US3617261A - Wrought nickel base superalloys - Google Patents

Wrought nickel base superalloys Download PDF

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Publication number
US3617261A
US3617261A US703978A US3617261DA US3617261A US 3617261 A US3617261 A US 3617261A US 703978 A US703978 A US 703978A US 3617261D A US3617261D A US 3617261DA US 3617261 A US3617261 A US 3617261A
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alloy
percent
nickel base
properties
strength
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US703978A
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Louis W Lherbier
Frank J Rizzo
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CYCLOPS CORP SPECIALTY STEEL D
CYCLOPS CORP SPECIALTY STEEL DIVISION
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CYCLOPS CORP SPECIALTY STEEL D
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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
    • C22C19/056—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

  • This invention relates to high-temperature alloys. More particularly, it relates to a nickel base alloy capable of being hot worked and having an exacting combination of elements for achievement of adequate strength, creep, ductility, and corrosion properties up to 1,900 F.
  • Our invention provides a nickel base alloy with acceptable strength properties up to 1,900 F. which is a significant improvement over currently employed alloys. The alloy still maintains adequate hot workability so it can be'extruded,
  • wrought as used herein to define our al-1' loy, is intended to define an alloy which can be hot worked; that is, extruded, forged and/or hot rolled.
  • nickel base superalloys consist primarily of gamma prime, carbide precipitates, and a gamma matrix.
  • the composition of the material is not adequately controlled, unwanted phases form by nucleating on carbides and feeding on the gamma matrix for their constituents. These unwanted phases deleteriously affect the stability and the strength of the material. They are the intermetallic phases sigma, mu, and Laves. Consequently, the composition of the matrix is of major concern in developing new nickel base superalloys.
  • the matrix of our alloy consists of nickel, cobalt, chromium, molybdenum, tungsten, andtantalum. The relative amounts of these alloying elements in the matrix are determined by the other elements in the alloy such as aluminum, titanium, carbon, and boron, all of which have reacted to form precipitating phases.
  • alloys of this invention have been vacuum melted although it is believed that with the use of other proper melting techniques the improvements mentioned herein would be attainable.
  • the carbon content should be between 0.25 percent and 0.45 percent with a preferred range of 0.30 percent to 0.40 percent. At least 0.25 percent which is high by present day standards is necessary in our alloy to make it workable. Howsolution ever, extremely high carbon contents (i.e., above 0.45 percent) are not desirable because the alloy will become brittle. The elements responsible for solid solution strengthening will form carbides, and the carbides will form in morphologies which are harmful to the desired properties.
  • Chromium content below 11.0 percent will not give the desired resistance to oxidation and corrosion, and chromium in excess of 17.0 percent makes the alloy difficult to hot work and the stability will be s'everelyimpaired.
  • Cobalt is employed in the broad range from 8.0-12.0 percent (9.0-1 1.0 percent preferred) for its strength properties at elevated temperatures. It also improves ductility, workability, and creep properties. Cobalt in excess of 12.0 percent impairs oxidation andcorrosion properties.
  • Molybdenum andtungsten also take part in carbide formation and solid solution-hardening.
  • the broad range of molybdenum is.2.06.5 percent and the preferred range is 2.5-3.5 percent.
  • the low end of the range is desirable because the presence of highmolybdenum can lead to the precipitation of deleterious phases.
  • the tungsten content ranges from 4.0 to 8.0 percent with a preferred range of 5.5 to 6.5 percent.
  • Aluminum and titanium are also critical elements because of their contribution to the strengthening of nickel base superalloys.
  • the broad composition range for aluminum is 4.0 to
  • the broad composition range for titanium is 2.2 to 3.2 percent with a preferred range of 2.8 to 3.2 percent. Titanium which is also a carbide former has essentially the same effect as the aluminumf Boron and zirconium both enhance the'creep resistance at elevated temperatures.
  • the broad range for boron is 0.0005 to 0.030 percent with a preferred range of 0.008 to 0.018 percent.
  • Zirconium has a broad range of 0.001 to 0.25 percent and a preferred range of 0.005 to 0.150 percent. An excess of either of these elements will have deleterious effects on the ductility and stability of the alloy.
  • the base metal for the alloy is nickel. lts ability to harden by precipitation .of secondary phases and carbides in addition to solid solution strengthening makes it ideal for this application.
  • iron may be present in amounts up to 2.00 1,388 fgdfi 3 2 percent, but it is preferred that the iron content be kept below 1:900 000 5 1 7 1 0 percent 20 1,000 15,888 28.11 20 1 2 1 1 000 14. J .5 0 .1'
  • Table 11 1 in order to com are the stress ru ture ro erties of our P y P P P P A 1 alloy with the present day alloy, the Larson-Miller parameter method, which is well known to those skilled in the art, was 25, employed on our stress rupture data to provide the rupture stress at 100 hours at various test temperatures.
  • Table IV The results TABLE II.MECHANICAL PROPERTIES g are shown 1n table IV:
  • Oxidation resistance as determined by weight gain at measured time intervals and elevated temperatures and corrosion properties as determined by sulfidation resistance are comparable to the present day alloy.
  • the hot workability of the alloy is evidenced by the fact that the ingots produced have been extruded, forged, or hot rolled. The aforementioned three methods of hot workinghave also been successfully accomplished in various combinations thereof. Ingots have also been hot rolled directly into billets, bars and sheets.
  • the alloying elements in the material are converted to atomic percent.
  • the residual alloying elements are assumed to constitute the matrix.
  • the matrix elementamounts are scaled to 100 percent and the new matrix composition is then used to calculate the mean electron vacancy number by summation.
  • the electron vacancy number (N,.) is determined fromthe following equation:
  • FIG. 2 is a photomicrograph of a-sample from heat ,5 having anelectron vacancy number of 2.39.
  • FIG. 3 is a photomicrograph of a sample from heat "9 which has a chemical-composition outside of our broad range (see table V) and has an electron vacancy number of 2.97. Both photomicrographs are taken from sam- ,ples in theidentical as heat-treated state and are taken at 4,000 magnifications.
  • the properties aredetrimentally effected because alloying elements employed for solid solution strengthening are used to form the needle1ike" phase instead.
  • the strength decreases as the needles form and grow. Failure occurs because of excessive slip and the needles" act as excellent planes upon which slip can occur. Therefore, the more sigmatype phase present, the greater the resultant instability of the alloy.
  • the difference in microstructure becomes more acute after the alloy has received exposure, i.e., exposure for extended periods of time at elevated temperatures.
  • the presence of these unwanted second phases greatly reduce the stability of the alloy and therefore limit the type of use for which the alloy can be employed. Therefore, to maintain the stability of the alloy, it must meet a satisfactory N, range of values.
  • the composition must have the necessary high strength mechanical and stress rupture properties.
  • Alloys having electron vacancy numbers below 1.9 do not possess the requisite high-temperature properties. As the electron vacancy number is increased above 1.9, the requisite strength properties increase and the stability of the alloy remains satisfactory. The first notable transition from stability to the presence of deleterious second phases occurs above an N of 2.5 in the exposed state. In the heat-treated state before exposure, the formation of the deleterious phases usually occurs above an electron vacancy number of 2.7. In addition, above an N of 2.5 the strength and ductility properties start to diminish. However, an alloy having an N number from 2.5 to 2.7 is still quite satisfactory for many applications both from the standpoint of mechanical properties and stability. However, the optimum high-temperature properties are found in compositions having an N, range from 2.3 to 2.5.
  • a wrought nickel base alloy for use up to l,900 F. composing by weight percent 0.25 to 0.45 carbon, 0 to 2.00 manganese, 0 to 1.50 silicon, 11.00 to 17.00 chromium 8.00 to 12.00 cobalt, 2.00 to 6.50 molybdenum, 4.00 to 8.00 tungsten, 1.00 to 3.00 tantalum, 4.00 to 5.00 aluminum, 2.20 to 3.20 titanium, 0.0005 to 0.030 boron, 0.001 to 0.250 zirconium, 2.0 max. iron, and the balance nickel.
  • An alloy of the composition set forth in claim 1 characterized by an electron vacancy number of 1.9 to 2.7.
  • An alloy of the composition set forth in claim 3 characterized also by an electron vacancy number in the range of 2.3 to 2.5.
  • the alloy of claim 3 containing up to 0.50 percent by weight misch metal, the misch metal composing a mixture of rare earth elements in metallic form.

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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 Alloys Or Alloy Compounds (AREA)
  • Soft Magnetic Materials (AREA)
US703978A 1968-02-08 1968-02-08 Wrought nickel base superalloys Expired - Lifetime US3617261A (en)

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FR (1) FR2001516A1 (fr)
GB (1) GB1252966A (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4080201A (en) * 1973-02-06 1978-03-21 Cabot Corporation Nickel-base alloys
US4492672A (en) * 1982-04-19 1985-01-08 The United States Of America As Represented By The Secretary Of The Navy Enhanced microstructural stability of nickel alloys
US4615658A (en) * 1983-07-21 1986-10-07 Hitachi, Ltd. Shroud for gas turbines
US5403546A (en) * 1989-02-10 1995-04-04 Office National D'etudes Et De Recherches/Aerospatiales Nickel-based superalloy for industrial turbine blades
WO1999037825A1 (fr) * 1998-01-27 1999-07-29 Jeneric Pentron Incorporated Alliage dentaire a forte teneur en tungstene et en aluminium au silicium

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE788719A (fr) * 1971-09-13 1973-01-02 Cabot Corp Alliage a base de nickel resistant a l'oxydation aux temperatures elevees et thermiquement stables

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3164465A (en) * 1962-11-08 1965-01-05 Martin Metals Company Nickel-base alloys
US3304176A (en) * 1963-12-26 1967-02-14 Gen Electric Nickel base alloy
US3322534A (en) * 1964-08-19 1967-05-30 Int Nickel Co High temperature nickel-chromium base alloys

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3164465A (en) * 1962-11-08 1965-01-05 Martin Metals Company Nickel-base alloys
US3304176A (en) * 1963-12-26 1967-02-14 Gen Electric Nickel base alloy
US3322534A (en) * 1964-08-19 1967-05-30 Int Nickel Co High temperature nickel-chromium base alloys

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4080201A (en) * 1973-02-06 1978-03-21 Cabot Corporation Nickel-base alloys
US4492672A (en) * 1982-04-19 1985-01-08 The United States Of America As Represented By The Secretary Of The Navy Enhanced microstructural stability of nickel alloys
US4615658A (en) * 1983-07-21 1986-10-07 Hitachi, Ltd. Shroud for gas turbines
US5403546A (en) * 1989-02-10 1995-04-04 Office National D'etudes Et De Recherches/Aerospatiales Nickel-based superalloy for industrial turbine blades
WO1999037825A1 (fr) * 1998-01-27 1999-07-29 Jeneric Pentron Incorporated Alliage dentaire a forte teneur en tungstene et en aluminium au silicium
US6103383A (en) * 1998-01-27 2000-08-15 Jeneric/Pentron Incorporated High tungsten, silicon-aluminum dental alloy

Also Published As

Publication number Publication date
GB1252966A (fr) 1971-11-10
DE1904814B2 (de) 1973-02-08
DE1904814A1 (de) 1969-09-11
FR2001516A1 (fr) 1969-09-26

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