US3723107A - Nickel-chromium-cobalt alloys for use at relatively high temperatures - Google Patents

Nickel-chromium-cobalt alloys for use at relatively high temperatures Download PDF

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Publication number
US3723107A
US3723107A US00016091A US3723107DA US3723107A US 3723107 A US3723107 A US 3723107A US 00016091 A US00016091 A US 00016091A US 3723107D A US3723107D A US 3723107DA US 3723107 A US3723107 A US 3723107A
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alloys
chromium
nickel
molybdenum
titanium
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US00016091A
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E Richards
P Fontaine
M Fleetwood
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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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  • Nickel-chromium-cobalt-base alloys containing correlated amounts of titanium, aluminum, columbium and, when present, molybdenum, as well as carbon and other constituents offer a combination of high temperature stress-rupture strength, ductility and impact resistance together with good corrosion resistance of such magnitude as to render the materials suitable for various gas turbine engine components.
  • alloys capable of delivering in use certain metallurgical properties.
  • Such alloys have been of the nickel-chromium or cobaltchromium-base variety (rather exotically termed superalloys) and have found extensive utility in a number of high temperature applications.
  • these alloys contain one or more such elements as titanium, aluminum, columbium (niobium), molybdenum, etc., primarily for the purpose of imparting strength and hardness properties.
  • alloys contemplated herein contain (in weight percent) from 19.5% to 23% chromium, about 0.01% to 0.2% carbon, about 10% to 24% cobalt, from 3% to 7% in total of titanium plus aluminum, the ratio of titanium to aluminum being from about 1:1 to 4: 1, from about 0.5% to 2% columbium, with the proviso that the total percentage of titanium plus aluminum is so related to the percentage of columbium that it is represented by a point in the area ABCDEA of the accompanying drawing, up to 4.5% molybdenum, from 0.001% to 0.05% boron, e.g.
  • 0.01% to 0.01% or 0.02% up to 0.15% zirconium, with the further proviso that ten times the percentage of boron plus the percentage of zirconium is at least 0.02%, upto about 0.1% hafnium, up to about 0.04% magnesium, up to about 0.3% rare earth metal, up to about 2% yttrium, and the balance, apart from impurities, being essentially nickel.
  • the minimum chromium content of 19.5% is dictated by the need for the greatest corrosion-resistance, but more than 23%, having in mind the relatively high total percentage of titanium, aluminum, columbium and molybdenum that can be employed, leads to embrittlement or loss of stressrupture strength or both. 'In striving for the best combination of results the chromium should be from 20.5% to 22.5%.
  • Cobalt strengthens the alloys and at least 10%, preferably at least 14%, is required for this purpose. Should the cobalt exceed 24% the alloys tend to .undesirably embrittle on prolonged heating and advantageously it does not exceed 22%.
  • the alloys are further and principally strengthened by titanium, aluminum, columbium and, provided certain conditions are observed, the presence of molybdenum is also most advantageous.
  • the percentages of columbium and molybdenum and the sum of the contents of titanium and aluminum must also be interrelated in a manner that will be described with reference to FIG. 1 of the accompanying drawing. Prefacing this however, it should be emphasized that stress-rupture life is generally improved by colurnbium, and the alloys must contain at least 0.5% and preferably at least 1.0% thereof. Should the columbium exceed 3% the alloys have inadequate stress-rupture lives and may tend to embrittle. Moreover, subject to what is set forth hereinafter, as the molybdenum content increases stress-rupture life increases, and it is most beneficial that the alloys contain at least about 2% molybdenum.
  • the (Ti+Al) and Ch contents must be represented by a point in the area ABCDEA, where the point C is 6% (Ti+Al) and 3% Ch.
  • the amounts of (Ti+Al) and Cb must be represented by a point in the area A B C D EA where the point C is 5.65% (Ti+Al) and 2.7% Cb
  • the alloys when the alloys contain 4% molybdenum, the (Ti+Al) and Cb percentages must be represented by a point in the area A B C D4EA where the point C, is 4.6% (T i+Al) and 1.8% Cb.
  • Corresponding areas defining the relationship between (Ti+Al) and Cb for other contents of molybdenum between 0 and 4.5% are obtained by the following geometrical construction.
  • a line is drawn from the point X (7.9% Ti-l-Al and 3.4% Cb) through the point of the line AF corresponding to the molybdenum content (n percent) of the alloy, and extended to interwere generally inferior in respect of one or other propsect the line AB in the point A which represents the erty to the alloys according to the invention having commaximum (Ti-t-Al) content of the alloy.
  • the ingots were hot-worked to Spam h d h y bar from which stress-rupture test-pieces were machined F f f ,iescalmg m mo ten so mm y mm 1 wlt the and given a heat treatment consisting of solution heating 9 Welght before exposure
  • the resistant for 4 hours at 11500 C air cooling, aging for 16 hours terials are those that show the least loss in weight. at 850 C., and again air cooling.
  • the stress-rupture The tests were Performed in two Ways: life and elongation to rupture were determined on speci- Test A: Samples of each alloy were half-immersed in mens of each alloy under a stress of 17 ton-f./1n. at the Salt mixture While heated in air.
  • Test B Samples of each alloy were heated in a vertical 815 C. Further test-pieces were solution heated for 4 0 hours at 1150 C., air cooled, and then heated for 1000 hours at 850 C., and again air cooled, the Charpy V-notch impact strength being thereafter determined at open-top furnace into which the salt mixture was con tinuously fed as a fine dispersion at a rate of 5 g./hour.
  • FIGS. 2 to 4 of the accompanying drawing represent the areas from FIG. 1
  • composition Wt. percent 1 0.036
  • boron and to a lesser extent zirconium both improve the stress-rupture strength, and the alloys must contain at least 0.001% but not more than 0.05% boron, since amounts larger than 0.05% boron impair the forgeability of the alloys.
  • Zirconium may be present in amounts up to 0.15%, and the combined amount of boron and zirconium, as expressgd by percent B+percent Zr should be at least 0.02 o.
  • Hafnium can be present in amounts up to 0.1%, for example, from 0.02% to 0.07%, to improve weldability, 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 and make working more difiicult. 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 may be added, for example, in the form of Mischmetall.
  • rare earth metals e.g., from 0.03% to 0.08%, is added.
  • yttrium additions also improve the oxidation and scaling resistance of the alloys and their resistance to sulfidation, and yttrium can advantageously be added in amounts from 0.2% to 2%, for example, from 0.5% to 10%.
  • yttrium-containing alloy Alloy No. 18, which contains 0.04% C, 22% Cr, Co, 4% Mo, 3.1% Ti, 1.6% A1, 1% Cb, 0.05% Zr, 0.003% B and 1% Y, the balance, apart from impurities, being nickel, had after heat treating as for the alloys in Table I, a stress-rupture life at 17 ton-f./in. at 815 C. of 403 hours with an elongation of 8.6% and a Charpy V- notch impact strength at room temperature, after heating at 850 C. for 1000 hours, of 12.2 ft. lb.
  • 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%. Tantalum may be introduced incidentally with the columbium in an amount up to about one-tenth of the columbium content. For the purposes of the present invention, such amounts of tantalum are to be regarded as part of the columbium content.
  • 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 be interposed between the solution treatment and the final aging stages.
  • the alloys may be cooled at any convenient rate after each heat treatment stage, e.g., by air cooling 6 (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 also require heat treatments to develop their strength properties.
  • 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 dispersion-hardened 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 good resistance to various corrosive media, the stress rupture strength being at least about 300 hours at a temperature of about 815 C. under a stress of 17 ton-f./in.
  • said alloy consisting of from 19.5% to 23% chromium, about 0.01% to about 0.2% carbon, from 10% to 24% cobalt, about 3.7% to 7% in total of titanium plus aluminum, the ratio of titanium to aluminum being from 1:1 to 4:1, from 0.5% to 3% columbium, up to 4.5% molybdenum, with the proviso that the total percentage of titanium plus aluminum is correlated with the columbium and molybdenum so as to represent a point within the area ABCDEA of FIG.
  • An alloy in accordance with claim 1 containing from 20.5% to 22.5 chromium, from 0.015% to 0.08% carbon, 15% to 22% cobalt, 4% to 5% titanium plus aluminum, the ratio of titanium to aluminum being up to 3:1, 1.0% to 1.7% columbium, 3.5% to 4.2% 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Heat Treatment Of Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US00016091A 1969-03-07 1970-03-04 Nickel-chromium-cobalt alloys for use at relatively high temperatures Expired - Lifetime US3723107A (en)

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GB02261/69A GB1298943A (en) 1969-03-07 1969-03-07 Nickel-chromium-cobalt alloys

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AT (1) AT304092B (de)
BE (1) BE746970A (de)
CA (1) CA923340A (de)
CH (1) CH517830A (de)
DE (1) DE2010054A1 (de)
FR (1) FR2037773A5 (de)
GB (1) GB1298943A (de)
NL (1) NL7003138A (de)
SE (1) SE364995B (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898109A (en) * 1973-09-06 1975-08-05 Int Nickel Co Heat treatment of nickel-chromium-cobalt base alloys
US4014691A (en) * 1972-12-18 1977-03-29 Mohammed M Hamdi A Dental bridge alloy
US4213026A (en) * 1978-06-06 1980-07-15 United Technologies Corporation Age hardenable nickel superalloy welding wires containing manganese
US4219592A (en) * 1977-07-11 1980-08-26 United Technologies Corporation Two-way surfacing process by fusion welding
US4352970A (en) * 1978-02-09 1982-10-05 Centre De Recherches Metallurgiques-Centrum Voor Research In De Metallurgie Wet welding electrodes
US4755240A (en) * 1986-05-12 1988-07-05 Exxon Production Research Company Nickel base precipitation hardened alloys having improved resistance stress corrosion cracking
US4764225A (en) * 1979-05-29 1988-08-16 Howmet Corporation Alloys for high temperature applications
WO1999067436A1 (en) * 1998-06-19 1999-12-29 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
US20060222557A1 (en) * 2004-09-03 2006-10-05 Pike Lee M Jr Ni-Cr-Co alloy for advanced gas turbine engines
EP2274453A4 (de) * 2008-04-10 2011-05-04 Huntington Alloys Corp Legierung für einen ultrasuperkritischen kocher und verfahren zu ihrer herstellung
CN109536781A (zh) * 2018-12-27 2019-03-29 北京科技大学 一种高纯净低夹杂镍基粉末高温合金及其制备方法和应用
CN116121595A (zh) * 2021-11-12 2023-05-16 江苏新华合金有限公司 一种高电阻电热合金Cr20Ni80Zr及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1367661A (en) * 1971-04-07 1974-09-18 Int Nickel Ltd Nickel-chromium-cobalt alloys
US4820356A (en) * 1987-12-24 1989-04-11 United Technologies Corporation Heat treatment for improving fatigue properties of superalloy articles

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014691A (en) * 1972-12-18 1977-03-29 Mohammed M Hamdi A Dental bridge alloy
US3898109A (en) * 1973-09-06 1975-08-05 Int Nickel Co Heat treatment of nickel-chromium-cobalt base alloys
US4219592A (en) * 1977-07-11 1980-08-26 United Technologies Corporation Two-way surfacing process by fusion welding
US4352970A (en) * 1978-02-09 1982-10-05 Centre De Recherches Metallurgiques-Centrum Voor Research In De Metallurgie Wet welding electrodes
US4213026A (en) * 1978-06-06 1980-07-15 United Technologies Corporation Age hardenable nickel superalloy welding wires containing manganese
US4764225A (en) * 1979-05-29 1988-08-16 Howmet Corporation Alloys for high temperature applications
US4755240A (en) * 1986-05-12 1988-07-05 Exxon Production Research Company Nickel base precipitation hardened alloys having improved resistance stress corrosion cracking
US6258317B1 (en) 1998-06-19 2001-07-10 Inco Alloys International, Inc. Advanced ultra-supercritical boiler tubing alloy
WO1999067436A1 (en) * 1998-06-19 1999-12-29 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
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
EP2274453A4 (de) * 2008-04-10 2011-05-04 Huntington Alloys Corp Legierung für einen ultrasuperkritischen kocher und verfahren zu ihrer herstellung
US10041153B2 (en) 2008-04-10 2018-08-07 Huntington Alloys Corporation Ultra supercritical boiler header alloy and method of preparation
CN109536781A (zh) * 2018-12-27 2019-03-29 北京科技大学 一种高纯净低夹杂镍基粉末高温合金及其制备方法和应用
CN116121595A (zh) * 2021-11-12 2023-05-16 江苏新华合金有限公司 一种高电阻电热合金Cr20Ni80Zr及其制备方法

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NL7003138A (de) 1970-09-09
BE746970A (fr) 1970-09-07
DE2010054A1 (de) 1971-02-25
GB1298943A (en) 1972-12-06
FR2037773A5 (de) 1970-12-31
SE364995B (de) 1974-03-11
CA923340A (en) 1973-03-27
AT304092B (de) 1972-12-27
CH517830A (fr) 1972-01-15

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