US3343950A - Nickel-chromium alloys useful in the production of wrought articles for high temperature application - Google Patents

Nickel-chromium alloys useful in the production of wrought articles for high temperature application Download PDF

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Publication number
US3343950A
US3343950A US420102A US42010264A US3343950A US 3343950 A US3343950 A US 3343950A US 420102 A US420102 A US 420102A US 42010264 A US42010264 A US 42010264A US 3343950 A US3343950 A US 3343950A
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United States
Prior art keywords
alloys
titanium
aluminum
columbium
vanadium
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US420102A
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English (en)
Inventor
Richards Edward Gordon
Twigg Peter Lindsay
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Huntington Alloys Corp
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International Nickel Co Inc
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056Alloys 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 age-hardenable alloys particuarly suitable for use at elevated temperatures and, more particularly, to age-hardenable, nickel-base alloys having an advantageous combination of mechanical characteristics at elevated temperatures.
  • the alloys described and claimed therein contain from 0.02 to 0.09% carbon, from 14 to 22% chromium, from 10 to 20% cobalt, from 3 to 10% molybdenum, from 2 to 3.5% titanium, from to 0.8% aluminum, the sum of the titanium and aluminum contents being greater than 2.5%, from 2 to 5.25% columbium, from 0 to 25% iron, from 0.001 to 0.01% boron, and from 0.01 to 0.1% zirconium, the balance, apart from impurities and residual deoxidants, being nickel.
  • Molybdenum may be replaced by an equal atomic percentage of tungsten up to a maximum tungsten content of by weight, and columbium by an equal Weight of tantalum up to a maximum tantalum content of 3%.
  • the contents of iron and columbium in these alloys have to be specially correlated within the ranges set forth, the highest columbium contents being associated with the lowest iron contents and vice versa.
  • age-hardenable, nickelbase alloys having excellent mechanical properties at temperatures above 600 C.
  • specific alloying '7 atent C 3,343,950 Patented Sept. 26, 1967 ice elements contained therein such as chromium, titanium, aluminum, columbium and vanadium.
  • Another object of the invention is to provide an agehardenable, nickel-base alloy having an advantageous combination of mechanical characteristics at temperatures above about 600 C. and which is particularly resistant to high temperature embrittlement and is notch-insensitive.
  • the invention also contemplates providing a rotor disc formed from an age-hardenable, nickel-base alloy having an advantageous combination of mechanical characteristics at temperatures above about 600 C. and which is particularly resistant to high temperature embrittlement and is notch-insensitive.
  • alloys contemplated herein advantageously contain, in percentages by weight, from about 11% to about 16% cobalt, from about 10.1% to about 17% chromium, from about 0.02% to about 0.1% carbon, from about 5% to about 9% molybdenum, from about 2.53% to about 5.2% aluminum, up to about 1.73% titanium, about 1% to about 2.5% columbium, up to about 1.75% vanadium, about 0.001% to about 0.01% boron, about 0.01% to about 0.1% Zirconium, the balance being essentially nickel.
  • balance essentially nickel does not exclude small amounts of other incidental elements, e.g., deoxidizers and impurities, which are commonly present in nickel alloys and do not adversely affect the novel charateristics of the present invention.
  • small amounts of manganese and silicon e.g., up to about 1% of each, are tolerable in the present alloys.
  • Iron is an undesirable impurity in the present alloys since it increases their tendency to embrittle on prolonged exposure to high temperatures, and its content should therefore not exceed 1%, though greater amounts, up to 5%, may be tolerated J at chromium contents within the lower part of the range.
  • the total content of all impurities and residual deoxidants does not exceed 2%.
  • the amounts of aluminum and titanium must be such that the ratio of aluminum to titanium (Al:T i) is at least 2:1 by weight and the total content of aluminum and titanium (AH-Ti) is from 3.8% to 5.2%.
  • Al:T i the ratio of aluminum to titanium
  • AH-Ti aluminum and titanium
  • a total aluminum-l-titanium content of at least 3.8% is needed to ensure that the alloys have adequate strength at high temperatures, but if this total exceeds 5.2% the tensile ductility of the alloys at high temperature is reduced and hot working becomes very difiicult or even impossible.
  • Columbium and vanadium also contribute to the strength of the alloys, and to obtain adequate high temperature strength these elements must be present in a total amount (Cb-t-V) of at least 2%.
  • vanadium for an equal weight of columbium in the alloys improves their tensile ductility and hot workability, and preferably the alloys contain at least 0.5% vanadium.
  • vanadium impairs the high temperature tensile and creep strengths of the alloys and reduces their resistance to oxidation. For this reason the vanadium content must not exceed 2% and the ratio of vanadium to columbium (VzCb) must not exceed 1.5:1.
  • tantalum Commercially available sources of columbium are usually contaminated by tantalum and small amounts of tantalum will, therefore, usually be present in the alloys of the invention. If desired, tantalum may also be deliberately added to the alloys so that up to one half or even the whole of the columbium content is replaced atom for atom by tantalum.
  • the chromium content is at least 12%. If the chromium content exceeds 17% the alloys become brittle on prolonged exposure to high temperatures, and preferably the chromium content does not exceed 16%.
  • the cobalt content has a very marked elfect on the strength of the alloys. Their high temperature tensile strength is reduced when the cobalt content is decreased below 11% or increased above 16%, and preferably the cobalt content is from 13% to 15 Molybdenum has a beneficial effect on both tensile strength and ductility at high temperatures, and the presence of at least 5% molybdenum is very desirable. On the other hand, excessive additions of molybdenum carry the penalties of increased density, decreased machinability and increased ditficulty in hot working, and the content should, therefore, not exceed 9%.
  • tungsten is not equivalent to molybdenum and its presence has many disadvantages. It reduces the tensile ductility of the alloys, increases their density and thus the stress in rotating components made from them, and impairs the workability of the alloys. Nevertheless small amounts of tungsten, up to a maximum of 2%, can be tolerated as a replacement for half its weight of molybdenum. Preferably, however, the alloys are entirely free from tungsten.
  • the total amount of the hardening elements aluminum, titanium, columbium and vanadium is also important. To ensure adequate high temperature strength this total must be at least 6.3%. Increasing the total hardener content increases the high temperature strength, but at the same time it tends to make alloys notchsensitive, reduces their tensile ductility at high temperatures, increases their tendency to embrittle, and makes them harder to forge. For these reasons the total hardener content must not exceed 8.5% or even 8%, and prefera'bly it is not more than 7.5%
  • the alloys can be air melted, but to ensure the best creep properties and workability they are preferably melted and cast under vacuum. If they are melted in air they are preferably deoxidized by means of calcium or magnesium and refined by holding under vacuum in the molten state for some time before casting.
  • the pressure during this refining treatment should not be more than 0.1 mm. Hg and is preferably lower, e.g. 5 microns or less; the temperature is suitably from 1400 C. to 1600 C.; and the holding time is at least 5 minutes and preferably is at least 10 minutes.
  • the cast ingots may be processed to bar or rotor disc form by conventional extrusion, forging or pressing techniques and may be further processed to sheet by extrusion, forging, hot rolling and col-d rolling.
  • the alloys of the present invention are of the age hardenable type and require suitable heat treatment in order to develop the critical combination of properties required. Both solution heating and aging treatments are required. The former is most important since it largely decides the values of creep strength and proof strength that can be achieved in a given alloy. Very high solution heating temperatures give the highest possible creep re-. sistance, while on the other hand lower solution heating temperatures favor increased proof strength.
  • a suitable heat treatment for parts made from the alloys comprises solution treatment for from V2 to 8 hours at 900 C. to 1150 C., followed by cooling at any practical rate (e.g., by air cooling or oil quenching or, in the case of sheet, water quenching) and then aging. Aging treatments can be carried out at temperatures in the range of 650 C.
  • a preferred heat treatment to give the highest level of proof strength, together with reasonable creep strength, consists in solution heating for from 1 to 8 hours at 1050 C. to 1150 followed by aging for from 4 to 20 hours at 750 C. to 850 C.
  • Example I A series of tensile tests was carried out at 750 C. and impact tests at room temperature on a number of alloys that contained, besides the elements set forth in Table I, 0.05% carbon, 14% cobalt, 7% molybdenum, 0.003% boron, 0.05 zirconium, balance nickel.
  • the test pieces were machined from forged bar of the alloys, and the tensile test pieces were given the following heat treatment before testing; solution heated for 1 hour at 1130 C., air cooled, aged for 4 hours at 820 C., air cooled, again aged for 16 hours at 700 C. and air cooled. Elongations were measured on a gauge length of one inch.
  • Alloys Nos. 1 to 5 are in accordance with the present invention, while Nos. 6 to 9 are not.
  • Alloys 7 and 8 deviate from the invention in having an aluminum to titanium ratio (Al:Ti) of less than 2:1, while Alloy 6 has too high a chromium content.
  • alloys within the invention exhibit high temperature mechanical properties and resistance to embrittlement superior to those outside the invention, which include No. 9, one of the best disc alloys hitherto available and which is in accordance with our US. Patent No. 3,151,981. This is true despite the fact that Alloy No. 9 was melted and cast under vacuum, whereas all the others in the above table were melted and cast 1n air.
  • Alloy No. 6 with 18% chromium, has very poor impact properties, and comparison of the impact properties of Alloys Nos. 4, 2 and 5 show how the impact strength decreases as the total content of niobium and vanadium is increased. Comparison of Alloy No. 2 with No. 3 shows that decrease in the aluminum content somewhat improves the impact strength at the expense of some loss in strength. The best all-round combination of properties is shown by Alloy No. 1.
  • Example II A series of Charpy V-notch tests were carried out to further illustrate the particularly good resistance to notch sensitivity and to high temperature embrittlement of an alloy containing chromium as compared with alloys having higher chromium contents.
  • the alloys tested contained, besides the amount of chromium set forth in Table II, 0.05% carbon, 14% cobalt, 7% molybdenum, 0.5% titanium, 4.0% aluminum, 1.5% columbium, 1.5% vanadium, 0.003% boron, 0.05% zirconium, balance nickel.
  • Each alloy was tested at room temperature after heating for a prolonged period of 1000 hours at one or X-ray examination of the specimens of Alloy No. 2 (15% chromium) heated at 750 C. and 900 C.
  • a most advantageous range of alloy composition contemplated herein for alloys having an advantageous combination of properties, including high temperature strength and ductility combined with resistance to notch sensitivity and high temperature embrittlement is as follows: about 0.04% to about 0.06% carbon, about 12% to about 16% chromium, about 13% to about 15% cobalt, about 6% to about 8% molybdenum, up to about 0.6% titanium, about 3.7% to about 4.8% aluminum, the total content of aluminum and titanium (Al+Ti) being about 4% to about 5%, about 1.4% to about 1.7% columbium, about 1.2% to about 1.7% vanadium, the total content of aluminum, titanium, columbium and vanadian being about 6.6% to about 7.4%, about 0.001% to about 0.01% boron, about 0.01% to about 0.1% zirconium, balance essentially nickel.
  • a particularly advantageous composition consists essentially of about 0.05% carbon, about 15 chromium, about 14% cobalt, about 7% molybdenum, about 0.5% titanium, about 4.0% aluminum, about 1.5% columbium, about 1.5% vanadium, about 0.003% boron, about 0.05% zirconium, balance essentially nickel.
  • alloys of the invention are particularly suitable for making wrought rotor discs for gas-turbine engines, their advantageous combination of properties also makes them useful as material for large bolts for service at elevated temperatures, for example, for securing the casings of steam turbines.
  • the threads of such bolts constitute notches, so it is most important that the alloy used be not notch-weakened.
  • An age-hardenable alloy having an advantageous combination of mechanical characteristics at temperatures above about 600 C. and which is further characterized by notch insensitivity and by resistance to high temperature embrittlement, said alloy consisting essentially of about 0.02% to about 0.1% carbon, about 10% to about 17% chromium, about 11% to about 16% cobalt, about to about 9% molybdenum, about 2.53% to about 5.2% aluminum, up to about 1.73% titanium, the total content of aluminum and titanium being about 3.8% to about 5.2% and the ratio of aluminum to titanium being at least 2:1, about 1% to about 2.5% columbium, up to about 2% vanadium, the total content of columbium and vanadium being about 2% to about 4% and the ratio of vanadium to columbium not exceeding 1.5 :1 about 0.001% to 0.01% boron, about 0.01% to about 0.1% zirconium, and the balance essentially nickel, the total content of aluminum, titanium, columbium and vanadium being about 6.3 to about 8.5%.
  • An age-harden-able alloy having an advantageous combination of mechanical characteristics at temperatures above about 600 C. and which is further characterized by notch insensitivity and by resistance to high temperature embrittlement, said alloy consisting essentially of about 0.04% to about 0.06% carbon, about 12% to about 16% chromium, about 13% to about 15% cobalt, about 6% to about 8% molybdenum, about 3.7% to about 4.8% aluminum, up to about 0.6% titanium, the total content of aluminum and titanium being about 4% to about 5%, about 1.4% to about 1.7% columbium, about 1.2% to about 1.7% vanadium, about 0.001% to about 0.01% boron, about 0.01% to about 0.1% zirconium, and the balance essentially nickel, the total content of aluminum, titanium, columbium and vanadium being about 6.6% to about 7.4%.
  • An age-hardenable alloy having an advantageous combination of mechanical characteristics at temperatures above about 600 C. and which is further characterized by notch insensitivity and resistance to high temperature embrittlement, said alloy consisting essentially of about 0.05% carbon, about 15% chromium, about 14% cobalt, about 7% molybdenum, about 4% aluminum, about 0.5% titanium, about 1.5% columbium, about 1.5% vanadium, about 0.003% boron, about 0.05% zirconium, and the balance essentially nickel.
  • lines 6 and 7 for "International Nickel Company” read The International Nickel Company, Inc column 2, line 45, for "10.1%” read 10% lines 56 and S7, for “charateristlcs” read -character1st1cs column 5, line 59, for "0H 1% boron” read 0.01% boron line 47, for "10% of the” read 10% the column 7, line 11, after "1.5:1" insert a comma.

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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Conductive Materials (AREA)
US420102A 1963-12-23 1964-12-21 Nickel-chromium alloys useful in the production of wrought articles for high temperature application Expired - Lifetime US3343950A (en)

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GB50804/63A GB1075216A (en) 1963-12-23 1963-12-23 Nickel-chromium alloys

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US (1) US3343950A (fr)
AT (1) AT250683B (fr)
CH (1) CH427306A (fr)
DE (1) DE1458421A1 (fr)
GB (1) GB1075216A (fr)
SE (1) SE301726B (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3411898A (en) * 1966-03-25 1968-11-19 Union Carbide Corp Nickel base alloy
US3902862A (en) * 1972-09-11 1975-09-02 Crucible Inc Nickel-base superalloy articles and method for producing the same
US4685977A (en) * 1984-12-03 1987-08-11 General Electric Company Fatigue-resistant nickel-base superalloys and method
FR2652611A1 (fr) * 1989-10-04 1991-04-05 Gen Electric Disque de turbine constitue de deux alliages.
EP0421228A1 (fr) * 1989-10-04 1991-04-10 General Electric Company Pièce en alliage résistant aux fendillements par fatigue et ayant une bonne résistance mécanique
EP0421229A1 (fr) * 1989-10-04 1991-04-10 General Electric Company Alliage résistant au fluage et à la charge de rupture présentant une bonne résistance aux fendillements par fatigue après un maintien prolongé
DE4412031A1 (de) * 1993-04-07 1994-10-13 Aluminum Co Of America Verfahren zur Herstellung von Schmiedeteilen aus Nickellegierungen
US5374323A (en) * 1991-08-26 1994-12-20 Aluminum Company Of America Nickel base alloy forged parts
US20040253102A1 (en) * 2003-06-13 2004-12-16 Shinya Imano Steam turbine rotor and steam turbine plant
US6974508B1 (en) 2002-10-29 2005-12-13 The United States Of America As Represented By The United States National Aeronautics And Space Administration Nickel base superalloy turbine disk

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5130086A (en) * 1987-07-31 1992-07-14 General Electric Company Fatigue crack resistant nickel base superalloys
US5130088A (en) * 1987-10-02 1992-07-14 General Electric Company Fatigue crack resistant nickel base superalloys
US4867812A (en) * 1987-10-02 1989-09-19 General Electric Company Fatigue crack resistant IN-100 type nickel base superalloys
US5037495A (en) * 1987-10-02 1991-08-06 General Electric Company Method of forming IN-100 type fatigue crack resistant nickel base superalloys and product formed
US5129971A (en) * 1988-09-26 1992-07-14 General Electric Company Fatigue crack resistant waspoloy nickel base superalloys and product formed
US5156808A (en) * 1988-09-26 1992-10-20 General Electric Company Fatigue crack-resistant nickel base superalloy composition
US5130089A (en) * 1988-12-29 1992-07-14 General Electric Company Fatigue crack resistant nickel base superalloy
US4983233A (en) * 1989-01-03 1991-01-08 General Electric Company Fatigue crack resistant nickel base superalloys and product formed
JP3371423B2 (ja) 1999-01-28 2003-01-27 住友電気工業株式会社 耐熱合金線

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061426A (en) * 1960-02-01 1962-10-30 Int Nickel Co Creep resistant alloy
US3151981A (en) * 1961-02-28 1964-10-06 Int Nickel Co Nickel-chromium-cobalt alloy
US3155501A (en) * 1961-06-30 1964-11-03 Gen Electric Nickel base alloy
US3166412A (en) * 1962-08-31 1965-01-19 Int Nickel Co Cast nickel-base alloy for gas turbine rotors

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061426A (en) * 1960-02-01 1962-10-30 Int Nickel Co Creep resistant alloy
US3151981A (en) * 1961-02-28 1964-10-06 Int Nickel Co Nickel-chromium-cobalt alloy
US3155501A (en) * 1961-06-30 1964-11-03 Gen Electric Nickel base alloy
US3166412A (en) * 1962-08-31 1965-01-19 Int Nickel Co Cast nickel-base alloy for gas turbine rotors

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3411898A (en) * 1966-03-25 1968-11-19 Union Carbide Corp Nickel base alloy
US3902862A (en) * 1972-09-11 1975-09-02 Crucible Inc Nickel-base superalloy articles and method for producing the same
US4685977A (en) * 1984-12-03 1987-08-11 General Electric Company Fatigue-resistant nickel-base superalloys and method
US5143563A (en) * 1989-10-04 1992-09-01 General Electric Company Creep, stress rupture and hold-time fatigue crack resistant alloys
EP0421228A1 (fr) * 1989-10-04 1991-04-10 General Electric Company Pièce en alliage résistant aux fendillements par fatigue et ayant une bonne résistance mécanique
EP0421229A1 (fr) * 1989-10-04 1991-04-10 General Electric Company Alliage résistant au fluage et à la charge de rupture présentant une bonne résistance aux fendillements par fatigue après un maintien prolongé
FR2652611A1 (fr) * 1989-10-04 1991-04-05 Gen Electric Disque de turbine constitue de deux alliages.
US5360496A (en) * 1991-08-26 1994-11-01 Aluminum Company Of America Nickel base alloy forged parts
US5374323A (en) * 1991-08-26 1994-12-20 Aluminum Company Of America Nickel base alloy forged parts
DE4412031A1 (de) * 1993-04-07 1994-10-13 Aluminum Co Of America Verfahren zur Herstellung von Schmiedeteilen aus Nickellegierungen
US6974508B1 (en) 2002-10-29 2005-12-13 The United States Of America As Represented By The United States National Aeronautics And Space Administration Nickel base superalloy turbine disk
US20040253102A1 (en) * 2003-06-13 2004-12-16 Shinya Imano Steam turbine rotor and steam turbine plant
US7459035B2 (en) * 2003-06-13 2008-12-02 Hitachi, Ltd. Steam turbine rotor and steam turbine plant

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Publication number Publication date
DE1458421A1 (de) 1969-10-09
AT250683B (de) 1966-11-25
GB1075216A (en) 1967-07-12
SE301726B (fr) 1968-06-17
CH427306A (fr) 1966-12-31

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