EP0073685B1 - Nickel-Chrom-Eisen-Legierung - Google Patents

Nickel-Chrom-Eisen-Legierung Download PDF

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Publication number
EP0073685B1
EP0073685B1 EP19820304610 EP82304610A EP0073685B1 EP 0073685 B1 EP0073685 B1 EP 0073685B1 EP 19820304610 EP19820304610 EP 19820304610 EP 82304610 A EP82304610 A EP 82304610A EP 0073685 B1 EP0073685 B1 EP 0073685B1
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EP
European Patent Office
Prior art keywords
alloy according
content
alloy
alloys
nickel
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Expired
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EP19820304610
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English (en)
French (fr)
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EP0073685A1 (de
Inventor
Trikur Anantharaman Ramanarayanan
Ruzica Petkovic-Luton
Raghavan Ayer
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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%

Definitions

  • This invention relates to alumina-forming nickel-based austenitic alloys having superior oxidation and carburization resistance, superior creep strength, good high temperature ductility, and good microstructural stability.
  • alloy steels containing various amounts of nickel, chromium, and silicon, as well as the addition of elements such as tungsten and/or niobium, are frequently used in high temperature applications.
  • alloy steels containing various amounts of nickel, chromium, and silicon, as well as the addition of elements such as tungsten and/or niobium are frequently used in high temperature applications.
  • elements such as tungsten and/or niobium
  • Carburization of such tubes which is the diffusion of carbon into the alloy steel causing the formation of additional carbides, principally at the grain boundaries, and the attendant depletion. of the matrix in chromium, brings about both a loss of creep strength and embrittlement of the grain boundaries. Once the steel has become embrittled, it is more susceptible to failure by creep rupture at high temperatures, brittle fracture at low temperatures, or both, because of thermal stress.
  • alumina-forming nickel-based austenitic alloys having improved oxidation and carburization resistance, improved creep rupture properties, good high temperature ductility, and good microstructural stability. These alloys are characterized by the following composition (% by weight):
  • the alloys according to the present invention are particularly adapted to constitute metallic parts to be used on the inside or outside of reforming and steam cracking furnaces wherein there exists an oxidizing and carburizing atmosphere and operating temperatures in the range of about 900°C to about 1100°C.
  • the alloys of the present invention simultaneously possess the following properties:
  • composition of the alloys of the present invention by weight percent based on the total weight of the alloy, can be characterized as follows: The rest being nickel with the usual minimum impurities.
  • Chromium also provides strength by virtue of its presence in solid solution and the formation of chromium carbide particles.
  • Carbon (C) provides strength at elevated temperatures in the presence of carbide forming elements through the formation of finely dispersed alloy carbides in the matrix and discontinuous blocky carbides in the grain boundaries. The latter inhibit grain boundary sliding and thereby constrain matrix deformation at a carbon level of 0.2-0.3. Higher levels of carbon promote the formation of a continuous layer of carbide at grain boundaries which serve as an easy path for crack propagation and thus impart poor ductility.
  • Hafnium (Hf) additions result in the formation of highly stable hafnium carbides (HfC). These form in preference to chromium carbides during solidifcation and precipitate as discrete particles at grain boundaries. This process removes carbon from solution and suppresses the precipitation of chromium carbides and thereby promotes the formation of discrete particles of hafnium carbides in preference to the continuous carbide boundary film formed in the absence of hafnium.
  • Yttrium (Y) in levels less than about 1 wt.% have been shown to significantly improve the adherence of A1 2 0 3 scales; therefore, a Y content of about 0.01 to 1 wt.%, preferably about 0.5 to 1 wt.% is employed for use in the present alloys.
  • Tungsten (W) contributes to solid solution strengthening at high temperatures and 1.5 to 3.25 wt.%, preferably 2.75 to 3.25 wt.% is employed in the alloys of the present invention.
  • Niobium (Nb) when present in the alloys of the present invention, will form fine niobium carbide precipitates on dislocations in the alloy structure and contributes to the strength of the alloy.
  • Niobium levels of about 1 to 2 wt.% are suitable for use herein, preferred is a niobium content of about 1.25 to 1.75 wt.%.
  • Nickel constitutes the balance of the alloys with residual impurities at as low a concentration as possible.
  • a coupon measuring 2 cmx1 cmx5 mm was taken from a cast tube comprised of 0.55 wt.% C, 2.31 wt.% Si, 1.21 wt.% Mn, 29.75 wt.% Cr, 28.70 wt.% Ni, balance Fe.
  • the coupon was pack carburized, that is, placed in a carbon bed having access to air, at 1100°C for 72 hours.
  • the coupon was then nickel-plated, cross-sectioned, polished, and examined under a scanning electron microscope. It was observed that carburization occurred throughout the coupon.
  • a coupon having the same dimensions as that of the above Comparative Example was taken from a cast tube comprised of 23.8 wt.% Cr, 12.2 wt.% Fe, 4.8 wt.% Al, 1.23 wt.% Hf, 2.85 wt.% W, 1.68 wt.% Nb, 0.48 wt.% Y, 0.2 wt.% C, and the balance Ni.
  • the coupon was pack carburized at 1100°C for 72 hours.
  • the coupon was then prepared and analyzed as in the above Comparative Example and it was found that a protective A1 2 0 3 scale had formed which enabled the coupon to resist carburization.
  • a coupon of the alloy of Example 1 above was oxidized in air at 1100°C for 100 hours. The coupon was then analyzed and it was found that a protective layer of AI 2 0 3 had formed on its surface, and that some internal Al 2 O 3 stringes were also present.
  • the alloys of the present invention are selectively oxidized to form AI 2 O 3 scales which resist further oxidation-thus evidencing the oxidation resistance of the presently claimed alloys.
  • microstructural stability of the alloy of Example 1 above was determined by studying samples of the alloy after one sample was exposed to air at 1100°C for 1000 hours and another sample was exposed to air at 1175°C for 100 hours. Both samples were found to be structurally stable, that is, the grain structure and precipitates remained unchanged throughout the experiment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (9)

1. Hitzebeständige, aluminiumoxidbildende, auf Nickel basierende austenitische Legierung mit verbesserter Oxidations- und Kohlungsbeständigkeit, verbesserter Dauerstandfestigkeit und verbesserter Hochtemperatur-duktilität sowie mikrostruktureller Stabilität bestehend aus den folgenden Elementen in den folgenden Gewichtsanteilbereichen:
Figure imgb0005
2. Legierung nach Anspruch 1, bei der der Chromgehalt etwa 24 bis 25 Gew.% beträgt.
3. Legierung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Eisengehalt etwa 12 bis 14 Gew.% beträgt.
4. Legierung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Aluminiumgehalt etwa 4 bis 5 Gew.% beträgt.
5. Legierung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Hafniumgehalt etwa 1,5 bis 2 Gew.% beträgt.
6. Legierung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Wolframgehalt etwa 2,75 bis 3,25 Gew.% beträgt.
7. Legierung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Niobgehalt etwa 1,25 bis 1,75 Gew.% beträgt.
8. Legierung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Yttriumgehalt etwa 0,5 bis 1 Gew.% beträgt.
9. Legierung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Kohlenstoffgehalt etwa 0,3 Gew.% beträgt.
EP19820304610 1981-09-02 1982-09-02 Nickel-Chrom-Eisen-Legierung Expired EP0073685B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29859181A 1981-09-02 1981-09-02
US298591 1981-09-02

Publications (2)

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EP0073685A1 EP0073685A1 (de) 1983-03-09
EP0073685B1 true EP0073685B1 (de) 1986-01-22

Family

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Family Applications (1)

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EP19820304610 Expired EP0073685B1 (de) 1981-09-02 1982-09-02 Nickel-Chrom-Eisen-Legierung

Country Status (5)

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EP (1) EP0073685B1 (de)
JP (1) JPS5873739A (de)
AU (1) AU547863B2 (de)
CA (1) CA1196805A (de)
DE (1) DE3268674D1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992013179A1 (en) * 1991-01-23 1992-08-06 Man B&W Diesel A/S Valve with hard-facing

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008051014A1 (de) * 2008-10-13 2010-04-22 Schmidt + Clemens Gmbh + Co. Kg Nickel-Chrom-Legierung
JP5920047B2 (ja) * 2012-06-20 2016-05-18 新日鐵住金株式会社 オーステナイト系耐熱部材

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE734745C (de) * 1938-04-15 1943-04-29 Heraeus Vacuumschmelze Ag Verwendung von Nickel-Chrom-Eisenlegierungen fuer Gegenstaende hoechster Warmfestigkeit
FR1251688A (fr) * 1960-03-18 1961-01-20 Thomson Houston Comp Francaise Alliages réfractaires
GB1190047A (en) * 1967-08-18 1970-04-29 Int Nickel Ltd Nickel-Chromium-Iron Alloys
GB1512984A (en) * 1974-06-17 1978-06-01 Cabot Corp Oxidation resistant nickel alloys and method of making the same
US3976436A (en) * 1975-02-13 1976-08-24 General Electric Company Metal of improved environmental resistance
US4077801A (en) * 1977-05-04 1978-03-07 Abex Corporation Iron-chromium-nickel heat resistant castings

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992013179A1 (en) * 1991-01-23 1992-08-06 Man B&W Diesel A/S Valve with hard-facing

Also Published As

Publication number Publication date
DE3268674D1 (en) 1986-03-06
AU547863B2 (en) 1985-11-07
CA1196805A (en) 1985-11-19
EP0073685A1 (de) 1983-03-09
JPS5873739A (ja) 1983-05-04
AU8789082A (en) 1983-03-10

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