EP0264357A2 - Alliage réfractaire austénitique et son procédé de fabrication - Google Patents

Alliage réfractaire austénitique et son procédé de fabrication Download PDF

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Publication number
EP0264357A2
EP0264357A2 EP19870890201 EP87890201A EP0264357A2 EP 0264357 A2 EP0264357 A2 EP 0264357A2 EP 19870890201 EP19870890201 EP 19870890201 EP 87890201 A EP87890201 A EP 87890201A EP 0264357 A2 EP0264357 A2 EP 0264357A2
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EP
European Patent Office
Prior art keywords
values
weight
alloy
service life
workpiece
Prior art date
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Granted
Application number
EP19870890201
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German (de)
English (en)
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EP0264357A3 (en
EP0264357B1 (fr
Inventor
Herbert Dipl.-Ing. Aigner
Hans-Peter Dr. Degischer
Robert Dr. Danzer
Werner Dr. Mitter
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.)
Boehler GmbH
Original Assignee
Vereinigte Edelstahlwerke AG
Boehler GmbH
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Application filed by Vereinigte Edelstahlwerke AG, Boehler GmbH filed Critical Vereinigte Edelstahlwerke AG
Publication of EP0264357A2 publication Critical patent/EP0264357A2/fr
Publication of EP0264357A3 publication Critical patent/EP0264357A3/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • 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

Definitions

  • the invention relates to high-temperature, essentially austenitic alloys or primary materials, semi-finished products, workpieces or components made from these alloys, obtained by melt metallurgy, which are intended for use at elevated temperatures, in particular in the range above 550 ° C., with at least 15% by weight.
  • Alloys of this type are particularly suitable for components in systems with high continuous operating temperatures. At these, possibly also changing, high temperatures, they should maintain their strength and dimensional stability as well as further corrosion resistance over the longest possible periods of use and are used in particular for pipelines, pressure vessels, reactors, heat exchangers, engines, turbines, fittings and the like, especially in in the chemical and petroleum industries, as well as in energy generation and driving and aircraft drives.
  • Such improvements in properties can, for example with a specific modification of the alloy components and their quantitative ratios or through specific changes in the structure or substructure of the grain and matrix.
  • Workpieces and components that have the alloys initially specified globally with their basic components, for which a number of known and commercially available high-temperature alloys can be calculated, can be produced in the intended state of use, usually after a solution annealing and controlled cooling based on their basic character, often have an economically viable service life at the appropriate temperatures.
  • the operating time of the systems and / or the level of the operating temperature are limited by the time-expansion behavior of the alloys.
  • the invention has set itself the task for the described wide range of high-temperature alloys within the framework of the criteria mentioned above, the composition, the high heat resistance materials with compared to previously significantly improved long-term properties, such as service life and in particular much lower creep rate or reduced long-term -Extension in the longer service life without adversely affecting their manufacturability and / or the other properties.
  • the invention thus relates to highly heat-resistant, essentially austenitic alloys or primary materials, semi-finished products, workpieces or components made from these alloys, obtained by melt metallurgy, which are intended for use at higher temperatures, in particular in the range above 550 ° C., with at least 15 % By weight of chromium, at least 25% by weight of nickel and / or cobalt, up to 18% by weight of molybdenum and / or up to 10% by weight of tungsten, up to 0.15% by weight of carbon and / or nitrogen, and carbide - And nitride-forming elements and at most 60 wt.% Iron, which are characterized in that in the austenitic matrix of the alloy at least in the When used for increased mechanical stress, the intended volume ranges of the workpieces or components are intracrystalline secondary secreted particles of carbides and / or nitrides and / or carbonitrides with a single particle volume of 103 to 106 nm3 in a homogene
  • the materials according to the invention or components made from them have, as has surprisingly been shown, an increased service life which goes far beyond the increase in creep rupture strength to be expected in the case of customary production and separation of particles in the matrix and, in particular, very significantly improved creep resistance. In some cases, it was even possible to observe ten times the service life of the alloys in the solution annealing condition.
  • the workpieces or components formed with the alloy according to the invention have the above-mentioned structure and long-term properties over their entire volume, such as e.g. is advantageous for pipes, reactors and vessels that are used at high temperatures.
  • Rotating and / or components with different cross sections can have different material stresses during operation at high temperatures.
  • the homologous temperature is the value from the ratio of the temperature to the melting temperature of the alloy in degrees Kelvin.
  • the lower limit of the test voltages during the tests was 10 - 25 N / mm2.
  • Homogeneous distribution of the particles means that there is essentially the same number of particles in each volume element, at least in the areas of the workpieces which are subject to higher mechanical stresses. However, they can be spatially isotropic or anisotropically distributed.
  • the alloy with a composition of in% by weight 0.04 - 0.18 C, to 1 Si, to 1.5 Mn, 19 - 23 Cr, 30 - 34 Ni, 0.1 - 0.6 Ti, up to 0.6 Al, remainder Fe and contamination due to melting at the temperatures of their later use, in particular at 750 - 850 ° C with test voltages of up to 150 N / mm2 compared to the corresponding values in the solution-annealed state at least 3- times the values of the service life up to the break and at least 5 times, in particular at least 10 times the values of the service life until the 1% creep elongation is reached.
  • This alloy which can be used very widely, provides a synergism with regard to the heat resistance properties on the basis of composition, particle size and density.
  • an alloy with increased heat resistance has proven to be advantageous, which is characterized in that it has a composition of 0.05-0.1 C, 0.5-1 Si, 0.5-1 Mn, in% by weight. 19 - 23 Cr, 15 - 19 Fe, 1 - 2 Co, 0.5 - 1.5 W, 8 - 10 Mo, balance Ni and melting-related impurities at the temperatures of their later use, especially at 750 - 850 ° C at Test voltages of up to 150 N / mm2 compared to the corresponding values in the solution-annealed state have at least 3 times the service life values and at least 5 times, in particular at least 8 times the service life values until the 1% creep elongation is reached. This material is particularly suitable for turbine blades.
  • cold working after solution annealing is within the specified range, with a particularly high level of safety in the preferred range being essential for achieving the high level of properties union structure and density of the excretions is guaranteed, a particularly high number or density of intracrystalline, excretion latency-containing germ centers is created and with the hot aging treatment at practically all of these centers the manifest formation of the finely dispersed secondary excretions is initiated.
  • the cold working can be carried out in the usual way by rolling, drawing, pressing, vocationalage or the like. It is very important that the workpiece in each case at the points exposed to the use of high mechanical stress or in total in all volume ranges is ensured, which ensures that in any case these areas or the workpiece as a whole has a significantly increased service life.
  • the step of hot aging after the introduction of a large number of dislocations into the crystals of the material by means of the cold deformation downstream of the solution annealing is essential, since secondary particles are guaranteed under defined conditions by growing the particles at the dislocations. It will In all of the volume units of the workpiece intended for higher loads, fixation of the dislocations introduced by the cold-forming in the grains of the austenitic matrix is achieved, whereby this essentially homogeneous, fixed internal state of tension per se achieves increased strength while maintaining ductility.
  • Rotating and / or components with different cross sections can have different material tensions during operation at high temperatures.
  • the variant of introducing the cold deformation particularly into the areas which are mechanically highly stressed during later use is favorable.
  • Typical times for economical hot aging are about 1 - 48 hours.
  • the elongation at break at 800 ° C was 45% with a strength of 250 N / mm2 for the solution-annealed material only, and 261 N / mm2 for the 47% according to the invention.
  • the 0.2% proof stress increased by 22.6% in the alloy according to the invention.
  • Tube strip samples are taken and subjected to the test according to DIN 50118 at a test voltage of 70 N / mm2 at 800 ° C.
  • the graphs in FIGS. 7 and 8 show the results of the creep rupture strength and 1% time-elastic limit obtained.
  • the advantageous effect is demonstrated by comparing the test values of strip samples of the pipe material which was not subjected to cold deformation with subsequent hot aging (continuous lines) with those (broken lines) which had the secondary separation structure provided according to the invention.
  • the curves show the substantial increase in the service life up to the break with a factor of approx. 5 and the 1% time-elastic limit with a factor of approx. 13 of the parts produced according to the invention compared to the alloy in the solution-annealed state in various tests temperatures.
  • the graphs of FIGS. 9 and 10 show the results of the creep rupture strength and 1% time-elastic limit obtained.
  • the advantageous effect is demonstrated by comparing the test values of samples of the solution-annealed forging material which has not been subjected to cold deformation with subsequent hot aging (continuous lines) with those (broken lines) which have the secondary separation structure provided according to the invention.
  • the curves show the substantial increase in the service life up to the break with a factor of approx. 4 and the 1% time-elastic limit with a factor of approx. 10 of the material produced according to the invention compared to the alloy in the solution-annealed state at different test temperatures.
  • the elongation at break at 800 ° C was 53% for the solution-annealed alloy with a strength at 800 ° C of 410 N / mm2, for the inventive 53% at 429 N / mm2. A 21.5% higher 0.2% proof stress was determined for the alloy according to the invention.
  • Table 2 shows the quotients found for the alloys from creep rupture strength "deformed” to “undeformed” (Qs) and from the service life until the 1% creep elongation is reached “deformed” to “undeformed” (Qz) in each case at 800 ° C. .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)
  • Powder Metallurgy (AREA)
EP19870890201 1986-09-08 1987-09-02 Alliage réfractaire austénitique et son procédé de fabrication Expired - Lifetime EP0264357B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT2399/86 1986-09-08
AT239986A AT391484B (de) 1986-09-08 1986-09-08 Hochwarmfeste, austenitische legierung und verfahren zu ihrer herstellung

Publications (3)

Publication Number Publication Date
EP0264357A2 true EP0264357A2 (fr) 1988-04-20
EP0264357A3 EP0264357A3 (en) 1989-04-26
EP0264357B1 EP0264357B1 (fr) 1992-07-29

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ID=3533639

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870890201 Expired - Lifetime EP0264357B1 (fr) 1986-09-08 1987-09-02 Alliage réfractaire austénitique et son procédé de fabrication

Country Status (3)

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EP (1) EP0264357B1 (fr)
AT (1) AT391484B (fr)
DE (1) DE3780749D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023199902A1 (fr) * 2022-04-11 2023-10-19 日本製鉄株式会社 Matériau d'alliage

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1071449A (en) * 1965-05-26 1967-06-07 Int Nickel Ltd Corrosion-resistant nickel alloys
US4359349A (en) * 1979-07-27 1982-11-16 The United States Of America As Represented By The United States Department Of Energy Method for heat treating iron-nickel-chromium alloy
GB2138446A (en) * 1983-03-19 1984-10-24 Nippon Steel Corp Austenitic heat-resistant alloys
EP0154601A2 (fr) * 1984-02-24 1985-09-11 MANNESMANN Aktiengesellschaft Application d'un alliage inoxydable austénitique pour pièces de contruction soudables à haute résistance mécanique
EP0154600A2 (fr) * 1984-02-24 1985-09-11 MANNESMANN Aktiengesellschaft Application d'un alliage inoxydable austénitique au chrome-nickel-azote pour pièces de construction à haute résistance mécanique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2415149A1 (fr) * 1978-01-19 1979-08-17 Creusot Loire Alliage a base de fer a haute limite elastique resistant a la corrosion par l'eau de mer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1071449A (en) * 1965-05-26 1967-06-07 Int Nickel Ltd Corrosion-resistant nickel alloys
US4359349A (en) * 1979-07-27 1982-11-16 The United States Of America As Represented By The United States Department Of Energy Method for heat treating iron-nickel-chromium alloy
GB2138446A (en) * 1983-03-19 1984-10-24 Nippon Steel Corp Austenitic heat-resistant alloys
EP0154601A2 (fr) * 1984-02-24 1985-09-11 MANNESMANN Aktiengesellschaft Application d'un alliage inoxydable austénitique pour pièces de contruction soudables à haute résistance mécanique
EP0154600A2 (fr) * 1984-02-24 1985-09-11 MANNESMANN Aktiengesellschaft Application d'un alliage inoxydable austénitique au chrome-nickel-azote pour pièces de construction à haute résistance mécanique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
E. HOUDREMONT; "Handbuch der Sonderstahlkunde", Band 1, 1956, Auflage 3, Seiten 486-490, Verlag Stahleisen mbH, D}sseldorf, DE; "Karbidbilden den Elemente" *
E. HOUDREMONT; "Handbuch der Sonderstahlkunde", Band 2, 1956, Auflage 3, Seite 1298, Verlag Stahleisen mbH, D}sseldorf, DE; "Stickstoff im Stahl" *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023199902A1 (fr) * 2022-04-11 2023-10-19 日本製鉄株式会社 Matériau d'alliage

Also Published As

Publication number Publication date
DE3780749D1 (de) 1992-09-03
ATA239986A (de) 1990-04-15
EP0264357A3 (en) 1989-04-26
AT391484B (de) 1990-10-10
EP0264357B1 (fr) 1992-07-29

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