EP0184038A1 - Eisen-Nickel-Chrom-Molybdänlegierung - Google Patents

Eisen-Nickel-Chrom-Molybdänlegierung Download PDF

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Publication number
EP0184038A1
EP0184038A1 EP85114419A EP85114419A EP0184038A1 EP 0184038 A1 EP0184038 A1 EP 0184038A1 EP 85114419 A EP85114419 A EP 85114419A EP 85114419 A EP85114419 A EP 85114419A EP 0184038 A1 EP0184038 A1 EP 0184038A1
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EP
European Patent Office
Prior art keywords
molybdenum
chromium
nickel
alloy according
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP85114419A
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English (en)
French (fr)
Inventor
William Lawrence Mankins
David Gary Tipton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntington Alloys Corp
Original Assignee
Inco Alloys International Inc
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Filing date
Publication date
Application filed by Inco Alloys International Inc filed Critical Inco Alloys International Inc
Publication of EP0184038A1 publication Critical patent/EP0184038A1/de
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent

Definitions

  • the subject invention is directed to a novel iron-nickel-chromium (Fe-Ni-Cr) alloy characterized by a high degree of resistance to carburization and which affords a combination of other desirable metallurgical properties, including structural stability at elevated temperatures of ca. 980-1095°C, the ability to be both hot and cold worked, good resistance to corrosion including resistance to chloride attacks, etc.
  • Fe-Ni-Cr iron-nickel-chromium
  • iron-base, nickel-chromium alloys are extensively used in a host of diverse applications by reason of one or more (and within limits) strength, ductility, corrosion resistance, etc.
  • this type of alloy generally suffers from an inability to resist satisfactorily the destructive toll occasioned by carburization, a phenomenon by which the alloy structure is environmentally degraded from the surface inward.
  • the load bearing capacity of the alloy is adversely affected as manifested by impaired strength (stress rupture, creep), lowered ductility, etc.
  • the initial attack is along the grain boundaries and this tends to accelerate failure, or at least premature removal of a given alloy component from its operational environment.
  • an iron-nickel-chromium alloy of special chemistry and containing carefully correlated percentages of iron, nickel, chromium, molybdenum and carbon and certain other constituents discussed herein results in a (i) markedly enhanced carburization resistant material at temperature levels at least as high as 980-1095°C.
  • the subject alloy is (ii) workable , (iii) not prone to form deleterious amounts of topological closepacked phases prematurely such as sigma, and otherwise offers (iv) structural stability over substantial periods of time upon exposure to elevated temperature.
  • the alloy is (v) weldable and (vi) affords a high degree of resistance to pitting attack in aggressive corrosive media.
  • the contemplated alloy offers enhanced oxidation resistance, a phenomenon by which the alloy surface undergoes attack in oxygen-containing environments at high temperature. As a consequence, the material continuously undergoes weight loss, the surface "spalls off.” As would be expected the oxidation problem is particularly acute in "thin section” mill product forms, strip, sheet, thin wall tubing, etc.
  • the subject invention contemplates an iron-nickel-chromium alloy containing about 24% to 35% nickel, about 19 to 25% chromium, about 1.5 to 6% molybdenum, carbon in an amount not exceeding about 0.12%, up to 1.5 or 2% manganese, up to 1% aluminum, up to 1% titanium, up to 1% silicon and up to about 0.3% nitrogen, the balance, apart from residual amounts of deoxidizing and cleaning elements,and impurities, being iron.
  • molybdenum plays a major positive role in maximizing resistance to carburization.
  • the molybdenum content should be maintained at a level of about 2% or more in seeking optimum carburization resistance. Percentages much beyond 4% do not offer an appreciable advantage in this respect, given cost considerations, and generally it will not exceed 4.5%.
  • the molybdenum can be as high as about 6%.
  • Chromium imparts resistance to corrosion but should not exceed about 24 or 25% since it lends to sigma formation at elevated temperature and attendant embrittlement problems. A range of 20-23% is quite satisfactory.
  • the total chromium plus molybdenum content preferably does not exceed 26% or 27% since molybdenum also lends to sigma formation. Where high temperature applications are not involved, the chromium plus molybdenum content can be extended to 29%.
  • Nickel contributes to good workability and mechanical properties. Should the nickel level fall much below 24% the stability of the alloy could be impaired, particularly if the chromium and/or molybdenum is at the high end of their respective ranges. On the other hand, nickel percentages above 35% (up to 42%) increase cost without significant property degradation. A nickel range of 28% to 35% is considered most beneficial.
  • titanium should be present, but amounts above 1% are not required. A range from 0.1 or 0.2 to 0.75% is quite beneficial. Aluminum can be used as a deoxidizer and as an aid to workability. A range of 0.05 to 0.5% is quite satisfactory.
  • the alloys are not only workable but can be produced using air melting practice. This is not to say vacuum processing is precluded but there is an economic advantage in the former.
  • Manganese and silicon can both be present in amounts up to 2% and 1%, respectively. Higher amounts are unnecessary. Where oxidation resistance is of importance manganese should not exceed about 0.6%. Manganese promotes weldability, particularly at the higher end of its range with aluminum at the lower end of its range. It is deemed that nitrogen, a potent austenite former, can be present, a range of 0.05 to 0.25% being considered satisfactory. Nitrogen is considered to be beneficial at the lower nickel levels.
  • One advantageous composition comprises about 28 to 35% nickel, 20 to 24% chromium, at least 1.5% and up to 4.5% molybdenum, carbon present up to 0.12%, titanium present up to 1%, up to 1% aluminum, up to 2% manganese, up to 1% silicon and up to 0.3% nitrogen, the balance, apart from impurities and residual deoxidizing and cleaning elements, being iron.
  • Impurities that may be present are those usually associated with alloys of this type, in amounts that do not adversely affect their basic characteristics.
  • Weight gain is essentially a measure of how many atoms of carbon have been absorbed but without regard as to to the depth of effect. Thus, concentration versus depth profiles were determined and Figure 1 reflects this information. Figure 1 confirms, in essence, the data of Table II. As is manifest, with increasing molybdenum percentages the penetration profile shrinks indicating that less diffusion has occurred.
  • Figure 2 depicts surface potential versus molybdenum content. This may be viewed as the chemical effect of molybdenum on carbon diffusion, or specifically the effect of molybdenum on gas-metal reaction at the surface, carbon solubility, or carbon activity coefficient.
  • the surface potential appears to be a quite linear decreasing function of molybdenum, at least up to 4X. The behavior at 8X molybdenum is not clearly understood.
  • Tables III(chemistry) and IV (data) afford a comparison of the oxidation resistance behavior of alloys within the invention versus commercial (control) alloys of somewhat similar composition.
  • the oxidation test was one of cyclic oxidation using 14 kg. samples (air melted) forged to flats, hot rolled to 7.9 m ⁇ and cold rolled to 3.2 mm.
  • the test comprised subjecting specimens for 15 minutes at 1093°C, cooling for 5 minutes in air, heating again to 1093°C holding for 15 minutes, again cooling 5 minutes in air, until testing was completed. Specimens were checked at 100 hr. intervals. Prior to test the specimens were annealed at 1177°C and water quenched. Oxide was removed bv grinding to 120 grit.
  • the alloys within the invention compared more than favorably with the Control alloys. Maintaining manganese at low levels, i.e., below 0.6 or 0.5X contributes to enhanced oxidation resistance.
  • alloys of the invention were quite resistant to premature embrittlement as evident from Table VII. Even upon 3000 hour testing the alloys within the invention performed satisfactorily. Alloy D (9.62% Mo) did not stand up at 760°C/100 hr. It was sigma prone.
  • compositions for weldability are given in Table VIII.
  • two alloy series were evaluated one involving variations in aluminum and manganese (Alloys 5-8), the other (Alloys A, B, 1, 2, and C) exploring the effect of molybdenum.
  • Material was provided as 1 ⁇ 2" thick x 2" wide hot forged flats which were overhauled and rolled to 7.87mm thick x 50.8 mm wide for Varestraint test samples. Included for purposes of comparison is a well known commercial alloy (Control).
  • alloys within the invention are both hot and cold workable. Using Alloys 3, 4 and D of Table VI, these alloys forged readily and the forgings upon inspection were of high quality.
  • Hardness data are given in Table XI for given annealing temperatures. Also included is hardness in the cold worked condition. In this connection, specimens were cold rolled to about 3.2 mm thick from thickness given in Table XII.
  • the hardness measurements reflect that the alloys are relatively readily workable. From Table XII, it will be noted that cold reductions of more than 60X could be achieved without intermediate annealing. This together with the hardness data reflects that the alloys have excellent cold workability and a low work hardening rate. It might be added that high carbon is not beneficial to workability.

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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 And Refinement Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Soft Magnetic Materials (AREA)
EP85114419A 1984-11-13 1985-11-13 Eisen-Nickel-Chrom-Molybdänlegierung Ceased EP0184038A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67076784A 1984-11-13 1984-11-13
US670767 1984-11-13

Publications (1)

Publication Number Publication Date
EP0184038A1 true EP0184038A1 (de) 1986-06-11

Family

ID=24691783

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85114419A Ceased EP0184038A1 (de) 1984-11-13 1985-11-13 Eisen-Nickel-Chrom-Molybdänlegierung

Country Status (3)

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EP (1) EP0184038A1 (de)
JP (1) JPS61153262A (de)
CA (1) CA1263041A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0626460A1 (de) * 1993-05-28 1994-11-30 Creusot-Loire Industrie Austenitisches rostfreies Stahl mit hoher Korrosionsbeständigkeit in Chlorid- und Schwefelenthaltende Umgebung, und seine Verwendung

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2532728B2 (ja) * 1990-07-26 1996-09-11 日本冶金工業株式会社 耐高温腐食性に優れるＦｅ―Ｎｉ系合金およびその製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB531466A (en) * 1939-04-06 1941-01-06 Harry Etchells Improvements in alloys
GB638007A (en) * 1942-06-24 1950-05-31 Westinghouse Electric Int Co Improvements in or relating to alloys
GB741558A (en) * 1951-10-27 1955-12-07 Deutsche Edelstahlwerke Ag Improvements in and relating to apparatus for use in the production of ammonium sulphate from coke oven gases
US3175902A (en) * 1962-11-06 1965-03-30 Allegheny Ludlum Steel Austenitic alloy
GB993613A (en) * 1963-11-22 1965-06-02 Sandvikens Jernverks Ab Alloy steels and articles made therefrom
GB1508205A (en) * 1974-07-02 1978-04-19 Westinghouse Electric Corp High temperature alloys
GB2117792A (en) * 1982-04-02 1983-10-19 Cabot Corp Corrosion resistant nickel-iron alloy

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5456018A (en) * 1977-10-12 1979-05-04 Sumitomo Metal Ind Ltd Austenitic steel with superior oxidation resistance for high temperature use
JPS54110917A (en) * 1978-02-21 1979-08-30 Hitachi Metals Ltd Improvement of feeniicr alloy
JPS5741356A (en) * 1980-08-23 1982-03-08 Sumitomo Metal Ind Ltd Austenite steel with superior oxidation resistance at high temperature
JPS57134546A (en) * 1981-02-13 1982-08-19 Sumitomo Metal Ind Ltd Corrosion resistant alloy
JPS57149458A (en) * 1981-03-09 1982-09-16 Daido Steel Co Ltd Corrosion-resistant material
JPS5877557A (ja) * 1981-11-04 1983-05-10 Hitachi Ltd 超高温高圧蒸気タ−ビン
JPS58196192A (ja) * 1982-05-10 1983-11-15 Hitachi Ltd 高温用オ−ステナイト系溶接構造物
JPS5923855A (ja) * 1982-07-28 1984-02-07 Nippon Kokan Kk <Nkk> 炭化物形成元素を含有する高温高強度鋼

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB531466A (en) * 1939-04-06 1941-01-06 Harry Etchells Improvements in alloys
GB638007A (en) * 1942-06-24 1950-05-31 Westinghouse Electric Int Co Improvements in or relating to alloys
GB741558A (en) * 1951-10-27 1955-12-07 Deutsche Edelstahlwerke Ag Improvements in and relating to apparatus for use in the production of ammonium sulphate from coke oven gases
US3175902A (en) * 1962-11-06 1965-03-30 Allegheny Ludlum Steel Austenitic alloy
GB993613A (en) * 1963-11-22 1965-06-02 Sandvikens Jernverks Ab Alloy steels and articles made therefrom
GB1508205A (en) * 1974-07-02 1978-04-19 Westinghouse Electric Corp High temperature alloys
GB2117792A (en) * 1982-04-02 1983-10-19 Cabot Corp Corrosion resistant nickel-iron alloy

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0626460A1 (de) * 1993-05-28 1994-11-30 Creusot-Loire Industrie Austenitisches rostfreies Stahl mit hoher Korrosionsbeständigkeit in Chlorid- und Schwefelenthaltende Umgebung, und seine Verwendung
FR2705689A1 (fr) * 1993-05-28 1994-12-02 Creusot Loire Acier inoxydable austénitique à haute résistance à la corrosion par les milieux chlorurés et sulfuriques et utilisations.

Also Published As

Publication number Publication date
CA1263041A (en) 1989-11-21
JPS61153262A (ja) 1986-07-11

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