EP2722407A2 - Acier martensitique durcissable par précipitation et aube allongée pour turbine de vapeur - Google Patents

Acier martensitique durcissable par précipitation et aube allongée pour turbine de vapeur Download PDF

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Publication number
EP2722407A2
EP2722407A2 EP13189010.5A EP13189010A EP2722407A2 EP 2722407 A2 EP2722407 A2 EP 2722407A2 EP 13189010 A EP13189010 A EP 13189010A EP 2722407 A2 EP2722407 A2 EP 2722407A2
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EP
European Patent Office
Prior art keywords
less
stainless steel
steam turbine
precipitation hardening
martensitic stainless
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13189010.5A
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German (de)
English (en)
Other versions
EP2722407A3 (fr
Inventor
Shinji Oikawa
Hideo Yoda
Masahiko Arai
Hiroyuki Doi
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.)
Mitsubishi Power Ltd
Original Assignee
Hitachi Ltd
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Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Publication of EP2722407A2 publication Critical patent/EP2722407A2/fr
Publication of EP2722407A3 publication Critical patent/EP2722407A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
    • 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
    • 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
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • the present invention relates to a precipitation hardening martensitic stainless steel having excellent texture stability, mechanical properties, and corrosion-resistance; and also a long blade for a steam turbine using the same.
  • a long blade material having both excellent mechanical properties and corrosion-resistance is required to improve the reliability of the steam turbine.
  • a precipitation hardening martensitic stainless steel has a large amount of Cr and a small amount of C and thus has excellent corrosion-resistance.
  • a balance between strength and toughness thereof is poor (refer to, e.g., JP-A-2005-194626 ).
  • An object of the invention is to provide precipitation hardening martensitic stainless steel having excellent mechanical properties and corrosion-resistance.
  • the precipitation hardening martensitic stainless steel of the present invention contains, by mass, 0.1% or less of C; 0.1% or less of N; 10.0% ⁇ 15.0% of Cr; 10.0% ⁇ 15.0% of Ni; 0.5% ⁇ 2.5% of Mo; 1.0% ⁇ 3.0% of Al, 1.0% or less of Si; 1.0% or less of Mn, and the rest is Fe and inevitable impurities.
  • the amount of constituent elements is represented by mass ratio (%).
  • Carbon (C) forms a Cr carbide, and there are problems that toughness is reduced due to excessive precipitation of carbides and corrosion resistance deteriorates due to reduction in a Cr concentration near a grain boundary. Further, C remarkably reduces an end point of the martensitic transformation temperature. Consequently, the amount of C needs to be suppressed.
  • the amount of C may be preferably 0.1% or less, and more preferably 0.05% or less.
  • Nitrogen (N) forms TiN and AlN to reduce fatigue strength, and also adversely affects toughness.
  • the amount of N added needs to be suppressed.
  • the amount may be preferably 0.1% or less, and more preferably 0.05% or less.
  • Chromium (Cr) is an element that forms a passive film on the surface and thus contributes to an improvement in the corrosion-resistance.
  • the lower limit of addition is set to 10.0% so that the corrosion resistance may be sufficiently secured.
  • the upper limit thereof is set to 15.0%. From above, the amount of Cr added needs to be set to 10.0 to 15.0%.
  • the amount may be preferably 11.0 - 14.0%, and particularly preferably 12.0 - 13.0%.
  • Nickel (Ni) is an element that suppresses a formation of ⁇ ferrite and also contributes to an improvement in the strength through the precipitation hardening of Ni-Al compounds. Moreover, Ni also improves hardenability and toughness. To sufficiently achieve effects described above, the lower limit of addition needs to be set to 10.0%. On the other hand, when the amount added is more than 15.0%, a harmful phase is precipitated. As a result, an intended mechanical property is not obtained. Judging from the above points, the amount of Ni added needs to be set to 10.0 ⁇ 15.0%. The amount may be more preferably 11.0 ⁇ 14.0%, and particularly preferably 12.0 ⁇ 13.0%.
  • Molybdenum (Mo) is an element that improves corrosion resistance. To obtain the intended corrosion resistance, the amount of Mo added of at least 0.5% is needed. On the other hand, when the amount of Mo added is more than 2.5%, a formation of a harmful phase is assisted and conversely the properties deteriorate. Judging from the above points, the amount of Mo added needs to be set to 0.5 - 2.5%. The amount may be more preferably 1.0 ⁇ 2.0%, and particularly preferably 1.25 ⁇ 1.75%.
  • Aluminum (Al) is an element that forms a Ni-Al compound and contributes to precipitation hardening.
  • the amount of Al added of at least 1.0% or more is needed.
  • the amount of Al added is more than 3.0%, the mechanical property is reduced due to the excessive precipitation of the Ni-Al compounds and the formation of harmful phases. Judging from the above points, the amount of Al added needs to be set to 1.0 ⁇ 3.0%.
  • the amount may be more preferably 1.5 ⁇ 2.5%, and particularly preferably 1.75 - 2.25%.
  • Silicon (Si) is a deoxidizing agent, and the amount of Si added may be preferably set to 1.0% or less. When the amount is more than 1.0%, there arises a problem that ⁇ ferrite is precipitated.
  • the amount of Si added may be more preferably 0.5% or less, and may be particularly preferably 0.25% or less. It is possible to omit the addition of Si by applying carbon vacuum deoxidization and electro slag remelting. In that case, no addition of Si is preferable.
  • Manganese (Mn) is added as a deoxidizing agent and a desulfurizing agent.
  • the amount of Mn added is more than 1.0%, harmful phases are excessively formed and necessary strength is not obtained. Therefore, the amount of Mn added needs to be set to 1.0% or less.
  • Mn need not be added.
  • the amount of Mn added may be more preferably 0.5% or less, and particularly preferably 0.25% or less.
  • tungsten (W) exerts an effect of improving the corrosion resistance as well as Mo. W further improves this effect through the addition in combination with Mo. In this case, to prevent harmful phases from being precipitated, the sum of the amount of Mo and W added needs to be the same as the amount of Mo added alone.
  • niobium (Nb) is an element that forms carbides and contributes to an improvement in the strength; however, deteriorates productivity.
  • the amount of Nb added needs to be set to 1.0% or less.
  • tantalum (Ta) it is possible to substitute tantalum (Ta) for Nb.
  • the sum of the amount of Nb and Ta added needs to be the same as the amount of Nb added alone.
  • Inevitable impurities in the present invention are components originally contained in the raw materials or incorporated during production and so on, and refer to components that are unintentionally added.
  • Inevitable impurities include P, S, Sb, Sn, and As, and at least one of them may be contained in the precipitation hardening martensitic stainless steel of the present invention.
  • P is set to be 0.5% or less and S is set to be 0.5% or less. It is particularly preferable that P is set to be 0.1% or less and S is set to be 0.1% or less.
  • As, Sb, and Sn make it possible to improve toughness.
  • the solution treatment in the present invention refers to a heat treatment for both dissolving components relating to the formation of precipitates such as Al and Ni into the texture and obtaining a martensite texture at the same time.
  • the martensite texture is a kind of matrix of steel and is a texture excellent in the balance between strength and toughness.
  • the aging treatment of the present invention refers to a heat treatment to obtain excellent strength by finely precipitating Ni-Al compounds and so on in the texture, performed after the solution treatment.
  • a sub-zero treatment may be performed.
  • the sub-zero treatment it is necessary to keep the residual austenite for at least four hours or more at -70°C or less and raise it up to room temperature in the atmosphere by using organic solvents such as dry ice and isopentane.
  • stellite plates of a Co-based alloy may be joined to a front end portion of the blade by TIG welding. This is a measure to protect the steam turbine long blade from erosion damaging the blade by the high-speed collision of condensed steam.
  • Other techniques for the installation of stellite plates include silver soldering, plasma transfer arc, and laser build-up welding.
  • Other measures to protect the steam turbine long blade from erosion include modification of the surface with a titanium nitride coating, etc.
  • Test samples were prepared to evaluate a relationship between the chemical composition of the precipitation hardening martensitic stainless steel of the present invention, tensile strength thereof, 0.02% yield strength, Charpy impact absorption energy, pitting potential, and micro-texture. Table 1 illustrates a chemical composition of each test sample.
  • raw materials were melted by using a high-frequency vacuum melting furnace (5.0 ⁇ 10 -3 Pa or less, 1600°C or higher) to obtain compositions listed in Table 1.
  • the obtained ingot was hot-forged by using a press forging machine and a hammer forging machine, and formed into a square bar having a width ⁇ thickness ⁇ length of 100 mm ⁇ 30 mm ⁇ 1000 mm.
  • the square bar was cut and processed to a width ⁇ thickness ⁇ length of 50 mm ⁇ 30 mm ⁇ 120 mm, thereby giving stainless steel starting materials.
  • the stainless steel starting materials were subjected to various heat treatments by using a box electric furnace.
  • Alloys 1 to 13 of the invention were maintained at 925°C for 1 hour as a solution heat treatment, followed by rapid water cooling of immersing in room-temperature water.
  • the alloys were maintained at an arbitrary temperature of 450 to 650°C for 2 hours as an aging heat treatment, followed by air cooling for removing them to room-temperature air.
  • a test piece (distance between evaluation points: 30 mm, outer diameter: 6 mm) was prepared from each of the samples obtained above and subjected to a tensile test at room temperature in accordance with JIS Z 2241.
  • the determination criteria of tensile strength and 0.02% yield strength are as follows. A tensile strength and 0.02% yield strength of 1500 MPa or more and 1000 MPa or more, respectively, were rated as "acceptable", while those of less than these values were rated as "unacceptable”. Further, an elongation and drawing of 10% or more and 30% or more, respectively, were rated as "acceptable”, while those of less than these values were rated as "unacceptable”.
  • Charpy impact absorption energy For the measurement of Charpy impact absorption energy, a test piece having a 2-mm V notch was prepared from each of the samples obtained above and subjected to a Charpy impact test at room temperature in accordance with JIS Z 2242.
  • the determination criteria of Charpy impact absorption energy are as follows. A Charpy impact absorption energy of 20 J or more was rated as “acceptable”, while that of less than this value was rated as "unacceptable”.
  • a plate-like test piece (15 mm in length, 15 mm in width, and 3 mm in thickness) was prepared from each of the samples obtained above, and coated with an insulator so that an area of a measurement surface becomes equal to 1.0 cm 2 .
  • the evaluation was performed under the following conditions: test solution: 3.0% NaCl solution, temperature of the solution: 30°C, sweep rate: 20 mV/min.
  • the determination criteria of pitting potential are as follows. A pitting potential of 150 mV or more was rated as "acceptable", while that of less than this value was rated as "unacceptable.”
  • micro-texture The determination criteria of micro-texture are as follows. Those having a martensite texture in which the amounts of ⁇ ferrite and residual austenite precipitated are 1.0% or less and 10% or less in an area ratio, respectively, were rated as "acceptable”. Others were rated as "unacceptable”. The amount of ⁇ ferrite precipitated was measured in accordance with a point counting method described in JIS G 0555. The amount of residual austenite precipitated was measured by X-ray diffraction.
  • alloys 1 to 13 of the invention mechanical properties of tensile strength, 0.02% yield strength, elongation, drawing, and impact absorption energy were also rated as "acceptable”. Also for pitting potential, preferable results were obtained. In addition, the ⁇ ferrite phase and residual austenite in the metal texture were within a target range, and they were thus confirmed to have a martensite texture.
  • any of the comparative alloys 1 to 12 all aimed values of the respective properties were not satisfied.
  • effects on principal components such as Cr, Ni, Mo, and Al were studied.
  • the comparative alloy 5 is a sample in which the amount of Al added is high, and in which tensile strength and 0.02% yield strength were high; however, elongation, drawing, and impact absorption energy were remarkably lower than their aimed values. The reason is considered that the amount of a reinforcing phase precipitated is excessive.
  • the comparative alloy 6 the amount of Al added is low, and tensile strength and 0.02% yield strength were lower than their aimed values. Further, a large amount of residual austenite was precipitated in the texture.
  • the comparative alloy 9 is a sample in which the amount of C added is high, and its tensile strength, 0.02% yield strength, elongation, and impact absorption energy were lower than their aimed values. Further, pitting potential was also lower than its aimed value. The reason is considered that a Cr concentration near a grain boundary is reduced through the formation of Cr carbides and corrosion resistance is deteriorated. In addition, a large amount of residual austenite was precipitated in the texture.
  • the comparative alloy 12 is a sample in which the amount of N added is high, and its elongation, drawing, and impact absorption energy were lower than their aimed values. Further, a large amount of residual austenite was precipitated in the texture.
  • Electro-slag remelting was thus performed to give a high-grade steel ingot by self-dissolving the electrode bar by Joule heat generated upon the application of current at the time when this electrode bar was immersed in molten slag, and then coagulating it in a water-cooled die.
  • the steel ingot was hot-forged, and then press-forged by using a 48-inch blade die.
  • the resulting product was heated and maintained at 925°C for 2.0 hours, followed by forced cooling of rapid cooling by using a fan.
  • the product was formed into a predetermined shape through a cutting step and then, as an aging treatment, heated and maintained at 525°C for 4.0 hours, followed by air cooling. As the final finishing, the curve was eliminated and the surface was polished, thereby giving a 48-inch long blade.
  • Test pieces were collected from the front end, center, and root portions of the steam turbine long blade obtained by the above steps, respectively, and subjected to evaluation tests in the same manner as in Example 1.
  • a direction of the collected test pieces is the direction of the length of the blade.
  • micro-texture of each portion was a uniform martensite texture. Neither residual austenite nor ⁇ ferrite was observed. In addition, regardless of the positions where the test pieces were collected, aimed values of the desired tensile strength, 0.02% yield strength, impact absorption energy, and pitting potential were achieved.
  • the precipitation hardening martensitic stainless steel of the present invention has excellent mechanical properties and corrosion-resistance, and thus can be applied to the steam turbine long blade. In addition, it can also be applied to a blade for a gas turbine compressor, and so on.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Heat Treatment Of Articles (AREA)
EP13189010.5A 2012-10-17 2013-10-16 Acier martensitique durcissable par précipitation et aube allongée pour turbine de vapeur Withdrawn EP2722407A3 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012229408A JP6113456B2 (ja) 2012-10-17 2012-10-17 析出硬化型マルテンサイト系ステンレス鋼とそれを用いた蒸気タービン長翼

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EP2722407A2 true EP2722407A2 (fr) 2014-04-23
EP2722407A3 EP2722407A3 (fr) 2017-10-25

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US (1) US20140105753A1 (fr)
EP (1) EP2722407A3 (fr)
JP (1) JP6113456B2 (fr)
CN (1) CN103774048B (fr)

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EP3472365A4 (fr) * 2016-06-16 2019-05-15 Uddeholms AB Acier approprié pour outils de moulage de plastique

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CN110565028B (zh) * 2019-10-28 2021-06-29 河南中原特钢装备制造有限公司 含硫马氏体沉淀硬化不锈钢的冶炼方法
JP7615607B2 (ja) * 2020-02-04 2025-01-17 大同特殊鋼株式会社 析出硬化型マルテンサイト系ステンレス鋼
CA3106648C (fr) 2020-02-04 2022-09-13 Daido Steel Co., Ltd. Acier inoxydable martensitique a durcissement structural
CN111705260B (zh) * 2020-04-30 2021-10-01 马鞍山市中桥金属材料有限公司 一种超纯15-5ph不锈钢电渣锭及其制备方法
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CN114507817A (zh) * 2022-01-20 2022-05-17 上海材料研究所 超低碳无钴高强耐蚀合金及其制备方法和应用
JP2024107512A (ja) 2023-01-30 2024-08-09 信越化学工業株式会社 水酸基含有オルガノポリシロキサン、その製造方法、該オルガノポリシロキサンを含有する硬化性組成物、コーティング剤および被覆物品
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US20140105753A1 (en) 2014-04-17
CN103774048B (zh) 2017-01-04

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