US20150203944A1 - Austenitic steel alloy having excellent creep strength and resistance to oxidation and corrosion at elevated use temeratures - Google Patents

Austenitic steel alloy having excellent creep strength and resistance to oxidation and corrosion at elevated use temeratures Download PDF

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US20150203944A1
US20150203944A1 US14/414,611 US201314414611A US2015203944A1 US 20150203944 A1 US20150203944 A1 US 20150203944A1 US 201314414611 A US201314414611 A US 201314414611A US 2015203944 A1 US2015203944 A1 US 2015203944A1
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steel
weight
steel alloy
creep strength
alloy according
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Juliane Mentz
Michael Spiegel
Joachim Konrad
Patrick Schraven
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Salzgitter Mannesmann Stainless Tubes GmbH
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Salzgitter Mannesmann Stainless Tubes GmbH
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Assigned to Salzgitter Mannesmann Stainless Tubes GmbH reassignment Salzgitter Mannesmann Stainless Tubes GmbH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KONRAD, JOACHIM, MENTZ, JULIANE, SPIEGEL, MICHAEL, SCHRAVEN, Patrick
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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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • 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
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • 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
    • 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12292—Workpiece with longitudinal passageway or stopweld material [e.g., for tubular stock, etc.]

Definitions

  • the invention relates to an austenitic steel alloy with excellent creep strength and oxidation and corrosion resistance at elevated operating temperatures according to patent claim 1 and work pieces made of the steel alloy according to claim 8 .
  • the invention relates to a heat resistant austenitic material for the production of pipes, steel sheets or as forging material for example for seamless super heater tubes in highly efficient power plants of the new generation which are suitable for steam temperatures up to about 750° C.
  • the demands on the material under these conditions are a sufficient creep strength in combination with a good oxidation resistance in water vapor and corrosion resistance in the presence of flue gases and ashes.
  • the specific demands at the upper temperature levels on the heat exchange tubes at these high operating temperatures are a sufficient creep strength in particular in combination with a high oxidation resistance in water vapor and corrosion resistance in the presence of flue gas and ashes.
  • High temperature materials with high creep strength and corrosion resistance for use for example in power plants are generally based either on ferritic, ferritic/martensitic or austenitic iron based alloys or on nickel based alloys.
  • Chromium rich ferritic steel is compared to austenitic steel significantly more cost effective and has a higher thermal conductivity coefficient and a lower heat expansion coefficient.
  • chromium rich ferritic steels also posses a high oxidation resistance, which is advantageous for hot steam applications for example in heaters or in boilers.
  • the known materials which are available for operating temperatures up to about 620° C. or 650° C., are ferritic/martensitic steels with Cr-contents of for example 8 to 15%. These materials mostly have further expensive alloy additives or are not suited for the use in temperature ranges above 620° C.
  • Austenitic steels for use in steam boilers with steam temperatures up to 700° C. and above are for example known form DE 60 2004 002 492 T2.
  • the creep strength is achieved in particular by adding titanium and oxygen in the stated limits.
  • a disadvantage in this steel is however the insufficient oxidation resistance in water vapor and the insufficient resistance against flue gas corrosion at these high operating temperatures.
  • a further object is to provide work pieces such as for example seamless or welded pipes, steel sheets and cast pieces or tool steels made of this steel alloy.
  • the austenitic ultra high temperature resistant alloy according to the invention has excellent creep strength properties and good oxidation resistance in water vapor and corrosion resistance in flue gas.
  • the alloy concept fundamentally differs from the known alloy concepts.
  • the strengthening of the austenitic matrix compared to dislocation creep occurs in known austenitic materials up to temperatures of 650° C. sufficiently by M 23 C 6 on the grain boundaries and fine carbides and nitride particles in grain boundaries and in the grain interior. At higher temperatures no sufficient creep properties are ensured.
  • the present alloy utilizes the fine particle sigma phase precipitated in the grain as strengthening component in combination with components M 23 C 6 and further fine-particle carbides, carbonitrides and nitrides in particular niobium precipitated on the grain boundaries for increasing the creep strength.
  • FIG. 1 shows the microstructure of the alloy according to the invention after annealing or creep strength test schematically.
  • the sum content of molybdenum, chromium and silicone is at least 29 weight %.
  • An advantageous refinement of the invention provides that for further improving the corrosion resistance at high temperatures the minimal chromium content is set to 26% and the minimal nickel content to 25%.
  • the increase of the lower limit of the chromium content achieves a higher chromium content in the austenitic matrix which significantly influences the oxidation and corrosion properties.
  • the upper limit of the chromium content is lowered to 30% for limiting the content of sigma-phase.
  • the nickel content is adjusted for stabilizing the austenitic structure.
  • the upper limit can here be lowered to 35%, which results in a further improvement of the corrosion properties in sulfur containing flue gases and under sulfate containing layers.
  • Optimal properties regarding creep strength and corrosion can be adjusted with further narrowed content ranges of the elements.
  • the contents of molybdenum are limited to 2-5% and that of silicone to 0.1-1% with regard to an optimal amount and distribution of the sigma phase.
  • the limitation of Nb(0.4-1%), N(0.05-1.12%) and C (0.05-1.12%) has a positive effect on the amount of niobium carbonitrides at high temperature (grain boundary pinning) on one hand and on the amount and distribution of M 23 C 6 as well as other carbides, carbonitrides and nitrides at operating temperature on the other hand.
  • the limitation of the upper limits also has a positive effect on a reduction of the tendency to segregations and on the processability of the steel.
  • Carbon the carbon content is a significant part of the alloy concept and serves for increasing the creep strength and yield strength by precipitation of carbides. A higher carbon content however decreases weldability. For this reason the upper limit is set to 1.15 weight % and the lower limit to 0.02 weight %.
  • Silicone is necessary in order to increase the corrosion resistance and to kinetically accelerate the precipitation of the sigma phase. A content of at least 0.1 weight % has proven advantageous. The weldability is negatively influenced by silicone, in addition silicone stabilizes the Laves-phase which is bound as a result of chromium precipitation so that an upper limit of 2 weight % should not be exceeded.
  • Manganese is a cost effective element, which stabilizes the austenitic matrix of the alloy. In addition manganese decelerates the chromium loss of the alloy during oxidation in water vapor by evaporation of volatile chromium oxides in water vapor due to the formation of ternary Mn—Cr-Oxides.
  • the Manganese content should on the other hand be kept low for avoiding accelerated oxidation in water vapor and flue gas. In addition an increased manganese content also negatively influences the creep strength. A content of maximally 2.0 weight % is not regarded as deleterious.
  • Chromium the oxidation resistance on water vapor but in particular the resistance against flue gas corrosion is achieved by a chromium content of greater than 25 weight %. Chromium is also necessary for forming carbides M 23 C 6 and for precipitation of fine particle sigma phase. Because the precipitation results in binding of chromium a content of at least 25 weight % is required in order to maintain the matrix concentration required to the corrosion resistance. In cooperation with molybdenum in the stated limits the dissolution of strengthening M 23 C 6 carbides on the grain boundary in favor of more brittle sigma-phase is also prevented. At high chromium contents however increasingly d-ferrite forms which leads to a more coarse grained sigma phase. The maximal chromium content is therefore limited to 33 weight %.
  • Nickel is a required element for achieving the austenitic structure and the strength advantages associated therewith, such as creep strength.
  • the durability in sulfur containing flue gases is rather adversely affected by high contents of nickel so that at most 38 weight % nickel should be added.
  • the lower limit should not fall below 22 weight % because due to the high chromium and molybdenum content the austenitic matrix is sought to be stabilized relative to the ⁇ -ferrite.
  • Molybdenum the addition of molybdenum to the alloy occurs for increasing the creep strength as a result of solid solution hardening.
  • a not too high content of molybdenum promotes the resistance against chloride containing gases and ashes.
  • Molybdenum stabilizes beside M 23 C 6 also the sigma phase and should therefore not fall below a minimal content of 1 weight %.
  • a molybdenum content of up to 6 weight % impedes in combination with chromium and boron the dissolution of strengthening M 23 C 6 on the grain boundary in favor of the more brittle sigma-phase.
  • molybdenum promotes precipitation of finely distributed sigma-phase in the grain for increasing the creep strength.
  • Molybdenum contents of higher than 6 weight % cause the formation of an excessive content of sigma-phase and should also be avoided due to the segregation tendency of molybdenum.
  • Wolfram can be added to the alloy as optional element and causes an accelerated oxidation in water vapor and corrosion under ash layers. Therefore the content should not exceed 2 weight %. At the same time wolfram causes an increase of the creep strength by solid solution hardening and formation of precipitations so that depending on the requirements a corresponding addition of wolfram can occur.
  • Niobium the precipitation of hardening niobium carbides, niobium carbonitrides and niobium nitrides in the grain leads to a significant increase of the creep strength at operating temperatures.
  • wolfram based on the grain boundary pinning due to the Nb(C,N) precipitated on the grain boundaries, has a positive effect on the formation of a homogenous microstructure under production conditions. Higher contents of niobium however lead to segregations and decreased hot formability and weldability. The upper limit of 1.5 weight % should therefore not be exceeded.
  • For an effective size of the precipitations the Nb, N and C contents have to be exactly adjusted to each other as described above.
  • Titanium, tantalum vanadium precipitations that involve titanium, tantalum and/or vanadium can also lead to a significant increase of the creep strength.
  • the upper limit is set however to respectively 0.5 weight %.
  • Boron the addition of boron increases the creep strength due to a reduction of the tendency of increased coarseness and additional chemical stabilizing of M 23 C 6 -particles. In addition it increases the stability of grain boundaries against creep damage and increases ductility. Boron prevents the coarsening of the sigma phase by interfacial segregation and their precipitations on the grain boundaries.
  • the lower limit for the effectiveness of boron is therefore about 0.0010 weight %. High boron contents adversely affect welding, which is why an upper limit of 0.0120 weight % is set.
  • Nitrogen increases the creep strength as a result of precipitation of nitrides and therefore has to be added to the alloy as described above in dependence on the carbon and niobium content; nitrogen also stabilizes the austenitic matrix.
  • the lower limit for nitrogen is therefore set to 0.01 weight %.
  • a high nitrogen content causes a decreased tenacity and ductility and reduces the warm formability, therefore an upper limit of 0.2 weight % is set.
  • Cobalt the optional addition of cobalt causes an increase of the solid solution hardening and with this the creep strength. Replacing nickel for cobalt is also conceivable for a sufficient stabilization of the austenitic matrix. At the same time the desired microstructure has to be maintained which is why an upper limit of 5 weight % is set.
  • Copper can be added to the alloy and can be used as further hardening mechanism for the creep strength (precipitation of a Cu-phase). Higher contents of copper reduce the processability so that an upper limit of 5 weight 5% is set.
  • Rare earths and reactive elements such as Ce, Hf, La, Re, Sc and/or Y can be optionally added at contents of together up to 1 weight percent for adjusting specific properties such as increased resistance to temperature changes.
  • FIG. 2 shows the excellent creep behavior at different operating temperatures of steels according to the invention compared to known steels
  • FIGS. 3 and 4 show the time expansion behavior by way of expansion rates at 740 and 700° C.
  • the steel alloy according to the invention can be used in the power plant field, its use is not limited thereto. Beside the production of pipes, which can be seamlessly extruded, hot and cold rolled or welded, this steel alloy can also be used for producing steel sheets, cast, forged and centrifugal casting parts or for tools for mechanical processing (tool steels), wherein their field of application includes pressure containers, boilers, turbines, nuclear plants or the chemical apparatus construction, i.e., all fields with corresponding demands at increased temperature.
  • the steel alloy according to the invention can be advantageously used particularly up to temperatures of 750° C. or above, the use of this steel is already advantageous at temperatures above 600° C. when the focus is more on the strength of the material.
US14/414,611 2012-07-13 2013-06-27 Austenitic steel alloy having excellent creep strength and resistance to oxidation and corrosion at elevated use temeratures Abandoned US20150203944A1 (en)

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Application Number Priority Date Filing Date Title
DE102012014068.1 2012-07-13
DE102012014068.1A DE102012014068B3 (de) 2012-07-13 2012-07-13 Austenitische Stahllegierung mit ausgezeichneter Zeitstandfestigkeit sowie Oxidations- und Korrosionsbeständigkeit bei erhöhten Einsatztemperaturen
PCT/DE2013/000369 WO2014008881A1 (de) 2012-07-13 2013-06-27 Austenitische stahllegierung mit ausgezeichneter zeitstandfestigkeit sowie oxidations- und korrosionsbeständigkeit bei erhöhten einsatztemperaturen

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US (1) US20150203944A1 (ko)
EP (1) EP2872664A1 (ko)
JP (1) JP2015528057A (ko)
KR (1) KR20150023935A (ko)
CN (1) CN104718306A (ko)
BR (1) BR112015000274A2 (ko)
DE (1) DE102012014068B3 (ko)
UA (1) UA113659C2 (ko)
WO (1) WO2014008881A1 (ko)

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US20170130603A1 (en) * 2015-11-11 2017-05-11 Mitsubishi Hitachi Power Systems, Ltd. Austenite steel, and austenite steel casting using same
US10519533B2 (en) 2015-06-15 2019-12-31 Nippon Steel Corporation High Cr-based austenitic stainless steel
SE2130240A1 (en) * 2021-09-07 2023-03-08 Alleima Emea Ab An austenitic alloy object

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10519533B2 (en) 2015-06-15 2019-12-31 Nippon Steel Corporation High Cr-based austenitic stainless steel
US20170130603A1 (en) * 2015-11-11 2017-05-11 Mitsubishi Hitachi Power Systems, Ltd. Austenite steel, and austenite steel casting using same
US10415423B2 (en) * 2015-11-11 2019-09-17 Mitsubishi Hitachi Power Systems, Ltd. Austenite steel, and austenite steel casting using same
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SE545185C2 (en) * 2021-09-07 2023-05-09 Alleima Emea Ab An austenitic alloy object

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JP2015528057A (ja) 2015-09-24
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UA113659C2 (uk) 2017-02-27
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