US3723108A - Nickel-chromium-cobalt alloys - Google Patents

Nickel-chromium-cobalt alloys Download PDF

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Publication number
US3723108A
US3723108A US00016367A US3723108DA US3723108A US 3723108 A US3723108 A US 3723108A US 00016367 A US00016367 A US 00016367A US 3723108D A US3723108D A US 3723108DA US 3723108 A US3723108 A US 3723108A
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alloys
chromium
nickel
titanium
columbium
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US00016367A
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English (en)
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P Twigg
P Parry
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Huntington Alloys Corp
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International Nickel Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%

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  • alloys contemplated herein contain (in weight 3,723,108 Patented Mar. 27, 1973 percent) from 23.5% to 26% chromium, about 0.01% to 0.2% carbon, about 10% to 24% cobalt, from 4.25% to 5.6% in total of titanium plus aluminum, the ratio of titanium to aluminum being from about 1:1 to 4:1, from about 0.25% to 2% columbium, with the proviso that the total percentage of titanium plus aluminum is so related to the percentage of columbium that it advantageously corresponds to a point in the area BCDEB in the accompanying drawing, from about 0.5% to 2% molybdenum, from 0.001% to 0.05% boron, e.g.
  • the minimum chromium content of 23.5% is dictated by the need for the greatest corrosion-resistance, but more than about 26% leads to embrittlement or loss of stress-rupture strength or both.
  • the chromium should be from 24% to 25%.
  • Cobalt strengthens the alloys and at least 10%, preferably at least 12%, and most advantageously at least 14% is required for this purpose. Should the cobalt much exceed 24% the alloys tend to undesirably embrittle on prolonged heating and this tendency can be lessened with cobalt levels that do not extend beyond 22%.
  • the alloys are further and principally strengthened by titanium, aluminum, columbium and molybdenum. If the combined titanium and aluminum content is less than 4.25%, stress-rupture life is inadequate. Moreover, having regard to the columbium content the impact strength after prolonged heating at 850 C. is also inadequate if the combined titanium plus aluminum is too great. This is illustrated by the point lying above and to the right of the line AC in the accompanying drawing, in which the sum of the titanium plus aluminum is correlated with (and plotted against) columbium. Stressrupture life is generally improved by the presence of columbium, and advantageously the alloys contain at least 0.25% and most beneficially at least 0.5%.
  • columbium exceeds about 2% the alloys have unnecessarily low stress-rupture lives and low room temperature impact resistance.
  • the amount of columbium can be reduced below 0.25 and down to the zero level provided that it is correlated with the titanium plus aluminum as to represent a point within the area ABEFA of the drawing.
  • each alloy nominally contained 0.003% boron and 0.05% zirconium.
  • the alloys were vacuum-melted, an addition of 0.03% magnesium being made as a Ni-15% magnesium at 1150 C., air cooled, and then exposed for a period of 1000 hours at 850 C.
  • ratios of titanium to aluminum less than 1:1 lead to loss of stress-rupture ductiliy and a lowering of impact resistance while if the ratio exceed 4:1 the stressrupture strength is inadequate.
  • the ratio is from 1:1 to 2.5:1.
  • alloys nominally containing, in addition to chromium, molybdenum and boron in the amounts shown, 0.04% carbon, 20% cobalt, 3% titanium, 1.5% aluminium, 1% niobium, 0.04% zirconium, balance, apart from impurities, nickel.
  • the alloys were prepared, heat-treated and tested as described with reference to Table I, but with additional stress-rupture property determinations being carried out at 14 ton-f./in. and 815 C.
  • the alloys In the absence of molybdenum, the alloys lack stressrupture strength, and at least 0.5% molybdenum must be present. As the molybdenum content increases, the stressrupture life increases up to about 2% molybdenum and then decreases slightly, but the impact strength after prolonged heating at 850 C. decreases progressively with increasing molybdenum contents. Though the molybdenum might be as high as 2.2% contents above about 2% tend to give rise to the risk of sigma-phase formation. Most beneficially, the molybdenum content is from 0.5 or 1% to 2%.
  • the molybdenum effect is shown in Table H concerning alloys nominally containing, in addition to molybdenum, titanium and aluminium in the amounts shown, at a TizAl ratio of 2:1, 0.04% carbon, 25% chromium, 20% cobalt, 0.003% boron, 0.05% zirconium, 0.02% magnesium, the balance being nickel and impurities.
  • the alloys were prepared, heat-treated and tested as described in connection with Table I. Alloy No. 2 is in accordance with the invention, but Alloys H and K are not.
  • the boron content should be at least 0.003%, the molybdenum content less than 2% and the chromium content less than 26%.
  • the resistance of alloys according to the invention to corrosion by the combustion products of impure hydrocarbon fuels and by marine salts has been determined by tests in which specimens were exposed to a molten mixture of 25 by Weight of sodium chloride and 75% sodium sulfate at 900 C. The corrosion damage was assessed by comparing the weight of each specimen, after removing the corrosion products by cathodic descaling in molten sodium hydroxide, with the initial weight before exposure.
  • Test A Samples of each alloy were half-immersed in the salt mixture while heated in air.
  • Test B Samples of each alloy were heated in a vertical open-top furnace into which the salt mixture was continuously fed as a fine dispersion at a rate of 5 g./hour.
  • hafnium can be present in amounts up to 0.1%, for example, from 0.02% to 0.07%, to improve the weldability of the alloys, especially those containing both boron and zirconium.
  • Magnesium is advantageously added in amounts up to 0.04% to improve workability, but larger amounts have the opposite effect rendering working more diflicult. Most suitably the magnesium content is from 0.01% to 0.03%.
  • the resistance of the alloys to oxidation and scaling is improved by the presence of rare earth metals, and one or more of these metals can be added, for example in the form of Mischmetall. From 0.01% to 0.3% of rare earth metal, e.g. from 0.03% to 0.08%, has distinct benefit.
  • yttrium additions also improve the oxidation and scaling resistance of the alloys and also their resistance to sulfidation.
  • yttrium can advantageously be added in amounts from 0.2% to 2%, for example, from 0.5% to 1%.
  • silicon has a deleterious effect on corrosion-resistance and should therefore be kept below 1% and preferably below 0.5%.
  • Other impurities may include manganese in amounts up to 1% and iron in amounts up to 2%.
  • Teantalum may be introduced incidentally with columbium in an amount up to about one-tenth thereof. For purposes herein, such amounts of tantalum are to be regarded as part of the columbium content.
  • alloys containing from 24% to chromium, 19% to 22% cobalt, 0.03% to 0.06% carbon, 2.8% to 3.2% titanium, 1.4% to 1.6% aluminum, 0.5% to 1.0% columbium, 1.8% to 2.0% molybdenum, 0.001% to 0.006% boron, 0.03% to 0.06% zirconium, up to 0.03% magnesium, up to 0.07% hafnium, up to 0.3% rare earth metal and up to 1% yttrium, the balance, apart from impurities, being nickel.
  • Other advantageous alloys contain from 14% to 17% cobalt, the balance of their composition being as set forth above.
  • Further advantageous alloys contain from 19% to 22% cobalt, 1.4% to 1.6% molybdenum and 0.010% to 0.015% boron, the balance of their composition being as set forth above.
  • a particularly preferred alloy has the nominal composition 24.5% chromium, 20% cobalt, 1.5% molybdenum, 3% titanium, 1.5% aluminum, 1% niobium, 0.04% zirconium, 0.012% boron, 0.04% carbon, balance nickel apart from impurities.
  • the solution treatment may consist of heating from 1 to 8 hours in the temperature range of 1050 C. to 1250" C., and the alloys may then be aged by heating for 1 to 24 hours in the temperature range of 600 C. to 950 C.
  • An intermediate aging treatment consisting of heating for 1 to 16 hours at 800 C. to 1050 C. may
  • the alloys may be cooled at any convenient rate after each heat treatment stage, e.g., by air cooling (generally to room temperature) or by direct transfer from a furnace at one temperature to one at a lower temperature.
  • the alloys can be air melted, but to ensure the best creep properties they are preferably melted and cast under vacuum. They can be readily processed by conventional means such as extrusion, forging or rolling. Although they are primarily intended for use in the wrought form as gas turbine blades, they are suitable for use in other applications where a combination of good-stressrupture strength and resistance to corrosion is required, particularly for articles and parts that are subject in use to stress at high temperatures while exposed to the combustion products of impure hydrocarbon fuels or to salt or both. They may also be used to make cast articles and parts, which may be used with or without heat treatment.
  • the alloys of the invention are also useful as matrix materials for alloys dispersion-hardened by the presence of finely divided refractory particles such as thoria, yttria, lanthana, ceria, or rare earth oxide mixtures, such as didimia.
  • the refractory compound may suitably be present in an amount of at least 0.2%, preferably 0.5 to 5%, by volume and the particles should preferably be maintained as fine as possible, for example below 0.5 micron, most suitably from 10 angstroms to 1000 angstroms (0.001 to 0.1 micron).
  • the present invention includes the use of the alloys as matrix materials in dispersionhardened alloys.
  • a nickel-chromium alloy characterized by a combination of good stress-rupture strength, tensile ductility and the ability to absorb impact energy together with resistance to various corrosive media, said alloy consisting of from 23.5% to 26% chromium, about 0.01% to about 0.2% carbon, from 10% to 24% cobalt, from 4.25% to 5.6% in total of titanium plus aluminum, the ratio of titanium to aluminum being from 1:1 to 4:1, from 0.25% to 2% columbium with the proviso that the total percentage of titanium plus aluminum is correlated with the columbium so as to represent a point within the area BCDEB of the accompanying drawing, from 0.5% to 2.2% molybdenum, from 0.001% to 0.05% boron, up to 0.15% zirconium, the sum of 10 percent B+ percent Zr being at least 0.02%, up to 2% iron, up to 1% silicon, up to 1% manganese, up to about 0.1% hafnium, up to 0.04% magnesium, up to 0.3% rare earth metal,
  • An alloy in accordance with claim 1 containing 24% to 25% chromium, at least 14% cobalt, magnesium present in an amount up to 0.03%, from 0.001% to 0.003% boron, up to 0.5% silicon, the alloy being characterized by a stress rupture strength on the order of 280 hours or higher at a temperature of about 815 C. under a stress of 17 ton-f./in. while concomitantly exhibiting an impact strength at room temperature of at least 10 ft.-lbs.
  • An alloy in accordance with claim 2 containin 0.015% to 0.08% carbon, 14% to 22% cobalt, and 0.5% to 2% columbium, the alloy being characterized by a stress rupture strength on the order of 280 hours or higher at a temperature of about 815 C. under a stress of 17 ton-f./in. while concomitantly exhibiting an impact strength at room temperature of at least 10 ft.-lbs.
  • a nickel-chromium alloy characterized by a stress rupture strength on the order of 280 hours or higher at a temperature of about 815 C. under a stress of 17 ton-f./in. while concomitantly exhibiting an impact strength at room temperature of at least 10 ft.-lbs.
  • said alloy consisting of from 23.5% to 26% chromium, about 0.01% to about 0.2% carbon, from 10% to 24% cobalt, from 4.25% to 5.6% in total of titanium plus aluminum, the ratio of titanium to aluminum being from 10 1:1 to 4:1, up to 2% columbium with the proviso that the total percentage of titanium plus aluminum is correlated with the columbium so as to represent a point within the area ACDFA of the accompanying drawing,

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
US00016367A 1969-03-07 1970-03-04 Nickel-chromium-cobalt alloys Expired - Lifetime US3723108A (en)

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GB02260/69A GB1298942A (en) 1969-03-07 1969-03-07 Nickel-chromium-cobalt alloys

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US (1) US3723108A (xx)
AT (1) AT304091B (xx)
BE (1) BE746969A (xx)
CA (1) CA922935A (xx)
CH (1) CH511943A (xx)
DE (1) DE2010055C3 (xx)
FR (1) FR2037772A5 (xx)
GB (1) GB1298942A (xx)
NL (1) NL7002990A (xx)
SE (1) SE364733B (xx)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4050929A (en) * 1975-12-01 1977-09-27 Kubota, Ltd. Heat resisting alloyed steel
US4050927A (en) * 1975-12-01 1977-09-27 Kubota, Ltd. Alloyed steel
US4140555A (en) * 1975-12-29 1979-02-20 Howmet Corporation Nickel-base casting superalloys
US6258317B1 (en) 1998-06-19 2001-07-10 Inco Alloys International, Inc. Advanced ultra-supercritical boiler tubing alloy
US6761854B1 (en) 1998-09-04 2004-07-13 Huntington Alloys Corporation Advanced high temperature corrosion resistant alloy
US20050069450A1 (en) * 2003-09-30 2005-03-31 Liang Jiang Nickel-containing alloys, method of manufacture thereof and articles derived thereform
US20060222557A1 (en) * 2004-09-03 2006-10-05 Pike Lee M Jr Ni-Cr-Co alloy for advanced gas turbine engines

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1484521A (en) * 1975-07-17 1977-09-01 Inco Europ Ltd Nickel-chromium-cobalt alloys
CA1202505A (en) * 1980-12-10 1986-04-01 Stuart W.K. Shaw Nickel-chromium-cobalt base alloys and castings thereof
US4755240A (en) * 1986-05-12 1988-07-05 Exxon Production Research Company Nickel base precipitation hardened alloys having improved resistance stress corrosion cracking
CN104762530A (zh) * 2014-05-21 2015-07-08 北京北冶功能材料有限公司 一种碳化物强化的高性能镍基铸造高温合金
CN112643024B (zh) * 2020-12-15 2021-12-10 上海海事大学 用于保护极地破冰船上破冰带的钴基合金粉末的制备方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4050929A (en) * 1975-12-01 1977-09-27 Kubota, Ltd. Heat resisting alloyed steel
US4050927A (en) * 1975-12-01 1977-09-27 Kubota, Ltd. Alloyed steel
US4140555A (en) * 1975-12-29 1979-02-20 Howmet Corporation Nickel-base casting superalloys
US6258317B1 (en) 1998-06-19 2001-07-10 Inco Alloys International, Inc. Advanced ultra-supercritical boiler tubing alloy
US6761854B1 (en) 1998-09-04 2004-07-13 Huntington Alloys Corporation Advanced high temperature corrosion resistant alloy
US20050069450A1 (en) * 2003-09-30 2005-03-31 Liang Jiang Nickel-containing alloys, method of manufacture thereof and articles derived thereform
US20060222557A1 (en) * 2004-09-03 2006-10-05 Pike Lee M Jr Ni-Cr-Co alloy for advanced gas turbine engines
US8066938B2 (en) 2004-09-03 2011-11-29 Haynes International, Inc. Ni-Cr-Co alloy for advanced gas turbine engines

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Publication number Publication date
CA922935A (en) 1973-03-20
FR2037772A5 (xx) 1970-12-31
GB1298942A (en) 1972-12-06
NL7002990A (xx) 1970-09-09
AT304091B (de) 1972-12-27
DE2010055A1 (de) 1971-02-25
DE2010055B2 (de) 1978-05-24
BE746969A (fr) 1970-09-07
CH511943A (fr) 1971-08-31
SE364733B (xx) 1974-03-04
DE2010055C3 (de) 1979-01-25

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