WO2017119415A1 - Alliage austénitique résistant à la chaleur et procédé pour la fabrication de ce dernier - Google Patents

Alliage austénitique résistant à la chaleur et procédé pour la fabrication de ce dernier Download PDF

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WO2017119415A1
WO2017119415A1 PCT/JP2017/000056 JP2017000056W WO2017119415A1 WO 2017119415 A1 WO2017119415 A1 WO 2017119415A1 JP 2017000056 W JP2017000056 W JP 2017000056W WO 2017119415 A1 WO2017119415 A1 WO 2017119415A1
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less
resistant alloy
content
heat
austenitic heat
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PCT/JP2017/000056
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Japanese (ja)
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礼文 河内
真木　純
西山　佳孝
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新日鐵住金株式会社
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Priority to US16/067,751 priority Critical patent/US20190010565A1/en
Priority to EP17735952.8A priority patent/EP3401415A4/fr
Priority to JP2017560386A priority patent/JP6493566B2/ja
Priority to CN201780005402.2A priority patent/CN108474072A/zh
Priority to SG11201805206PA priority patent/SG11201805206PA/en
Priority to KR1020187020362A priority patent/KR102090201B1/ko
Priority to CA3009770A priority patent/CA3009770A1/fr
Publication of WO2017119415A1 publication Critical patent/WO2017119415A1/fr

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    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/02—Hardening by precipitation
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    • 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
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
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    • 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
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    • 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
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C22C19/03—Alloys based on nickel or cobalt based on nickel
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    • 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
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C19/03—Alloys based on nickel or cobalt based on nickel
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    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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    • 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
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C22C38/48—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
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • 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
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • 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
    • C21D2211/001—Austenite

Definitions

  • the present invention relates to a heat resistant alloy and a method for producing the same, and more particularly to an austenitic heat resistant alloy and a method for producing the same.
  • 18-8 stainless steel is used as heat resistant steel in equipment such as boilers and chemical plants used in high temperature environments.
  • 18-8 stainless steel is an austenitic stainless steel containing about 18% Cr and about 8% Ni, and examples thereof include SUS304H, SUS316H, SUS321H, and SUS347H in the JIS standard.
  • Heat resistant materials with improved corrosion resistance have been proposed in, for example, Japanese Patent Application Laid-Open No. 02-115348 (Patent Document 1) and Japanese Patent Application Laid-Open No. 07-316751 (Patent Document 2). Since these Al alloys have a high Al content, an Al 2 O 3 film is formed on the surface at high temperatures during use. This coating provides high corrosion resistance.
  • the heat resistant alloys disclosed in Patent Documents 1 and 2 described above may have a low creep strength in a high temperature environment of 700 ° C. or higher.
  • heat-resistant material having high creep strength in a high temperature environment of 700 ° C. or higher
  • a heat-resistant alloy containing Ni and Co and a ⁇ ′ phase (Ni 3 Al) as a strengthening phase has been developed.
  • Such heat-resistant alloys are, for example, Ni-base alloys such as Alloys 617, 263, and 740.
  • the alloy raw materials for these heat-resistant alloys are expensive. Furthermore, since the processability is low, the manufacturing cost is also increased.
  • Patent Document 3 Japanese Patent Laid-Open No. 2014-43621
  • Patent Document 4 Japanese Patent Laid-Open No. 2013-227644
  • Patent Document 3 describes that the austenitic heat-resistant alloy has excellent high-temperature strength and toughness due to precipitation strengthening of Laves phase and ⁇ ′ phase.
  • the f3 represented has a chemical composition of 0.5 to 5.0.
  • Patent Document 4 describes that the austenitic heat-resistant alloy has excellent high-
  • An object of the present invention is to provide an austenitic heat resistant alloy having high creep strength and high toughness even in a high temperature environment.
  • the austenitic heat-resistant alloy according to the present embodiment is, in mass%, C: 0.03 to less than 0.25%, Si: 0.01 to 2.0%, Mn: 2.0% or less, Cr: 10 to 30 %, Ni: more than 25 to 45%, Al: more than 2.5 to less than 4.5%, Nb: 0.2 to 3.5%, N: 0.025% or less, Ti: 0 to 0.2 %: W: 0-6%, Mo: 0-4%, Zr: 0-0.1%, B: 0-0.01%, Cu: 0-5%, Rare earth elements: 0-0.1 %, Ca: 0 to 0.05%, and Mg: 0 to 0.05%, the balance is made of Fe and impurities, and P and S in the impurities are each P: 0.04% or less, And S: having a chemical composition of 0.01% or less.
  • the total volume ratio of precipitates having an equivalent circle diameter of 6 ⁇ m or more is 5% or less.
  • the precipitate is, for example, carbide, nit
  • the austenitic heat-resistant alloy according to the present embodiment has long-term high-temperature strength and excellent toughness even in a high-temperature environment.
  • the present inventors investigated and examined the creep strength and toughness of the austenitic heat resistant alloy in a high temperature environment of 700 ° C. or higher (hereinafter simply referred to as a high temperature environment), and obtained the following knowledge.
  • a heat-resistant alloy containing a Laves phase or a ⁇ ′ phase such as Ni 3 Al has a high creep strength in a high-temperature environment.
  • these precipitated phases become coarse when used for a long time in a high temperature environment, the creep strength and toughness of the heat-resistant alloy are lowered.
  • a precipitate such as carbide, nitride, NiAl, ⁇ -Cr, etc. can be finely dispersed while using a heat-resistant alloy in a high-temperature environment, high creep strength and high toughness can be maintained even after long-term use.
  • These precipitates increase the grain boundary strength by covering the crystal grain boundaries. Furthermore, if these precipitates precipitate in the grains, the deformation resistance of the heat-resistant alloy increases and the creep strength increases.
  • the structure of the heat-resistant alloy before use is controlled as follows.
  • the total volume ratio of coarse precipitates in the heat-resistant alloy is preferably as low as possible.
  • the total volume fraction of precipitates having an equivalent circle diameter of 6 ⁇ m or more (hereinafter referred to as coarse precipitates) is 5% or less in the structure of the heat-resistant alloy, a sufficient amount can be obtained while using the heat-resistant alloy in a high-temperature environment. Fine precipitates can be deposited, and high creep strength and toughness can be obtained.
  • the C content in the heat-resistant alloy is set to less than 0.25%. Furthermore, the cross-section reduction rate during hot forging is set to 30% or more. In this case, coarse precipitates are uniformly dispersed by hot forging. Therefore, the precipitate can be dissolved in the solution treatment in the subsequent step, and the total volume ratio of the coarse precipitate becomes 5% or less.
  • the austenitic heat-resistant alloy according to the present embodiment completed based on the above knowledge is mass%, C: 0.03 to less than 0.25%, Si: 0.01 to 2.0%, Mn: 2.0. %: Cr: 10 to less than 30%, Ni: more than 25 to 45%, Al: more than 2.5 to less than 4.5%, Nb: 0.2 to 3.5%, N: 0.025% or less Ti: 0 to less than 0.2%, W: 0 to 6%, Mo: 0 to 4%, Zr: 0 to 0.1%, B: 0 to 0.01%, Cu: 0 to 5%, Rare earth elements: 0 to 0.1%, Ca: 0 to 0.05%, and Mg: 0 to 0.05%, the balance is composed of Fe and impurities, and P and S in the impurities are respectively It has a chemical composition of P: 0.04% or less and S: 0.01% or less. In the structure, the total volume ratio of precipitates having an equivalent circle diameter of 6 ⁇ m or more is 5% or less.
  • the chemical composition is, by mass, Ti: 0.005 to less than 0.2%, W: 0.005 to 6%, Mo: 0.005 to 4%, Zr: 0.0005 to 0.1%, And B: One or more selected from the group consisting of 0.0005 to 0.01% may be contained.
  • the chemical composition may contain one or more selected from the group consisting of Cu: 0.05 to 5% and rare earth elements: 0.0005 to 0.1% by mass.
  • the chemical composition may contain at least one selected from the group consisting of Ca: 0.0005 to 0.05% and Mg: 0.0005 to 0.05% by mass.
  • the method for producing the austenitic heat-resistant alloy includes a step of performing hot forging at a cross-section reduction rate of 30% or more on a cast material having the above-described chemical composition, and heating the material after hot forging.
  • the austenitic heat-resistant alloy according to the present embodiment is, for example, an alloy tube.
  • the chemical composition of the austenitic heat-resistant alloy contains the following elements.
  • Carbon (C) forms a carbide and increases the creep strength. Specifically, during use in a high temperature environment, C combines with an alloy element within a grain boundary and within the grains to form fine carbides. Fine carbides increase deformation resistance and increase creep strength. If the C content is too low, this effect cannot be obtained. On the other hand, if the C content is too high, many coarse eutectic carbides are formed in the solidified structure after casting of the heat-resistant alloy. Since the eutectic carbide remains coarse in the structure even after the solution treatment, the toughness of the heat-resistant alloy is lowered.
  • the C content is 0.03 to less than 0.25%.
  • the minimum with preferable C content is 0.05%, More preferably, it is 0.08%.
  • the upper limit with preferable C content is 0.23%, More preferably, it is 0.20%.
  • Si 0.01 to 2.0% Silicon (Si) deoxidizes the heat-resistant alloy. Si further enhances the corrosion resistance (oxidation resistance and steam oxidation resistance) of the heat-resistant alloy. Si is an element inevitably contained, but the content of Si may be as small as possible when deoxidation can be sufficiently performed with other elements. On the other hand, if the Si content is too high, the hot workability decreases. Therefore, the Si content is 0.01 to 2.0%. The minimum with preferable Si content is 0.02%, More preferably, it is 0.03%. The upper limit with preferable Si content is 1.0%.
  • Mn 2.0% or less Manganese (Mn) is unavoidably contained. Mn combines with S contained in the heat-resistant alloy to form MnS and enhances the hot workability of the heat-resistant alloy. However, if the Mn content is too high, the heat-resistant alloy becomes too hard and the hot workability and weldability deteriorate. Therefore, the Mn content is 2.0% or less. The minimum with preferable Mn content is 0.1%, More preferably, it is 0.2%. The upper limit with preferable Mn content is 1.2%.
  • Chromium (Cr) improves the corrosion resistance (oxidation resistance, steam oxidation resistance, etc.) of the heat-resistant alloy in a high-temperature environment. Further, Cr is finely precipitated as ⁇ -Cr during use in a high temperature environment, thereby increasing the creep strength. If the Cr content is too low, these effects cannot be obtained. On the other hand, if the Cr content is too high, the stability of the structure decreases and the creep strength decreases. Therefore, the Cr content is 10 to less than 30%.
  • the minimum with preferable Cr content is 11%, More preferably, it is 12%.
  • the upper limit with preferable Cr content is 28%, More preferably, it is 26%.
  • Ni Over 25-45% Nickel (Ni) stabilizes austenite. Ni further enhances the corrosion resistance of the heat-resistant alloy. If the Ni content is too low, these effects cannot be obtained. On the other hand, if the Ni content is too high, these effects are not only saturated, but hot workability is reduced. If the Ni content is too high, the raw material cost further increases. Therefore, the Ni content is more than 25 to 45%.
  • the minimum with preferable Ni content is 26%, More preferably, it is 28%.
  • the upper limit with preferable Ni content is 44%, More preferably, it is 42%.
  • Al more than 2.5 to less than 4.5%
  • Aluminum (Al) is combined with Ni to form fine NiAl during use in a high temperature environment, and increases the creep strength. Further, Al enhances corrosion resistance in a high temperature environment of 1000 ° C. or higher. If the Al content is too low, these effects cannot be obtained. On the other hand, if the Al content is too high, the structural stability is lowered and the strength is lowered. Therefore, the Al content is more than 2.5 to less than 4.5%.
  • the minimum with preferable Al content is 2.55%, More preferably, it is 2.6%.
  • the upper limit with preferable Al content is 4.4%, More preferably, it is 4.2%.
  • the Al content means the total amount of Al contained in the steel material.
  • Niobium (Nb) forms a Laves phase and a Ni 3 Nb phase as precipitation strengthening phases, and precipitates and strengthens the crystal grain boundaries and crystal grains, thereby increasing the creep strength of the heat-resistant alloy. If the Nb content is too low, the above effect cannot be obtained. On the other hand, if the Nb content is too high, the Laves phase and the Ni 3 Nb phase are excessively generated, and the toughness and hot workability of the alloy are lowered. If the Nb content is too high, the toughness after aging for a long time further decreases. Therefore, the Nb content is 0.2 to 3.5%. The minimum with preferable Nb content is 0.35%, More preferably, it is 0.5%. The upper limit with preferable Nb content is less than 3.2%, More preferably, it is 3.0%.
  • N 0.025% or less Nitrogen (N) stabilizes austenite and is inevitably contained in a normal dissolution method. In addition, during use in a high temperature environment, N combines with the alloy element in the grain boundaries and grains to form fine nitrides. Fine nitride increases deformation resistance and increases creep strength. However, if the N content is too high, coarse nitrides that remain undissolved even after the solution treatment are formed and the toughness of the alloy is lowered. Therefore, the N content is 0.025% or less. The upper limit of the preferable N content is 0.02%, more preferably 0.01%.
  • P 0.04% or less Phosphorus (P) is an impurity. P decreases the weldability and hot workability of the heat-resistant alloy. Therefore, the P content is 0.04% or less. The upper limit with preferable P content is 0.03%. The P content is preferably as low as possible.
  • S 0.01% or less Sulfur (S) is an impurity. S decreases the weldability and hot workability of the heat-resistant alloy. Therefore, the S content is 0.01% or less. The upper limit with preferable S content is 0.008%. The S content is preferably as low as possible.
  • the balance of the chemical composition of the austenitic heat-resistant alloy of this embodiment is composed of Fe and impurities.
  • the impurities are those mixed from the ore, scrap, or production environment as raw materials when industrially producing austenitic heat-resistant alloys, and are allowed within a range that does not adversely affect the present invention. Means what will be done.
  • the chemical composition of the austenitic heat-resistant alloy described above may further contain one or more selected from the group consisting of Ti, W, Mo, Zr and B, instead of a part of Fe. All of these elements are optional elements and increase the creep strength.
  • Titanium (Ti) is an optional element and may not be contained. When it is contained, a Laves phase and a Ni 3 Ti phase that are precipitation strengthening phases are formed, and the creep strength is increased by precipitation strengthening. However, if the Ti content is too high, the Laves phase and the Ni 3 Ti phase are excessively generated, and the hot ductility and hot workability are reduced. If the Ti content is too high, the toughness after aging for a long time further decreases. Therefore, the Ti content is 0 to less than 0.2%. The minimum with preferable Ti content is 0.005%, More preferably, it is 0.01%. The upper limit with preferable Ti content is 0.15%, More preferably, it is 0.1%.
  • W 0-6% Tungsten (W) is an optional element and may not be contained. When contained, it dissolves in the austenite of the matrix (matrix), and increases the creep strength by solid solution strengthening. Further, W forms a Laves phase in the crystal grain boundaries and in the crystal grains, and increases the creep strength by precipitation strengthening. However, if there is too much W content, a Laves phase will be generated excessively and hot ductility, hot workability, and toughness will fall. Accordingly, the W content is 0 to 6%.
  • the minimum with preferable W content is 0.005%, More preferably, it is 0.01%.
  • the upper limit with preferable content of W is 5.5%, More preferably, it is 5%.
  • Mo 0-4% Molybdenum (Mo) is an optional element and may not be contained. When contained, it dissolves in the austenite of the parent phase and increases the creep strength by solid solution strengthening. Mo further forms a Laves phase in the grain boundaries and in the crystal grains, and increases the creep strength by precipitation strengthening. However, if the Mo content is too high, the Laves phase is excessively generated and the hot ductility, hot workability, and toughness are reduced. Therefore, the Mo content is 0 to 4%. The minimum with preferable Mo content is 0.005%, More preferably, it is 0.01%. The upper limit with preferable Mo content is 3.5%, More preferably, it is 3%.
  • Zr 0 to 0.1%
  • Zirconium (Zr) is an optional element and may not be contained. When contained, Zr increases creep strength by grain boundary strengthening. However, if the Zr content is too high, the weldability and hot workability of the heat-resistant alloy are lowered. Therefore, the Zr content is 0 to 0.1%.
  • the minimum with preferable Zr is 0.0005%, More preferably, it is 0.001%.
  • the upper limit with preferable Zr content is 0.06%.
  • B 0 to 0.01%
  • Boron (B) is an optional element and may not be contained. When contained, the creep strength is increased by grain boundary strengthening. However, if the B content is too high, weldability decreases. Therefore, the B content is 0 to 0.01%.
  • a preferable lower limit of B is 0.0005%, and more preferably 0.001%. The upper limit with preferable B content is 0.005%.
  • the chemical composition of the austenitic heat-resistant alloy described above may further contain one or more selected from the group consisting of Cu and rare earth elements instead of a part of Fe. Any of these elements is an arbitrary element and improves the corrosion resistance of the heat-resistant alloy.
  • Copper (Cu) is an optional element and may not be contained. When contained, it promotes the formation of an Al 2 O 3 film in the vicinity of the surface and enhances the corrosion resistance of the heat-resistant alloy. However, if the Cu content is too high, not only the effect is saturated, but also the high temperature ductility is lowered. Therefore, the Cu content is 0 to 5%.
  • the minimum with preferable Cu content is 0.05%, More preferably, it is 0.1%.
  • the upper limit with preferable Cu content is 4.8%, More preferably, it is 4.5%.
  • the rare earth element is an optional element and may not be contained. When it is contained, S is fixed as a sulfide to enhance hot workability. REM further forms oxides to increase corrosion resistance, creep strength, and creep ductility. However, if the REM content is too high, inclusions such as oxides increase, thereby reducing hot workability and weldability and increasing manufacturing costs. Therefore, the REM content is 0 to 0.1%.
  • the minimum with preferable REM content is 0.0005%, More preferably, it is 0.001%.
  • the upper limit with preferable REM content is 0.09%, More preferably, it is 0.08%.
  • REM is a general term for a total of 17 elements of Sc, Y, and a lanthanoid.
  • the REM content means the content of an element when the REM contained in the heat-resistant alloy is one of these elements.
  • the REM content means the total content of these elements.
  • REM is generally contained in misch metal. For this reason, for example, it may be added in the form of misch metal so that the REM content falls within the above range.
  • the chemical composition of the austenitic heat-resistant alloy described above may further include one or more selected from the group consisting of Ca and Mg instead of a part of Fe. Any of these elements is an arbitrary element and improves the hot workability of the heat-resistant alloy.
  • Ca 0 to 0.05%
  • Calcium (Ca) is an optional element and may not be contained. When it is contained, S is fixed as a sulfide to enhance hot workability. On the other hand, if the Ca content is too high, toughness, ductility and cleanliness will be reduced. Therefore, the Ca content is 0 to 0.05%.
  • a preferable lower limit of Ca is 0.0005%.
  • the upper limit with preferable Ca content is 0.01%.
  • Mg 0 to 0.05%
  • Magnesium (Mg) is an optional element and may not be contained. When contained, it fixes S as a sulfide and improves the hot workability of the heat-resistant alloy. On the other hand, if the Ca content is too high, toughness, ductility and cleanliness will be reduced. Therefore, the Ca content is 0 to 0.05%. A preferable lower limit of Ca is 0.0005%. The upper limit with preferable Ca content is 0.01%.
  • the austenitic heat-resistant alloy of the present embodiment precipitates fine precipitates during use in a high temperature environment, increases creep strength, and maintains toughness.
  • the precipitate include carbide, nitride, NiAl, and ⁇ -Cr. If the precipitate is coarse, creep strength and toughness are lowered. Therefore, in the heat-resistant alloy before use, it is preferable that there are few coarse precipitates.
  • the equivalent circle diameter means the diameter ( ⁇ m) when the area of the precipitate is converted into the area of the circle.
  • the total volume ratio of coarse precipitates in the structure of the austenitic heat-resistant alloy of this embodiment can be measured by the following method.
  • the austenitic heat-resistant alloy material is an alloy pipe
  • a test piece is sampled from the central thickness portion of the cross section perpendicular to the axial direction.
  • observation surface After polishing the cross section (observation surface) of the collected specimen, the observation surface is etched with a mixed acid solution of hydrochloric acid and nitric acid.
  • a scanning electron microscope (SEM) is used to photograph 10 fields of view on the observation surface to create an SEM image (reflection electron image). Each field of view is 100 ⁇ m ⁇ 100 ⁇ m.
  • the precipitates and the matrix have different contrasts.
  • the area of the precipitate specified by the difference in contrast is obtained, and the equivalent circle diameter of each precipitate is calculated. After the calculation, a precipitate (coarse precipitate) having an equivalent circle diameter of 6 ⁇ m or more is specified.
  • the shape of the austenitic heat-resistant alloy according to this embodiment is not particularly limited.
  • An austenitic heat-resistant alloy is, for example, an alloy tube.
  • Austenitic heat-resistant alloy pipes are used as boiler pipes and chemical plant reaction pipes.
  • the austenitic heat-resistant alloy may be a plate material, a rod material, or a wire material.
  • the manufacturing method of the present embodiment includes a step of preparing a material having the above-described chemical composition (preparation step), a step of hot forging the prepared material (hot forging step), and a hot forged material. And a step of producing an intermediate material by performing hot working (hot working step) and a step of performing solution heat treatment on the intermediate material (solution heat treatment step).
  • preparation step a step of preparing a material having the above-described chemical composition
  • hot forging step hot forging step
  • a hot forged material a step of producing an intermediate material by performing hot working (hot working step) and a step of performing solution heat treatment on the intermediate material (solution heat treatment step).
  • a molten steel having the above chemical composition is produced.
  • a well-known degassing process is implemented with respect to molten steel as needed.
  • a raw material is manufactured by casting using molten steel.
  • the material may be an ingot obtained by an ingot-making method or a slab such as a slab, bloom or billet obtained by a continuous casting method.
  • precipitates such as eutectic carbides are present in the structure of the material produced by casting. These precipitates are coarse, and there are many that have an equivalent circle diameter of 6 ⁇ m or more. Such coarse precipitates are difficult to dissolve in a solution treatment in a later step.
  • the cross-section reduction rate in the hot forging process is 30% or more, coarse precipitates are destroyed during hot forging and the size is reduced. For this reason, the precipitate is easily dissolved in the solution heat treatment in the subsequent step. As a result, the volume ratio of precipitates having an equivalent circle diameter of 6 ⁇ m or more is 5% or less.
  • the preferable cross-sectional reduction rate is 35% or more, and more preferably 40% or more.
  • the upper limit of the cross-section reduction rate is not particularly limited, it is 90% in consideration of productivity.
  • Hot working is performed on the hot-forged material (cylindrical material) to manufacture an alloy base tube that is an intermediate material.
  • a through hole is formed in the center of a cylindrical material by machining.
  • Hot extrusion is performed on the cylindrical material in which the through holes are formed, and an alloy base tube is manufactured.
  • a cylindrical raw material (intermediate material) may be manufactured by piercing and rolling a cylindrical material.
  • Cold working may be performed on the intermediate material after hot working.
  • the cold working is, for example, cold drawing or the like.
  • An intermediate material is manufactured by the above process.
  • Solution heat treatment process Solution heat treatment is performed on the manufactured intermediate material.
  • the precipitate in the intermediate material is dissolved by solution heat treatment.
  • the heat treatment temperature in the solution heat treatment is 1100 to 1250 ° C. If the heat treatment temperature is less than 1100 ° C., the precipitate is not sufficiently dissolved, and as a result, the volume fraction of the coarse precipitate exceeds 5%. On the other hand, if the heat treatment temperature is too high, the austenite grains are coarsened and the productivity is lowered.
  • the precipitate is sufficiently dissolved, and the total volume ratio of the coarse precipitate is 5% or less.
  • the solution heat treatment time is not particularly limited.
  • the solution heat treatment time is, for example, 1 minute to 1 hour.
  • pickling treatment may be performed for the purpose of removing scale formed on the surface.
  • pickling for example, a mixed acid solution of nitric acid and hydrochloric acid is used.
  • the pickling time is, for example, 30 to 60 minutes.
  • a blasting process using a projection material may be performed on the intermediate material after the pickling process.
  • blasting is performed on the inner surface of the alloy tube.
  • a processed layer is formed on the surface, and corrosion resistance (oxidation resistance and the like) is increased.
  • the austenitic heat-resistant alloy of this embodiment is manufactured by the above manufacturing method.
  • the manufacturing method of the alloy pipe was demonstrated above.
  • a cylindrical ingot (30 kg) having an outer diameter of 120 mm was manufactured using the molten steel.
  • the ingot was hot forged at a cross-sectional reduction rate shown in Table 2 to produce a rectangular material.
  • the rectangular material was hot-rolled and cold-rolled to produce a plate-like intermediate material having a thickness of 1.5 mm.
  • the intermediate material was subjected to a solution treatment for 10 minutes at the heat treatment temperature shown in Table 2. After holding for 10 minutes, the intermediate material was water-cooled to produce an alloy sheet.
  • Test results The test results are shown in Table 2.
  • the chemical compositions of Test No. 1 to Test No. 11 were appropriate, and the volume fraction of coarse precipitates was 5% or less.
  • the creep strength was 140 MPa or more, indicating an excellent creep strength.
  • the Charpy impact value was 40 J / cm 2 or more, and excellent toughness was exhibited even after long-term aging treatment.
  • test number 12 the C content was too high. Therefore, the volume ratio of the coarse precipitate exceeded 5%. As a result, the creep strength was less than 140 MPa, and the Charpy impact value was less than 40 J / cm 2 .
  • test number 17 the cross-sectional reduction rate during hot forging was less than 30%. Therefore, the total volume ratio of coarse precipitates exceeded 5%. As a result, the creep strength was less than 140 MPa, and the Charpy impact value was less than 40 J / cm 2 .
  • test number 18 the solution heat treatment temperature was less than 1100 ° C. Therefore, the total volume ratio of coarse precipitates exceeded 5%. As a result, the creep rupture strength was less than 140 MPa, and the Charpy impact value was less than 40 J / cm 2 .
  • the austenitic heat-resistant alloy of the present invention can be widely used in a high temperature environment of 700 ° C. or higher.
  • it is particularly suitable for use as an alloy pipe in a power generation boiler, a chemical industry plant or the like exposed to a high temperature environment of 700 ° C. or higher.

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Abstract

L'invention concerne un alliage austénitique résistant à la chaleur ayant une haute résistance au fluage et une ténacité élevée même dans un environnement à haute température. Cet alliage austénitique résistant à la chaleur a une composition chimique contenant, en termes de % en masse, de 0,03 à moins de 0,25 % de C, 0,01 à 2,0 % de Si, 2,0 % ou moins de Mn, 10 à moins de 30 % de Cr, de plus de 25 % à 45 % de Ni, de plus de 2,5 % à moins de 4,5 % d'Al, 0,2 à 3,5 % de Nb et 0,025 % ou moins de N, le reste comprenant Fe et des impuretés inévitables, P et S représentant 0,04 % ou moins et 0,01 % ou moins, respectivement, des impuretés. La quantité brute de précipités de 6 µm ou plus dans la structure de l'alliage austénitique résistant à la chaleur est inférieure ou égale à 5 %.
PCT/JP2017/000056 2016-01-05 2017-01-04 Alliage austénitique résistant à la chaleur et procédé pour la fabrication de ce dernier WO2017119415A1 (fr)

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US16/067,751 US20190010565A1 (en) 2016-01-05 2017-01-04 Austenitic Heat Resistant Alloy and Method for Producing the Same
EP17735952.8A EP3401415A4 (fr) 2016-01-05 2017-01-04 Alliage austénitique résistant à la chaleur et procédé pour la fabrication de ce dernier
JP2017560386A JP6493566B2 (ja) 2016-01-05 2017-01-04 オーステナイト系耐熱合金及びその製造方法
CN201780005402.2A CN108474072A (zh) 2016-01-05 2017-01-04 奥氏体系耐热合金及其制造方法
SG11201805206PA SG11201805206PA (en) 2016-01-05 2017-01-04 Austenitic heat resistant alloy and method for producing the same
KR1020187020362A KR102090201B1 (ko) 2016-01-05 2017-01-04 오스테나이트계 내열합금 및 그 제조 방법
CA3009770A CA3009770A1 (fr) 2016-01-05 2017-01-04 Alliage austenitique resistant a la chaleur et procede pour la fabrication de ce dernier

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WO2019131954A1 (fr) 2017-12-28 2019-07-04 日本製鉄株式会社 Alliage résistant à la chaleur à base d'austénite
CN111542639A (zh) * 2017-12-28 2020-08-14 日本制铁株式会社 奥氏体系耐热合金
WO2019189576A1 (fr) * 2018-03-28 2019-10-03 日鉄ステンレス株式会社 Tôle d'alliage et son procédé de production
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WO2020067444A1 (fr) * 2018-09-27 2020-04-02 日本製鉄株式会社 Alliage austénitique
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JP7205277B2 (ja) 2019-02-14 2023-01-17 日本製鉄株式会社 耐熱合金及びその製造方法
WO2021039266A1 (fr) * 2019-08-29 2021-03-04 日本製鉄株式会社 Acier austénitique résistant à la chaleur
JPWO2021039266A1 (fr) * 2019-08-29 2021-03-04
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