EP1805340B1 - Acier de traitement martensitique, durcissable et resistant au fluage - Google Patents

Acier de traitement martensitique, durcissable et resistant au fluage Download PDF

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Publication number
EP1805340B1
EP1805340B1 EP05795177A EP05795177A EP1805340B1 EP 1805340 B1 EP1805340 B1 EP 1805340B1 EP 05795177 A EP05795177 A EP 05795177A EP 05795177 A EP05795177 A EP 05795177A EP 1805340 B1 EP1805340 B1 EP 1805340B1
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EP
European Patent Office
Prior art keywords
weight
heat
creep
ductility
range
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Not-in-force
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EP05795177A
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German (de)
English (en)
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EP1805340A1 (fr
Inventor
Mohamed Youssef Nazmy
Markus Staubli
Andreas KÜNZLER
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General Electric Technology GmbH
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Alstom Technology AG
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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
    • C22C38/001—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
    • 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

Definitions

  • the invention relates to martensitic-hardenable steels with increased nitrogen contents, which are characterized by a very good combination of properties, in particular by a high resistance to creep and good ductility.
  • Martensite-hardenable steels based on 9-12% chromium are widely used materials in power plant technology. It is known that the addition of chromium in the abovementioned range not only provides good resistance to atmospheric corrosion but also complete through-hardenability of thick-walled forgings, for example as monobloc rotors or as rotor disks in gas and steam turbines. Proven alloys of this type usually contain about 0.08 to 0.2% carbon, which in solution allows the setting of a hard martensitic structure.
  • a good combination of heat resistance and ductility of martensitic steels is made possible by a tempering treatment in which Forming a particle-stabilized subgrain structure by the precipitation of carbon in the form of carbides with simultaneous recovery of the dislocation substructure.
  • the tempering behavior and the resulting properties can be effectively influenced by the choice and proportionate tuning of specific carbide formers such as Mo, W, V, Nb and Ta.
  • Strengths above 850 MPa for 9-12% chromium steels can be adjusted by keeping the tempering temperature low, typically in the range 600 to 650 ° C.
  • the use of low tempering temperatures leads to high transition temperatures from the brittle to the ductile state (above 0 ° C), with which the material exhibits brittle fracture behavior at room temperature.
  • Significantly improved ductilities can be achieved if the tempered strength is lowered below 700 MPa. This is achieved by raising the tempering temperature to over 700 ° C.
  • the use of increased tempering temperatures has the advantage that the set structural states are stable for longer times at elevated temperatures.
  • a typical representative who has found widespread use in steam power plants, in particular as rotor steel, is the German steel X20CrMoV12.1 known under DIN.
  • the ductility at a strength level of 850 MPa can be significantly improved by alloying nickel.
  • nickel by alloying about 2 to 3% nickel, even after a tempering treatment at temperatures of 600 to 650 ° C, the transition temperature from brittle to ductile state is still below 0 ° C, resulting in a significantly improved overall combination of strength and ductility.
  • Such alloys are therefore widely used where significantly higher demands are placed on both strength and ductility, typically as disk materials for gas turbine rotors.
  • a typical representative of such alloys, which in the gas turbine technology, in particular as a material for rotor disks width Has found use is known under DIN German steel X12CrNiMo12.
  • EP 0 931 845 A1 a nickel-containing 12% chromium steel similar in structure to the German steel X12CrNiMo12, in which the element molybdenum is reduced compared to the known steel X12 CrNiMo12, but an increased content of tungsten was added.
  • DE 198 32 430 A1 is a further optimization of the X12CrNiMo12 similar steel with the name M152 disclosed in which by the addition of rare earth elements, the embrittlement tendency in the temperature range between 425 and 500 ° C is limited.
  • EP 0 866 145 A2 describes a new class of martensitic chromium steels with nitrogen contents in the range 0.12 to 0.25%.
  • the entire structure of the structure is determined by the Formation of Sonderitriden, in particular controlled by Vanadiumnitriden, which can be distributed by the forging treatment, by the austenitization, by a controlled cooling treatment or by a tempering treatment in a variety of ways.
  • the high ductility setting in this patent application is aimed at by the distribution and morphology of the nitrides, but especially by limiting grain coarsening during forging and solution heat treatment. This is achieved in the cited document by an increased volume fraction as well as by a high particle coarsening resistance of sparingly soluble nitrides, so that a dense dispersion of nitrides is still capable of effectively limiting grain growth even at austenitizing temperatures of 1150 to 1200 ° C.
  • nitrides are only one factor for achieving maximum ductility.
  • Another factor is the effect of dissolved substitution elements such as nickel and manganese.
  • Manganese is known from carbon steels to be embrittling rather than promoting ductility. In particular, it causes embrittlement when the alloy is subjected to long-term annealing at temperatures in the range of 350 to 500 ° C. It is also known that nickel in carbon steels improves ductility but tends to lower high temperature hot strength as well. This is related to reduced carbide stability in nickel-containing steels.
  • a martensitic-hardenable tempering steel having the following chemical composition is known (in% by weight): 9 to 12 Cr, 0.001 to 0.25 Mn, 2 to 7 Ni, 0.001 to 8 Co, at least one of W and Mo in the sum between 0.5 and 4, 0.5 to 0.8, at least one of Nb, Ta, Zr Hf in the Sum between 0.001 to 0.1, 0.001 to 0.05 Ti, 0.001 to 0.15 Si, 0.01 to 0.1 C, 0.12 to 0.18 N, max. 0.025 P, max. 0.015 S, max. 0.01 Al, max. 0.0012 Sb, max. 0.007 Sn, max.
  • V / N 0.012 As, balance Fe and common impurities, and the proviso that the weight ratio of vanadium to nitrogen V / N ranges between 3.5 and 4.2.
  • These alloys are characterized by a very good combination of impact energy at room temperature and heat resistance at 550 ° C, especially at higher Cr contents.
  • the relatively high N content increases the creep rupture strength.
  • V and N are in the specified range in nearly stoichiometric proportions. This achieves optimum solubility and coarsening resistance of the vanadium nitrides.
  • the high solubility is required to dissolve as much of the precipitation hardening vanadium nitride as possible, while a high resistance to coarsening of the nitrides is needed in order to have the finest possible fine structure in the EP 1 158 067 A1 To achieve the described heat treatment.
  • the invention has for its object to provide a martensitic-hardenable tempering steel with high ductility in the temperature range between 350 and 500 ° C and good creep resistance in the temperature range up to 550 ° C.
  • Core of the invention is a martensitic-hardenable tempering steel having the following composition (in wt .-%): 8.5 to 9.5 Cr, 0.15 to 0.25 Mn, 2 to 2.7 Ni, 0.5 to 2.5 Mo, 0.4 to 0.8 V, 0.02 to 0.04 Nb , 0.001 to 0.15 Si, 0.06 to 0.1 C, 0.11 to 0.15 N, maximum 0.007 P, maximum 0.005 S, maximum 0.01 Al, balance iron and common impurities, and the requirement that the weight ratio of vanadium to nitrogen V / N in the range between 4.3 and 5.5.
  • the advantage of the invention is that in the said alloy, a compensation structure is set, which is characterized by a tough matrix and the presence of heat-resistant nitrides, at the same time a tendency to embrittlement in the range between 350 and 500 ° C is suppressed.
  • the toughness of the base matrix is adjusted by the presence of substitution elements, preferably nickel.
  • the contents of the substitution elements are determined so as to allow optimum unfolding of both martensite hardening and particle hardening by means of special nitrides, preferably vanadium nitrides, to provide high creep strength coupled with good ductility.
  • the embrittlement tendency of the inventive steel in the temperature range of 350 to 500 ° C due to precipitation of the ⁇ 'Cr phase is suppressed by the low compared to the prior art, the Cr content and moderate N content.
  • a weight content of 8.5 to 9.5% chromium allows a reasonable hardenability of thick-walled components and ensures sufficient oxidation resistance up to a temperature of 550 ° C.
  • a weight fraction below 8.5% impairs the through-hardenability. Contents above 9.5% lead to the accelerated formation of the ⁇ 'Cr phase during the tempering process, which leads to embrittlement of the material.
  • the range to be specified should be between 0.15 and 0.25% for manganese and between 0.001 and 0.15% for silicon, taking into account the possibilities of ladle metallurgy.
  • Nickel is used as an austenite stabilizing element to suppress delta ferrite. In addition, it is said to improve ductility as a dissolved element in the ferritic matrix. Nickel contents between 2 to 2.7 wt .-% are optimal, since on the one hand, the nickel is homogeneously dissolved in the matrix, on the other hand, there is still no increased proportion of retained austenite or tempering austenite in the tempered martensite.
  • This element improves creep strength by solid solution hardening as a partially dissolved element and precipitation hardening during a long-term stress.
  • an excessively high proportion of this element leads to embrittlement during a long-term aging, which is due to the excretion and coarsening of the sigma phase.
  • the maximum proportion of Mo must be limited to 2.5%.
  • a preferred range is about 1.4 to 1.6%.
  • microstructural forms are optimal when the elements vanadium and nitrogen are alloyed in a slightly more than stoichiometric V / N ratio.
  • a slightly more than stoichiometric ratio also increases the stability of the vanadium nitride over that of the chromium nitride.
  • a V / N ratio in the range between 4.3 to 5.5 is preferred.
  • the specific content of nitrogen and vanadium nitrides depends on the optimum volume fraction of the vanadium nitrides, which are to remain as insoluble primary nitrides during the solution annealing.
  • niobium is a preferred element among the special nitride formers.
  • the preferred range is 0.02 to 0.04% by weight.
  • the grain coarsening resistance in solution annealing is increased and the stability of primary and excrete V8N, C) nitrides is increased by partial substitution of V.
  • these elements together with silicon and manganese, these elements increase the embrittlement of long-term aging in the range between 350 and 500 ° C. These elements should therefore be limited to the minimum tolerable levels.
  • This element is a strong nitride former, which already sets nitrogen in the melt and thus strongly affects the effectiveness of the added nitrogen.
  • the aluminum nitrides formed in the melt are very coarse and reduce the ductility. Aluminum must therefore be limited to a weight fraction of 0.01%.
  • Table 1 shows the chemical composition (in% by weight) of a preferred alloy according to the invention (DM13) and of comparative alloys: Table 1: Chemical composition DM13A-2 St13TNiEL alloy Type "D" C 12:08 12:12 12:04 Cr 9.0 11.5 11.2 Mn 12:19 Max. 0.25 12:05 Ni 2.4 2.3 3:06 Co 4:02 Not a word 1.4 1.5 1.83 V 0.6 12:25 0.61 Nb 12:04 12:03 Si 12:13 12:25 ⁇ 00:02 N 0117 0035 0156 al 0008 ⁇ 00:02 P Max. 0.025 0004 S Max. 0.015 0002 V / N 5.13 7.24 3.91
  • Table 2 contains experimental data for determining the notched impact energy at room temperature: Table 2: Notch energy for various differently treated alloys alloy conditions Notch energy in J DM13A-2 Initial state after the above heat treatment 76 Outsourced at 400 ° C / 1032h 90 Outsourced at 480 ° C / 1032h 58 St13TNiEL Initial state after the above heat treatment > 40 (required) Alloy "D" Initial state after the above heat treatment 106 Outsourced at 300 ° C / 5000h 57 Outsourced at 380 ° C / 5000h 36 Outsourced at 450 ° C / 5000h 21 Outsourced at 500 ° C / 5000h 54
  • the alloy according to the invention is distinguished by a high heat resistance at 550 ° C., as well as by a high ductility and a good modulus of elasticity.
  • the voltage for 1% creep at 550 ° C for the alloys DM13A-2 and St13TNiEL is shown as a function of time.
  • the advantage of the alloy according to the invention comes into play at high removal times.
  • the invention is not limited to the embodiment described.

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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 Articles (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Heat Treatment Of Steel (AREA)
  • Paints Or Removers (AREA)

Claims (8)

  1. Acier de traitement durcissable martensitique, caractérisé par la composition chimique suivante (données en % en poids) : de 8,5 à 9,5 de Cr, de 0,15 à 0,25 de Mn, de 2 à 2,7 de Ni, de 0,5 à 2,5 de Mo, de 0,4 à 0,8 de V, de 0,001 à 0,15 de Si, de 0,06 à 0,1 de C, de 0, 11 à 0, 15 de N, de 0, 02 à 0,04 de Nb, au plus 0, 007 de P, au plus 0, 005 de S, au plus 0,01 de Al, le reste étant constitué de fer et d'impuretés habituelles, à condition que le rapport pondéral entre le vanadium et l'azote V/N soit dans la plage comprise entre 4,3 et 5,5.
  2. Acier de traitement durcissable martensitique selon la revendication 1, caractérisé par de 8,5 à 9 % en poids de Cr.
  3. Acier de traitement durcissable martensitique selon la revendication 1, caractérisé par 0,2 % en poids de Mn.
  4. Acier de traitement durcissable martensitique selon la revendication 1, caractérisé par de 2,3 à 2,6 % en poids de Ni.
  5. Acier de traitement durcissable martensitique selon la revendication 1, caractérisé par de 1,4 à 1,6 % en poids de Mo.
  6. Acier de traitement durcissable martensitique selon la revendication 1, caractérisé par de 0,5 à 0,6 % en poids de V.
  7. Acier de traitement durcissable martensitique selon la revendication 1, caractérisé par de 0,11 à 0,12 % en poids de N.
  8. Acier de traitement durcissable martensitique selon la revendication 1, caractérisé par de 0,06 à 0,08 % en poids de C.
EP05795177A 2004-10-29 2005-10-14 Acier de traitement martensitique, durcissable et resistant au fluage Not-in-force EP1805340B1 (fr)

Applications Claiming Priority (2)

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CH17922004 2004-10-29
PCT/EP2005/055252 WO2006045708A1 (fr) 2004-10-29 2005-10-14 Acier de traitement martensitique, durcissable et resistant au fluage

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EP1805340A1 EP1805340A1 (fr) 2007-07-11
EP1805340B1 true EP1805340B1 (fr) 2008-08-27

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US (1) US7686898B2 (fr)
EP (1) EP1805340B1 (fr)
JP (1) JP2008518103A (fr)
CN (1) CN100480414C (fr)
AT (1) ATE406466T1 (fr)
DE (1) DE502005005216D1 (fr)
ES (1) ES2313422T3 (fr)
WO (1) WO2006045708A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2240619B1 (fr) * 2007-03-29 2017-01-25 General Electric Technology GmbH Acier résistant au fluage
EP2116626B1 (fr) * 2008-02-25 2010-12-22 ALSTOM Technology Ltd Acier resistant au fluage
US20100037994A1 (en) * 2008-08-14 2010-02-18 Gopal Das Method of processing maraging steel
JP6128935B2 (ja) * 2012-05-22 2017-05-17 キヤノン株式会社 液体吐出ヘッド用基板、及び液体吐出ヘッド
CN102912248A (zh) * 2012-10-13 2013-02-06 山东理工大学 高韧性耐磨耐蚀马氏体不锈钢及其制造方法
CN104789894A (zh) * 2015-04-04 2015-07-22 王文姣 一种高强度汽车保险杠的热处理方法及该高强度汽车保险杠
GB2546809B (en) * 2016-02-01 2018-05-09 Rolls Royce Plc Low cobalt hard facing alloy
GB2546808B (en) * 2016-02-01 2018-09-12 Rolls Royce Plc Low cobalt hard facing alloy

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Publication number Publication date
CN100480414C (zh) 2009-04-22
US20070193661A1 (en) 2007-08-23
US7686898B2 (en) 2010-03-30
ATE406466T1 (de) 2008-09-15
DE502005005216D1 (de) 2008-10-09
WO2006045708A1 (fr) 2006-05-04
EP1805340A1 (fr) 2007-07-11
CN101048525A (zh) 2007-10-03
JP2008518103A (ja) 2008-05-29
ES2313422T3 (es) 2009-03-01

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