EP2307586B1 - Stahllegierung für einen ferritischen stahl mit ausgezeichneter zeitstandfestigkeit und oxidationsbeständigkeit bei erhöhten einsatztemperaturen - Google Patents

Stahllegierung für einen ferritischen stahl mit ausgezeichneter zeitstandfestigkeit und oxidationsbeständigkeit bei erhöhten einsatztemperaturen Download PDF

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Publication number
EP2307586B1
EP2307586B1 EP09775941.9A EP09775941A EP2307586B1 EP 2307586 B1 EP2307586 B1 EP 2307586B1 EP 09775941 A EP09775941 A EP 09775941A EP 2307586 B1 EP2307586 B1 EP 2307586B1
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Prior art keywords
max
steel
content
phase
ferritic
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German (de)
English (en)
French (fr)
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EP2307586A1 (de
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Bernd Hahn
Joachim Konrad
André Schneider
Charles Stallybrass
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Vallourec Deutschland GmbH
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Vallourec Deutschland GmbH
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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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles

Definitions

  • the invention relates to a steel alloy for a ferritic steel with excellent creep strength and oxidation resistance at elevated use temperatures according to claim 1.
  • the invention relates to seamless or welded tubes made of this steel alloy, the z. B. are used as heat exchanger tubes in heaters or power plant boilers in temperature ranges from about 620 ° C to about 750 ° C.
  • High temperature, high creep, and corrosion resistant high temperature materials for use, for example, in power plants are generally based on either ferritic, ferritic / martensitic or austenitic iron-based alloys, or nickel-base alloys.
  • the specific requirements in the lower temperature stages of the heat exchanger tubes consist in particular in a low thermal expansion.
  • Austenitic grades can not be used since their thermal expansion is too high in the described temperature range. For the elevated temperatures in the boiler, the previously available ferritic / martensitic materials are no longer in question, since with sufficient corrosion resistance their creep or heat resistance is no longer sufficient.
  • a sufficient combination of properties of corrosion resistance and heat resistance offer nickel-based alloys with nickel contents of over 50 wt .-%.
  • the steels are thus extremely expensive and the processing to seamless pipes is also quite problematic.
  • austenitic steels are currently being used. Of disadvantage here are the high alloying costs (Ni up to 30%), poor processability and lack of thermal conductivity.
  • Chromium-rich ferritic steel is significantly cheaper compared to austenitic stainless steel and has a higher coefficient of thermal conductivity and a lower coefficient of thermal expansion.
  • chromium-rich ferritic steel also has a high oxidation resistance, which is advantageous for a hot steam, z. B. in heaters or boilers, is.
  • oxide films form as a coating (scale or scale layer), they can detach at the corresponding boiler temperature and / or boiler pressure changes, settle in the steel pipes and clog them.
  • ferritic iron-based alloys for pipes or pipelines, which offer the required creep and corrosion properties even at higher operating temperatures above 620 ° C. For example, creep rupture strengths of 105 hours at this temperature stress for a load of 100 MPa without breakage should be achieved.
  • Steels available for use at temperatures of about 620 ° C and 650 ° C, respectively, are ferritic / martensitic steels with Cr contents of e.g. 8 to 15%.
  • Corresponding steels go, for example, from the scriptures DE 19941 411 A1 . DE 692 04 123 T2 . US 2006/0060270 A1 . DE 601 10 861 T2 and DE 69608 744 T2 out.
  • the alloy concepts disclosed there usually have expensive alloy additives or are also unsuitable for use in temperature ranges above 620 ° C.
  • the said excretion phases are not in sufficient volume proportions representable, since an increase in the content of the metallic (eg Ti, Nb or V) as well as the non-metallic components (C or N) not only leads to an increase in the phase content, but also increases the solution temperature of the phase. As a result, the formation temperature of the precipitates is above a reasonable heat treatment temperature and sometimes even above the solidus temperature of the alloy.
  • metallic eg Ti, Nb or V
  • C or N non-metallic components
  • the formation temperature of the precipitates is directly related to their size, one obtains either a relatively small volume fraction of effective reinforcing particles ( ⁇ 1%) or a high volume fraction of coarse particles (> 1 ⁇ m), which remain ineffective with regard to creep resistance.
  • the MX and M2X particles preferably precipitate out in the grain interior. It is to be expected that at use temperatures> 630 ° C the influence of grain boundary creep increases in relation to dislocation creep.
  • a depletion of reinforcement phases at grain boundaries is therefore to be regarded as particularly critical.
  • the incoherent precipitates are more prone to coarsening than coherent because, on the one hand, the interfacial energy as a driving force for interface minimization is higher than for coherent particles and, on the other hand, easily diffusing elements such as C and N are part of these particles.
  • the in the WO 03/029505 described alloy is a further development of known under the name Kanthai FeCrAI alloy, the z. B. is used for heating elements for temperatures above 1000 ° C.
  • This alloy has a high chromium and aluminum content in order to ensure the most efficient conversion of electrical energy into heat.
  • the combination of high chromium and aluminum contents means that these alloys are fully ferritic at chromium contents above 16% and aluminum contents above 4%, even at temperatures above 750 ° C, so that an austenite-ferrite transformation is possibly limited.
  • Such steels are not suitable for use in the power station sector, and chromium contents above 16% also impair the deformation capacity at typical processing temperatures when rolling seamless pipes (900 - 1200 ° C). This reduced deformability can lead to the formation of cracks during rolling. As a result, such alloys are not suitable for the production of pipes and sheets.
  • the US 6,332,936 B1 describes exclusively powder-metallurgically produced intermetallic alloys for the production of sheets on the basis of the system Fe-Al and contains the intermetallic phases Fe3Al, Fe2Al5, FeAl3, FeAl, FeAlC, Fe3AIC and combinations of these phases.
  • An unordered phase such. As ferrite, is not included.
  • the described FeAl-B2 phase is used exclusively as a matrix in these publications.
  • the powder metallurgy production of such an intermetallic alloy is unsuitable for the large-scale production of pipes and sheets.
  • the Japanese patent application JP H 03 236 449 A discloses a high chrome steel for use in boiler tubes in waste incineration.
  • the steel described is distinguished by particular oxidation resistance, especially at high temperatures, and the composition is given in% by weight as follows: C: 0.005 to 0.05; Si: ⁇ 2; Mn: ⁇ 2; Cr: 9 to 16; Ni: 2 to 10 and Al: 1 to 6.
  • the steel may contain one or more of Ti, Nb and Zr in the total content of 0.1 to 1% by weight.
  • the object of the invention is to provide a cost-effective steel alloy for a ferritic at use temperature steel, which satisfies the stated requirements with respect to creep rupture strength and oxidation resistance, even at operating temperatures up to 750 ° C.
  • Another object is to produce from this steel alloy workpieces such. As hot-rolled seamless or welded tubes, sheets, castings or tool steels to provide.
  • the inventive alloy concept differs fundamentally from the known alloy concepts.
  • the ferritic alloy which is fully ferritic at an operating temperature of up to about 750 ° C, obtains its excellent creep and corrosion properties according to the new innovative approach by coherent finely divided precipitates of nanoparticles of a chromium-stabilized (Ni, Co) Al-B2 intermetallic ordering phase.
  • the precipitates are coherent to the ferritic matrix and uniformly and finely distributed throughout the grain both within the grain and near grain boundaries. Advantages of this steel alloy are the significantly lower costs and also cause the coherent precipitates of the intermetallic (Ni, Co) AI-B2 phase over known alloy concepts significant increase in creep rupture at temperatures above 620 ° C and even above 650 ° C to about 750 ° C.
  • the concept underlying this invention dispenses with expensive or hard-to-obtain elements for producing an intermetallic amplification phase.
  • the (Ni, Co) Al phase with B2 structure requires significantly lower Ni or Co contents than available austenitic steels.
  • the special feature of the B2 phase in the Fe-Cr-Al (Ni, Co) system lies in the pronounced miscibility gap that can be controlled via the Cr content for (Ni, Co) Al.
  • B2 phase contents in steel above 8 mol% (VS2) are unfavorable because of the associated reduction in toughness and poorer machinability of the steel and should therefore be avoided.
  • the elements Ni, Al and small amounts of Fe could be detected.
  • Fe, Cr, Al and Si could be detected in the matrix.
  • the mean particle radius of the B2-NiAl phase is about 40 nm, the molar phase fraction about 5.6%.
  • the coarsening in the period of conventional qualifications is well below the maximum effective mean particle radius value of about 500 nm.
  • the steel is alloyed with Cr in amounts of from 2 to ⁇ 16% by weight.
  • an advantageous embodiment of the invention is obtained by setting an excess of Al in relation to Ni or Co (superstoichiometric for the adjustment of NiAl or CoAl) also a further significant increase in the oxidation resistance.
  • the composition should be chosen so that at the application temperature, a stable structure of ferritic structure and the (Ni, Co) AI-B2 phase is given as main components.
  • the elements Si and Mn can be present either only in the context of steel-like accompanying elements or alloyed for additional solid solution hardening in amounts of up to 1% in each case. As favorable contents of max. 0.4% for Si and 0.5% for Mn. Si serves to slightly increase the heat resistance. If this is in the foreground of the application, higher levels are recommended. Mn has a negative effect on the steam oxidation behavior at higher levels. If this risk does not exist in the application, Mn can be added as an additional element to increase the strength at room temperature and elevated temperatures.
  • the C content is of minor importance for the present alloy concept, but should not exceed 1.0%. As favorable, maximum contents of 0.5% have been found. Contents above 1% complicate the processability and favor the formation of coarse and thus harmful special carbides. At C contents below 0.5%, the formation of special carbides is already greatly reduced. Depending on the operating temperature, however, the C content must be adjusted in order to avoid a strong precipitation and growth of these special carbides when used.
  • the N content should be set as low as possible and is limited to max. Limit 0,0200%.
  • surfactants to both internal interfaces, such as grain boundaries and phase boundaries, as well as the protective oxide layer interfaces; to influence specifically.
  • These include the elements Hf, B, Y, Se, Te, Sb, La and Zr, which are alloyed in the range of the sum content of ⁇ 0.1%.
  • the steel alloy advantageous z. B. can be used for heat exchanger tubes in the power plant area, the use is not limited thereto.
  • this steel alloy can also be used for the production of sheet metal, castings, centrifugal castings or tools for machining (tool steels), whereby the field of application is pressure vessels; Boilers, turbines, nuclear power plants or chemical apparatus engineering, d. H. to all areas with appropriate temperature requirements and corrosion stresses extends.
  • the steel alloy according to the invention can be used particularly advantageously above 620 ° C. to about 750 ° C. because of the excellent creep rupture strength and oxidation properties, the use is advantageous, for example, even at temperatures above 500 ° C. when it depends more on the strength of the material.

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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)
  • Treatment Of Steel In Its Molten State (AREA)
EP09775941.9A 2008-07-23 2009-07-03 Stahllegierung für einen ferritischen stahl mit ausgezeichneter zeitstandfestigkeit und oxidationsbeständigkeit bei erhöhten einsatztemperaturen Active EP2307586B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102008034817 2008-07-23
DE102009031576A DE102009031576A1 (de) 2008-07-23 2009-06-30 Stahllegierung für einen ferritischen Stahl mit ausgezeichneter Zeitstandfestigkeit und Oxidationsbeständigkeit bei erhöhten Einsatztemperaturen
PCT/DE2009/000953 WO2010009700A1 (de) 2008-07-23 2009-07-03 Stahllegierung für einen ferritischen stahl mit ausgezeichneter zeitstandfestigkeit und oxidationsbeständigkeit bei erhöhten einsatztemperaturen

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EP2307586A1 EP2307586A1 (de) 2011-04-13
EP2307586B1 true EP2307586B1 (de) 2018-10-10

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US (1) US9080230B2 (es)
EP (1) EP2307586B1 (es)
JP (1) JP5844150B2 (es)
CN (1) CN102137948B (es)
AR (1) AR072594A1 (es)
DE (1) DE102009031576A1 (es)
WO (1) WO2010009700A1 (es)

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CN103352177B (zh) * 2013-06-17 2015-12-23 浙江浦宁不锈钢有限公司 一种强度增强的钢材
CN103614654A (zh) * 2013-10-22 2014-03-05 芜湖市鸿坤汽车零部件有限公司 一种用于发动机罩的合金钢材料及其制备方法
CN103667891A (zh) * 2013-11-08 2014-03-26 张超 一种用于输送含氯根的混酸液体泵的合金钢材料及其制备方法
CN103643175A (zh) * 2013-11-12 2014-03-19 铜陵市肆得科技有限责任公司 一种阀芯用合金钢材料及其制备方法
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CN104785775A (zh) * 2015-04-21 2015-07-22 苏州统明机械有限公司 一种用于热喷涂的耐氧化合金钢粉末及其制备方法
CN104895638B (zh) * 2015-05-17 2017-12-01 嵊州亿源投资管理有限公司 一种汽车发动机进气门
CN107794459B (zh) * 2015-05-18 2019-05-24 南京市星淳机械有限公司 一种汽车发动机气缸盖
CN104895639B (zh) * 2015-05-24 2018-03-16 新昌县勤勉贸易有限公司 一种耐高温气缸排气门组
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US10883160B2 (en) 2018-02-23 2021-01-05 Ut-Battelle, Llc Corrosion and creep resistant high Cr FeCrAl alloys
CN108330405A (zh) * 2018-03-30 2018-07-27 四川六合锻造股份有限公司 一种耐腐蚀性能优异且耐高温性能好的优质合金
CN109930076A (zh) * 2019-04-23 2019-06-25 洛阳中伟环保科技有限公司 一种磨机用无碳合金钢球
CN110042308A (zh) * 2019-04-23 2019-07-23 洛阳中伟环保科技有限公司 一种磨机用无碳合金衬板
CN110029273A (zh) * 2019-04-23 2019-07-19 洛阳中伟环保科技有限公司 一种磨机用无碳合金隔仓板
KR102255111B1 (ko) * 2019-07-31 2021-05-24 주식회사 포스코 내식성이 우수한 배기계용 페라이트계 강판
KR102324087B1 (ko) * 2019-12-18 2021-11-10 한전원자력연료 주식회사 페라이트계 합금 및 이를 이용한 핵연료 피복관의 제조방법
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CN102137948B (zh) 2014-06-11
DE102009031576A1 (de) 2010-03-25
JP5844150B2 (ja) 2016-01-13
US20110189496A1 (en) 2011-08-04
WO2010009700A1 (de) 2010-01-28
EP2307586A1 (de) 2011-04-13
US9080230B2 (en) 2015-07-14
CN102137948A (zh) 2011-07-27
AR072594A1 (es) 2010-09-08
JP2011528752A (ja) 2011-11-24

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