EP0087609B1 - Alliage de coulée nickel-fer, résistant aux températures élevées et présentant une structure très stable - Google Patents

Alliage de coulée nickel-fer, résistant aux températures élevées et présentant une structure très stable Download PDF

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Publication number
EP0087609B1
EP0087609B1 EP83101057A EP83101057A EP0087609B1 EP 0087609 B1 EP0087609 B1 EP 0087609B1 EP 83101057 A EP83101057 A EP 83101057A EP 83101057 A EP83101057 A EP 83101057A EP 0087609 B1 EP0087609 B1 EP 0087609B1
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EP
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Prior art keywords
alloy according
alloy
eff
resistance
castings
Prior art date
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EP83101057A
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German (de)
English (en)
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EP0087609A1 (fr
Inventor
Helmut Dr.-Ing. Brandis
Wolfgang Dr.-Ing. Spyra
Josef Reismann
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Thyssen Stahl AG
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Thyssen Edelstahlwerke AG
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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
    • 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%
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S376/00—Induced nuclear reactions: processes, systems, and elements
    • Y10S376/90—Particular material or material shapes for fission reactors

Definitions

  • the invention relates to a highly heat-resistant, temperature-insensitive, cobalt-free nickel-iron casting alloy with great thermodynamic stability of the structural components, which also has high thermal hardness, excellent resistance to oxidation, corrosion and wear as well as good welding properties and is particularly suitable as a material for nuclear reactor components .
  • alloys that can be used for example, in the flange area of nuclear reactors, the following limit values are required for certain accompanying elements: Co ⁇ 0.1%, B ⁇ 0.01%, Ta ⁇ 0.002%.
  • Iron-based alloys can generally only be used to a limited extent due to their low heat resistance and poor corrosion resistance.
  • Nickel-chromium-boron-silicon alloys cannot be used due to their insufficient toughness and corrosion resistance, so that their advantages, such as a low melting temperature range, cannot be exploited.
  • the object of the invention is to propose a structurally stable, heat-resistant nickel-iron cast alloy which, with otherwise the same good properties as that of the aforementioned alloy according to DE-PS27 14 674, has better scale resistance similar to that of cobalt alloys.
  • the inventive alloy differs from the known alloy according to DE-PS 27 14 674 in that the tungsten content is absent and the molybdenum content is increased. Tungsten is comparatively more expensive and more uncertainly available than molybdenum. Furthermore, the known alloy can be iron-free or have a maximum content of 59.3% Fe, while in the alloy according to the invention the iron content is narrowly limited at 18 to 26% with a view to achieving the required properties. The same applies to the chromium content, which must be present in amounts of 22 to 26%. Chromium dissolved in the mixed crystal primarily ensures great resistance to oxidation and corrosion, while the chromium bonded in the carbide also determines the wear resistance. For reasons of toughness, the formation of coarse primary carbides was counteracted by the upper limit of the chromium content. Higher chromium levels also deteriorate the welding behavior in an unacceptable manner.
  • Molybdenum in amounts of 12.5 to 14.5% in the alloy according to the invention when it is dissolved in the mixed crystal, improves the heat resistance and corrosion resistance and, in the carbide, improves the wear resistance.
  • a replacement of the carbide and intermetallic tungsten phase by the molybdenum, which does not necessarily have the same phase, is not taught by the D-PS 27 14 674, rather the known teaching is to provide a minimum content of 1.5% tungsten. Nor could it have been foreseen that the absence of tungsten in the alloy would result in the considerable improvement in scale resistance to be described below.
  • DE-PS 27 14 674 does not reveal the knowledge on which the invention is based, that by carefully limiting the mutually influencing elements nickel, iron, chromium and molybdenum, the catastrophic oxidation otherwise frequently observed on materials containing high molybdenum due to the formation of volatile oxides is omitted. It was therefore not foreseeable that by exceeding the maximum content of 12% for molybdenum specified in DE-PS 27 14 674, not only the same but significantly improved scale resistance can be achieved.
  • the carbon required for carbide formation has to meet a minimum value to achieve good sweat properties and is limited to a maximum value of 1.6% in order to avoid the formation of coarse primary carbides and to ensure sufficient hardness.
  • Manganese serves as a deoxidizer and desulfurization agent, but is limited to a maximum of 0.2% in order to avoid pore formation in the casting or weld metal.
  • Silicon increases the corrosion resistance in acidic reduced solutions and promotes the flow behavior in the liquid phase.
  • Niobium / tantalum is added to refine the grain.
  • the shape of the special carbides is controlled by suitable deoxidizing agents such as calcium, magnesium, aluminum, zirconium and rare earth metals.
  • the structure of the alloy according to the invention consists of primary dendrites with a cubic-bottle-centered structure and residual melt neectics, which are composed of mixed crystals and carbides of the types M, C 3 and M s C.
  • FIG. 2 shows this.
  • FIG. 2a shows the structure in 1000 times magnification for the rapidly quenched cast state
  • FIG. 2b shows the structure after a subsequent 1000-hour annealing at 600 ° C. Changes in structure are imperceptible.
  • the composition of the alloy according to the invention used in the tests shown in FIGS. 1 to 3 was as follows:
  • the structural stability is confirmed by hardness measurements. Since the application temperatures in the flange area of nuclear reactors are 350 ° C and sometimes even 500 ° C in the event of a malfunction, the hardness of cast and TIG weld metal was determined between staggered annealing between 350 and 600 ° C. 3 shows the relatively narrow scatter band of hardness with values between 45 and 48 HRC for annealing times up to 1000 h. The hardness is accordingly determined by the primary structure of the alloy according to the invention. Aging processes are not indicated in the hardness course up to 600 ° C.
  • the alloy according to the invention was tested with the commercially available cobalt base alloy, material no. 3177.0 compared.
  • the materials examined had the following composition:
  • the alloy according to the invention has a superior warm hardness up to at least 900 ° C. compared to the known cobalt alloy.
  • the comparatively large resistance to deformation at high temperature is characteristic of the heat resistance of the alloy according to the invention.
  • the resistance to temperature changes is favorably influenced by a large modulus of elasticity and small coefficients of expansion (FIG. 5).
  • the nickel alloy according to the invention has a smaller coefficient of expansion and a greater modulus of elasticity than the known cobalt alloy used for comparison.
  • the resistance of the claimed nickel alloy to oxidation is high, as shown in FIG. 6.
  • the oxidation behavior of the new alloy up to 900 ° C is the same as that of the cobalt alloy.
  • the commercially available alloy according to DE-PS 2714674 has a tendency to catastrophic oxidation, as can be seen from the sharp increase in oxidation above 800 ° C.
  • the alloy according to the invention is particularly suitable for nuclear reactor components and for armoring valves.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Arc Welding In General (AREA)
  • Heat Treatment Of Steel (AREA)

Claims (6)

1. Alliage de fonderie nickel-fer exempt de cobalt, de grande résistance à la chaleur, insensible à la variation de température, présentant une grande statiblité thermodynamique des constituants de structure, qui présente en outre une grande dureté à chaud, une excellente stabilité vis-à-vis de l'oxydation, de la corrosion et de l'usure ainsi que de bonnes propriétés de soudage et convient en particulier comme matériau pour composants de réacteurs nucléaires, formé de:
Figure imgb0010
2. Alliage selon la revendication 1, caractérisé par
Figure imgb0011
3. Alliage selon la revendication 1, avec cette condition que
1,1 < % Ceff < 1,3

pour % Ceff = % C + 0,86 · % N + 1,11 · % B.
4. Alliage selon la revendication 2, avec cette condition que
1,25 < % Ceff < 1,50

pour % Ceff = % C + 0,86 · % N + 1,11 · % B.
5. Utilisation de l'alliage selon les revendications 1 à 4 comme matériau pour des composants de réacteurs nucléaires.
6. Utilisation de l'alliage selon les revendications 1 à 4 comme matériau pour le blindage de pièces d'usure comme des valves, des accessoires pour vapeur surchauffée, des scies à chaîne.
EP83101057A 1982-02-27 1983-02-04 Alliage de coulée nickel-fer, résistant aux températures élevées et présentant une structure très stable Expired EP0087609B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3207162A DE3207162C1 (de) 1982-02-27 1982-02-27 Hochwarmfeste Nickel-Eisen-Gusslegierung mit grosser Gefuegestabilitaet
DE3207162 1982-02-27

Publications (2)

Publication Number Publication Date
EP0087609A1 EP0087609A1 (fr) 1983-09-07
EP0087609B1 true EP0087609B1 (fr) 1985-09-25

Family

ID=6156913

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Application Number Title Priority Date Filing Date
EP83101057A Expired EP0087609B1 (fr) 1982-02-27 1983-02-04 Alliage de coulée nickel-fer, résistant aux températures élevées et présentant une structure très stable

Country Status (4)

Country Link
US (1) US4464335A (fr)
EP (1) EP0087609B1 (fr)
CA (1) CA1208043A (fr)
DE (1) DE3207162C1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547338A (en) * 1984-12-14 1985-10-15 Amax Inc. Fe-Ni-Cr corrosion resistant alloy
DE10300298A1 (de) 2003-01-02 2004-07-15 Daimlerchrysler Ag Abgasnachbehandlungseinrichtung und -verfahren
US8613886B2 (en) * 2006-06-29 2013-12-24 L. E. Jones Company Nickel-rich wear resistant alloy and method of making and use thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB647701A (en) * 1944-02-24 1950-12-20 William Jessop And Sons Ltd Improvements in and relating to nickel chromium steels
GB670555A (en) * 1946-04-12 1952-04-23 Jessop William & Sons Ltd Improvements in or relating to nickel-chromium steels
JPS5040099B1 (fr) * 1971-03-09 1975-12-22
FR2346462A1 (fr) * 1976-04-02 1977-10-28 Commissariat Energie Atomique Super alliage a haute endurance sans cobalt applicable notamment dans l'industrie nucleaire
JPS5517403A (en) * 1978-07-24 1980-02-06 Hitachi Ltd Sliding mechanism for control rod

Also Published As

Publication number Publication date
EP0087609A1 (fr) 1983-09-07
US4464335A (en) 1984-08-07
DE3207162C1 (de) 1983-10-06
CA1208043A (fr) 1986-07-22

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