnium which did not obviate the problem, and would be expected to increase the weight of the alloy and decrease the incipient melting temperature of the alloy. Such a result would also restrict the available temperature window for solution heat treatment of articles, particularly larger articles such as land based gas turbine components. Accordingly, we prefer that the alloy and articles include a 0.01 wt% addition of hafnium.
- A number of modifications ("Mod") were prepared by investment casting columnar grain articles, and were evaluated as described below. Overall the composition of
Mod 4 is the claimed composition within the six listed below (all in wt.%) 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 effort was brought about, in part, by siginificant hot tearing during casting of large parts.Alloy Cr Ti Mo W Ta Al Co H Lr C Hf GTD 111 1 14 4 4.9 1.5 3.8 2.8 3 9.5 0.01 0.02 0.1 U 4,597,809 12.2 4.2 1.9 3.8 5 3.6 9 0 0 0.01 0 Mod1 * 11.56 4.03 1.84 3.75 5.1 3.55 8.9 0.005 U.014 0.U7 U.49 Mod2 * 11.68 4.04 1.83 3.12 4.96 3.58 8.86 0.005 0.015 0.U6 0.88 Mod3 * 12.25 4.01 1.83 3.69 5.01 3.5 8.82 0.018 0.091 0.11 0.48 Mod4 11.94 4.03 1.84 3.75 5.15 3.55 8.93 0.008 0.02 0.06 0.01 Mod5 * 11.61 4.05 1.84 3.74 5.29 3.57 8.89 0.008 0.032 0.07 0.49 Mod6 * 11.9 4 1.82 3.7 4.93 3.52 8.79 U.U19 0.103 0.12 0.94 * comparative examples - 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 µm) 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.
- FIG. 3 shows the relative uncoated, burner rig oxidation resistance of
Mod 4 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. - The time to produce 1% creep was tested (in many cases both transverse and longitudinal) in specimens at 1400°F (760°C) with an applied stress of 85 ksi (586 Pa) and at 1800°F (982°C) with an applied stress of 27 ksi (189 Pa). The results are illustrated in FIGS. 4, 5 and 6. Again, the inventive alloy exhibited creep rupture lives exceeding the -111 alloy.
- 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.
- In sum, 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. Using the prior art columnar grain article, the present invention includes among other things significantly increasing tantalum, aluminum and molybdenum contents, and significantly decreasing the titanium and chromium contents. Using the prior art single crystal article, 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). In any event, 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.
Claims (4)
- 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 of, in weight percent: 11.94 Cr, 4.03 Ti, 1.84 Mo, 3.75 W, 5.15 Ta, 3.55 Al, 8.93 Co, 0.008 B, 0.02 Zr, 0.06 C and 0.01 Hf, balance nickel.
- The article of claim 1, wherein the article comprises a columnar grain, directionally solidified article.
- The article of claim 1 or 2, wherein the article comprises a gas turbine engine component.
- The article of claim 3, comprising a turbine blade or vane.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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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 EP1329527A2 (en) | 2003-07-23 |
EP1329527A3 EP1329527A3 (en) | 2003-10-22 |
EP1329527B1 true EP1329527B1 (en) | 2006-05-10 |
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EP02258710A Revoked EP1329527B1 (en) | 2001-12-18 | 2002-12-18 | High strength hot corrosion and oxidation resistant, directionally solidified nickel base superalloy and articles |
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US (1) | US20030111138A1 (en) |
EP (1) | EP1329527B1 (en) |
JP (1) | JP4413492B2 (en) |
KR (1) | KR100954683B1 (en) |
CN (1) | CN1322157C (en) |
AT (1) | ATE325901T1 (en) |
DE (1) | DE60211297T2 (en) |
ES (1) | ES2261604T3 (en) |
IL (1) | IL153479A0 (en) |
RU (1) | RU2295585C2 (en) |
UA (1) | UA73989C2 (en) |
Cited By (1)
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WO2011047714A1 (en) | 2009-10-20 | 2011-04-28 | Siemens Aktiengesellschaft | Alloy for directional solidification and component made of stem-shaped crystals |
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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 |
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 (en) * | 2006-06-16 | 2009-02-11 | 中国科学院金属研究所 | High strength antithermal corrosion low segregation directional high temp alloy |
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 |
EP2248923A1 (en) * | 2009-04-27 | 2010-11-10 | Siemens Aktiengesellschaft | Nickel base y/ý superalloy with multiple reactive elements and use of said superalloy in complex material systems |
US20110076182A1 (en) * | 2009-09-30 | 2011-03-31 | General Electric Company | Nickel-Based Superalloys and Articles |
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 |
EP2431489A1 (en) * | 2010-09-20 | 2012-03-21 | Siemens Aktiengesellschaft | Nickel-base superalloy |
CN102011195B (en) * | 2010-11-23 | 2012-06-06 | 北京科技大学 | Preparation method of directional solidification high-Nb TiAl alloy single crystal |
WO2012097915A1 (en) * | 2011-01-19 | 2012-07-26 | Siemens Aktiengesellschaft | 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 (en) * | 2011-11-16 | 2016-01-27 | 中国科学院金属研究所 | A kind of High-strength hot-corrosion-resistnickel-base nickel-base monocrystal high-temperature alloy |
US9404388B2 (en) | 2014-02-28 | 2016-08-02 | General Electric Company | Article and method for forming an article |
ITUA20161551A1 (en) * | 2016-03-10 | 2017-09-10 | Nuovo Pignone Tecnologie Srl | LEAGUE HAVING HIGH RESISTANCE TO OXIDATION AND APPLICATIONS OF GAS TURBINES THAT USE IT |
CN109234655B (en) * | 2018-09-27 | 2020-09-11 | 北京科技大学 | Method for improving relaxation stability of GH4169 high-temperature alloy |
FR3094018B1 (en) * | 2019-03-20 | 2022-02-04 | Safran | SUPERALLOY WITH OPTIMIZED PROPERTIES AND LIMITED DENSITY |
CN117660810B (en) * | 2024-01-31 | 2024-04-16 | 四川航大新材料有限公司 | High-purity high-temperature master alloy for variable-cycle gas engine turbine blade and preparation method and application thereof |
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US3619182A (en) * | 1968-05-31 | 1971-11-09 | Int Nickel Co | Cast nickel-base alloy |
US3615376A (en) * | 1968-11-01 | 1971-10-26 | Gen Electric | Cast nickel base alloy |
GB1409628A (en) * | 1973-06-26 | 1975-10-08 | Avco Corp | Nickel base alloy containing hafnium |
GB1511562A (en) * | 1974-07-17 | 1978-05-24 | Gen Electric | Nickel-base alloys |
GB2033925B (en) * | 1978-09-25 | 1983-07-20 | 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 |
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US6355117B1 (en) * | 1992-10-30 | 2002-03-12 | United Technologies Corporation | Nickel base superalloy single crystal articles with improved performance in air and hydrogen |
EP0637476B1 (en) * | 1993-08-06 | 2000-02-23 | Hitachi, Ltd. | Blade for gas turbine, manufacturing method of the same, and gas turbine including the blade |
DE69800263T2 (en) * | 1997-01-23 | 2001-02-08 | Mitsubishi Heavy Industries, Ltd. | Nickel-based alloy of stem-shaped crystals with good high-temperature resistance to intergranular corrosion, process for producing the alloy, large workpiece, and process for producing a large workpiece from this alloy |
WO1999067435A1 (en) * | 1998-06-23 | 1999-12-29 | Siemens Aktiengesellschaft | Directionally solidified casting with improved transverse stress rupture strength |
EP1204776B1 (en) * | 1999-07-29 | 2004-06-02 | Siemens Aktiengesellschaft | High-temperature part and method for producing the same |
-
2001
- 2001-12-18 US US10/023,565 patent/US20030111138A1/en not_active Abandoned
-
2002
- 2002-12-16 RU RU2002135012/02A patent/RU2295585C2/en not_active IP Right Cessation
- 2002-12-16 IL IL15347902A patent/IL153479A0/en unknown
- 2002-12-17 UA UA20021210223A patent/UA73989C2/en unknown
- 2002-12-18 CN CNB021542112A patent/CN1322157C/en not_active Expired - Fee Related
- 2002-12-18 DE DE60211297T patent/DE60211297T2/en not_active Expired - Lifetime
- 2002-12-18 AT AT02258710T patent/ATE325901T1/en not_active IP Right Cessation
- 2002-12-18 EP EP02258710A patent/EP1329527B1/en not_active Revoked
- 2002-12-18 ES ES02258710T patent/ES2261604T3/en not_active Expired - Lifetime
- 2002-12-18 JP JP2002366323A patent/JP4413492B2/en not_active Expired - Fee Related
- 2002-12-18 KR KR1020020081052A patent/KR100954683B1/en active IP Right Grant
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011047714A1 (en) | 2009-10-20 | 2011-04-28 | Siemens Aktiengesellschaft | Alloy for directional solidification and component made of stem-shaped crystals |
US9068251B2 (en) | 2009-10-20 | 2015-06-30 | Siemens Aktiengesellschaft | Alloy for directional solidification and component made of stem-shaped crystals |
EP3363923A1 (en) | 2009-10-20 | 2018-08-22 | Siemens Aktiengesellschaft | Alloy for directional solidification and component made of stem-shaped crystals |
Also Published As
Publication number | Publication date |
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ATE325901T1 (en) | 2006-06-15 |
CN1322157C (en) | 2007-06-20 |
KR20030051386A (en) | 2003-06-25 |
ES2261604T3 (en) | 2006-11-16 |
US20030111138A1 (en) | 2003-06-19 |
DE60211297T2 (en) | 2007-04-26 |
EP1329527A2 (en) | 2003-07-23 |
KR100954683B1 (en) | 2010-04-27 |
DE60211297D1 (en) | 2006-06-14 |
UA73989C2 (en) | 2005-10-17 |
CN1432659A (en) | 2003-07-30 |
EP1329527A3 (en) | 2003-10-22 |
RU2295585C2 (en) | 2007-03-20 |
JP2003231933A (en) | 2003-08-19 |
JP4413492B2 (en) | 2010-02-10 |
IL153479A0 (en) | 2003-07-06 |
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