WO2018003823A1 - Acier inoxydable austénitique - Google Patents

Acier inoxydable austénitique Download PDF

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Publication number
WO2018003823A1
WO2018003823A1 PCT/JP2017/023657 JP2017023657W WO2018003823A1 WO 2018003823 A1 WO2018003823 A1 WO 2018003823A1 JP 2017023657 W JP2017023657 W JP 2017023657W WO 2018003823 A1 WO2018003823 A1 WO 2018003823A1
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stainless steel
austenitic stainless
steel
content
concentration
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PCT/JP2017/023657
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English (en)
Japanese (ja)
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礼文 河内
西山　佳孝
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新日鐵住金株式会社
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Application filed by 新日鐵住金株式会社 filed Critical 新日鐵住金株式会社
Priority to US16/310,613 priority Critical patent/US20190127832A1/en
Priority to EP17820177.8A priority patent/EP3480330A4/fr
Priority to KR1020197002265A priority patent/KR102124914B1/ko
Priority to CA3028610A priority patent/CA3028610A1/fr
Priority to SG11201810839TA priority patent/SG11201810839TA/en
Priority to JP2018525193A priority patent/JP6614347B2/ja
Priority to CN201780040380.3A priority patent/CN109415786A/zh
Publication of WO2018003823A1 publication Critical patent/WO2018003823A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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    • 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
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • 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
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • 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
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    • 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
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • 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 stainless steel, and more particularly to austenitic stainless steel.
  • heat-resistant steel austenitic stainless steel with increased Cr content and Ni content, or Ni base with increased Cr content
  • An alloy is used.
  • These heat resistant steels are austenitic stainless steels or Ni-based alloys containing about 20 to 30% by mass of Cr and about 20 to 70% by mass of Ni.
  • Piping for equipment such as thermal power boilers and chemical plants is manufactured from steel pipes.
  • the steel base tube is manufactured by hot working after the above-described austenitic stainless steel or Ni-based alloy is melted. Therefore, high heat workability is required for heat resistant steel.
  • austenitic stainless steel generally has high deformation resistance at high temperatures and low ductility. Therefore, an austenitic stainless steel having excellent hot workability is required.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2005-48284
  • the stainless steel disclosed in Patent Document 1 is, in mass%, C: 0.01 to 0.6%, Si: 0.1 to 5%, Mn: 0.1 to 10%, P: 0.08%
  • O (oxygen): 0.02% or less the balance being Fe and It consists of a base material having a chemical composition consisting of inevitable impurities.
  • This stainless steel is provided with a Cr-deficient layer in the surface layer portion, the Cr concentration in the Cr-deficient layer is 10% or more and less than the Cr concentration of the base material, and the thickness of the Cr-deficient layer is within 20 ⁇ m.
  • Patent Document 1 describes that carburization resistance and coking resistance are enhanced by forming a protective film mainly composed of a Cr 2 O 3 film.
  • the main component of the protective film is a Cr 2 O 3 film. Therefore, particularly in a high-temperature carburizing environment, the function of preventing the entry of oxygen and carbon from the external atmosphere is not sufficient. As a result, internal oxidation and carburization may occur in the material.
  • Patent Document 2 International Publication No. 2010/113830
  • Patent Document 3 International Publication No. 2004/066788
  • Patent Document 4 Japanese Patent Laid-Open No. 10-140296
  • Patent Document 4 replace Cr 2 O 3 coating.
  • a technique relating to a protective film is disclosed. Specifically, in these documents, a protective film mainly composed of thermodynamically stable Al 2 O 3 is formed on the surface of the heat-resistant steel as a protective film replacing the Cr 2 O 3 film.
  • the casting product disclosed in Patent Document 2 is, in mass%, C: 0.05 to 0.7%, Si: more than 0% to 2.5% or less, Mn: more than 0% to 3.0% %: Cr: 15-50%, Ni: 18-70%, Al: 2-4%, Rare earth elements: 0.005-0.4%, and W: 0.5-10% and / or Mo : It has a cast body of a heat-resistant alloy containing 0.1 to 5%, the balance being Fe and inevitable impurities.
  • a barrier layer is formed on the surface of the cast body in contact with the high-temperature atmosphere, and the barrier layer is an Al 2 O 3 layer having a thickness of 0.5 ⁇ m or more, and 80% by area or more of the outermost surface of the barrier layer is It is Al 2 O 3 , and Cr base particles having a Cr concentration higher than that of the base of the alloy are dispersed at the interface between the Al 2 O 3 layer and the cast body.
  • Patent Document 2 describes that by adding Al, a protective film mainly composed of an Al 2 O 3 film is formed, and the carburization resistance is improved.
  • the cast nickel-chromium alloy disclosed in US Pat. No. 6,057,059 contains up to 0.8% carbon, up to 1% silicon, up to 0.2% manganese, 15% -40% chromium, 0.5% -13. % Iron, 1.5% to 7% aluminum, up to 2.5% niobium, up to 1.5% titanium, 0.01% to 0.4% zirconium, up to 0.06% nitrogen, Up to 12% cobalt, up to 5% molybdenum, up to 6% tungsten, 0.019% to 0.089% yttrium, the rest being nickel.
  • Patent Document 3 the addition of REM in addition to Al, nickel enhanced peeling resistance of the Al 2 O 3 is a protective coating - chrome cast alloys are obtained are described as.
  • the austenitic stainless steel disclosed in Patent Document 4 is, by weight, C: 0.15% or less, Si: 0.9% or less, Mn: 0.2-2%, P: 0.04% or less, S: 0.005% or less, and S (%) and O (%) combined to 0.015% or less, Cr: 12-30%, Ni: 10-35%, Al: 1.5-5.5 %, B: 0.001 to 0.01%, N: 0.025% or less, Ca: 0 to 0.008%, Cu: 0 to 2%, Ti, Nb, Zr, V and 1 of Hf Contains 0 to 2% in total of one or more species, 0 to 3% in total of one or more of W, Mo, Co and Re, and 0 to 0.05% in total of one or more of rare earth elements The balance consists of Fe and inevitable impurities.
  • the heat-resistant alloy contains up to 50% of Cr. Therefore, Cr may form as a carbide on the steel surface in a high-temperature carburizing environment such as a hydrocarbon gas atmosphere. In this case, Al 2 O 3 which is a protective film is not uniformly formed. Therefore, carburization may occur.
  • the cast products and nickel-chromium cast alloys disclosed in Patent Documents 2 and 3 have a high C content, so the hot workability is significantly reduced.
  • Patent Document 3 since the Ni content is high, the raw material cost is remarkably increased.
  • An object of the present invention is to provide an austenitic stainless steel having excellent carburization resistance even in a high-temperature carburizing environment such as a hydrocarbon gas atmosphere, and further having excellent hot workability at the time of manufacture. .
  • the austenitic stainless steel according to the present embodiment in mass%, C: 0.03 to less than 0.25%, Si: 0.01 to 2.0%, Mn: 2.0% or less, P: 0.04 %: S: 0.01% or less, Cr: 10 to less than 22%, Ni: more than 30.0% to 40.0%, Al: more than 2.5% to less than 4.5%, Nb: 0.
  • the austenitic stainless steel according to the present embodiment has excellent carburization resistance even in a high-temperature carburizing environment such as a hydrocarbon gas atmosphere, and further has excellent hot workability during manufacturing.
  • the present inventors investigated and examined the carburization resistance of austenitic stainless steel in a high-temperature carburizing environment and hot workability during production, and obtained the following knowledge.
  • the high-temperature carburizing environment refers to an environment of 1000 ° C. or higher in a hydrocarbon gas atmosphere.
  • TEE effect Cr Third Element Effect
  • Cr Cr Third Element Effect
  • the mechanism of the TEE effect is as follows. At the very beginning of the heat treatment step described later, Cr is first preferentially oxidized on the steel surface to form Cr 2 O 3 . For this reason, the oxygen partial pressure on the steel surface is locally reduced. Thus, Al is formed as a uniform Al 2 O 3 film in the vicinity of the surface without internal oxidation. Thereafter, oxygen was used as a Cr 2 O 3 is incorporated into the Al 2 O 3. Then, the protective coating of only Al 2 O 3 is in the heat treatment step at the end is formed.
  • Cr has a TEE effect even in a high-temperature carburizing environment. That is, Cr promotes uniform formation of the Al 2 O 3 film even in a high-temperature carburizing environment. Therefore, in order to form a uniform Al 2 O 3 film, it is necessary to contain a certain amount or more of Cr.
  • the Cr content is set to less than 10 to 22% in the present invention.
  • (C) In the austenitic stainless steel, it is effective to make the ratio of the Cr concentration in the surface layer and the Al concentration in the surface layer appropriately smaller than the ratio between the Cr concentration other than the surface layer and the Al concentration other than the surface layer. That is, if the austenitic stainless steel satisfies the formula (1), the carburization resistance in a high-temperature carburizing environment is enhanced. 0.40 ⁇ (C Cr ′ / C Al ′) / (C Cr / C Al ) ⁇ 0.80 (1)
  • the Cr concentration (% by mass) in the surface layer of the austenitic stainless steel is substituted for C Cr ′ in the formula (1).
  • Al concentration (% by mass) in the surface layer of austenitic stainless steel is substituted for C Al '. Also, the C Cr Cr concentration than the surface layer of austenitic stainless steel (mass%) is substituted. Al concentration (mass%) other than the surface layer of austenitic stainless steel is substituted for C Al .
  • F1 (C Cr '/ C Al ') / (C Cr / C Al ). If F1 is 0.40 or more, the TEE effect by Cr is sufficiently obtained on the steel surface in a high-temperature carburizing environment. In this case, formation of the Al 2 O 3 film is promoted. If F1 is 0.80 or less, formation of Cr carbide on the steel surface is suppressed in a high-temperature carburizing environment. Therefore, uniform Al 2 O 3 film is formed. As a result, carburization resistance is increased.
  • the austenitic stainless steel according to the present embodiment completed on the basis of the above knowledge is in mass%, C: 0.03 to less than 0.25%, Si: 0.01 to 2.0%, Mn: 2.0 %: P: 0.04% or less, S: 0.01% or less, Cr: 10 to less than 22%, Ni: more than 30.0% to 40.0%, Al: more than 2.5% to 4.
  • the balance has a chemical composition consisting of Fe and impurities, and satisfies the formula (1).
  • the chemical composition is Ti: 0.005 to less than 0.2%, Mo: 0.01 to 0.5%, W: 0.01 to 0.5%, Cu: 0.005 to 0.5%, One or two or more selected from the group consisting of V: 0.005 to 0.2% and B: 0.0001 to 0.01 may be contained.
  • the chemical composition of the austenitic stainless steel according to the present embodiment contains the following elements.
  • C 0.03 to less than 0.25%
  • Carbon (C) mainly bonds with Cr to form Cr carbide in the steel, and increases the creep strength when used in a high-temperature carburizing environment. If the C content is too low, this effect cannot be obtained. On the other hand, if the C content is too high, a large number of coarse eutectic carbides are formed in the solidified structure after casting of steel, and the toughness of the steel is lowered. Therefore, 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 steel. In the case where deoxidation can be sufficiently performed with other elements, the Si content may be as small as possible. 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 steel to form MnS and enhances the hot workability of the steel. However, if the Mn content is too high, the steel 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%.
  • P 0.04% or less Phosphorus (P) is an impurity. P decreases the weldability and hot workability of steel. 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.
  • the lower limit of the P content is, for example, 0.0005%.
  • S 0.01% or less Sulfur (S) is an impurity. S decreases the weldability and hot workability of steel. 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 lower limit of the S content is, for example, 0.001%.
  • Chromium (Cr) promotes the formation of an Al 2 O 3 film during the heat treatment process and in a high-temperature carburizing environment due to the above-described TEE effect. Further, Cr combines with C in the steel to form Cr carbide in the steel, 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, Cr combines with C derived from atmospheric gas (hydrocarbon gas) in a high-temperature carburizing environment, and forms Cr carbide on the steel surface. When Cr carbide is formed on the steel surface, Cr on the steel surface is locally depleted. Therefore TEE effect decreases, uniform Al 2 O 3 film is not formed.
  • Chromium (Cr) promotes the formation of an Al 2 O 3 film during the heat treatment process and in a high-temperature carburizing environment due to the above-described TEE effect. Further, Cr combines with C in the steel to form Cr carbide in the steel, increasing the creep strength. If the Cr content is too low
  • the Cr content is 10 to less than 22%.
  • the minimum with preferable Cr content is 11%, More preferably, it is 12%.
  • the upper limit with preferable Cr content is 21%, More preferably, it is 20%.
  • Cr carbide is divided into Cr carbide formed in steel and Cr carbide formed on the steel surface. In the austenitic stainless steel of this embodiment, Cr carbide is formed in the steel, and Cr carbide on the steel surface is suppressed.
  • Ni more than 30.0% to 40.0%
  • Nickel (Ni) stabilizes austenite and increases creep strength. Ni further enhances the carburization resistance of the steel. 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 the raw material costs are increased. Therefore, the Ni content is more than 30.0% to 40.0%.
  • the minimum with preferable Ni content is 31.0%, More preferably, it is 32.0%.
  • the upper limit with preferable Ni content is 39.0%, More preferably, it is 38.0%.
  • Al more than 2.5% to less than 4.5%
  • Aluminum (Al) forms an Al 2 O 3 film on the steel surface during the heat treatment process and in a high-temperature carburizing environment, thereby improving the carburization resistance of the steel.
  • the Al 2 O 3 film is thermodynamically stable as compared with the conventionally used Cr 2 O 3 film. 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 creep strength is significantly 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 4.2%, More preferably, it is 4.0%.
  • the Al content means the total amount of Al contained in the steel material.
  • Niobium forms an intermetallic compound (Laves phase and Ni 3 Nb phase) that becomes a precipitation strengthening phase, and precipitates and strengthens the grain boundaries and inside the crystal grains, thereby increasing the creep strength of the steel.
  • Nb content is 0.01 to 3.5%.
  • the minimum with preferable Nb content is 0.05%, More preferably, it is 0.1%.
  • the upper limit with preferable Nb content is less than 3.2%, More preferably, it is 3.0%.
  • N 0.03% or less Nitrogen (N) stabilizes austenite and is unavoidably contained.
  • N content is 0.03% or less.
  • a preferable upper limit of the N content is 0.01%.
  • the lower limit of the N content is, for example, 0.0005%.
  • Ca 0.0005 to 0.05%
  • Ca fixes S as a sulfide and improves hot workability.
  • the Ca content is too high, toughness and ductility are reduced. Therefore, hot workability is reduced.
  • the Ca content is too high, the cleanliness is further deteriorated. Therefore, the Ca content is 0.0005 to 0.05%.
  • a preferable lower limit of Ca is 0.0006%, and more preferably 0.0008%.
  • the upper limit with preferable Ca content is 0.01%, More preferably, it is 0.008%.
  • Mg 0.0005 to 0.05%
  • Mg Magnesium (Mg) fixes S as a sulfide and improves the hot workability of steel.
  • Mg content is too high, toughness and ductility are reduced. Therefore, hot workability is reduced.
  • Mg content is too high, the cleanliness is further deteriorated. Therefore, the Mg content is 0.0005 to 0.05%.
  • a preferable lower limit of Mg is 0.0006%, and more preferably 0.0008%.
  • the upper limit with preferable Mg content is 0.01%, More preferably, it is 0.008%.
  • the balance of the chemical composition of the austenitic stainless steel of this embodiment is composed of Fe and impurities.
  • the impurities are those that are mixed from ore, scrap, or production environment as raw materials when industrially producing austenitic stainless steel, 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 stainless steel described above may further contain Ti instead of a part of Fe.
  • Titanium (Ti) is an optional element and may not be contained. When contained, Ti forms an intermetallic compound (Laves phase and Ni 3 Ti phase) that becomes a precipitation strengthening phase, and increases the creep strength by precipitation strengthening. On the other hand, if the Ti content is too high, an intermetallic compound is excessively produced, and high temperature 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%.
  • the chemical composition of the austenitic stainless steel described above may further include one or two selected from the group consisting of Mo and W instead of part of Fe. All of these elements are optional elements and increase the creep strength of steel.
  • Mo 0 to 0.5% Molybdenum (Mo) is an optional element and may not be contained. When contained, Mo dissolves in the austenite that is the parent phase. The solid solution Mo increases the creep strength by solid solution strengthening. On the other hand, if Mo content is too high, hot workability will fall. Therefore, the Mo content is 0 to 0.5%.
  • the minimum with preferable Mo content is 0.01%, More preferably, it is 0.05%.
  • the upper limit with preferable Mo content is 0.4%, More preferably, it is 0.3%.
  • W 0-0.5% Tungsten (W) is an optional element and may not be contained. When contained, W forms a solid solution in the austenite that is the parent phase. The solid solution W increases the creep strength by solid solution strengthening. On the other hand, if the W content is too high, the hot workability decreases. Accordingly, the W content is 0 to 0.5%.
  • the minimum with preferable W content is 0.01%, More preferably, it is 0.05%.
  • the upper limit with preferable W content is 0.4%, More preferably, it is 0.3%.
  • the chemical composition of the austenitic stainless steel described above may further contain Cu instead of part of Fe.
  • Cu 0 to 0.5% Copper (Cu) is an optional element and may not be contained. When contained, Cu stabilizes austenite. Cu further increases the strength of the steel by precipitation strengthening. On the other hand, if Cu content is too high, the ductility and hot workability of steel will fall. Therefore, the Cu content is 0 to 0.5%.
  • the minimum with preferable Cu content is 0.005%, More preferably, it is 0.01%.
  • the upper limit with preferable Cu content is 0.3%, More preferably, it is 0.1%.
  • the chemical composition of the austenitic stainless steel described above may further contain V instead of a part of Fe.
  • V 0 to 0.2%
  • Vanadium (V) is an optional element and may not be contained. When contained, V forms an intermetallic compound similar to Ti and increases the creep strength of steel. On the other hand, if the V content is too high, the volume ratio of the intermetallic compound in the steel becomes excessively high, and the hot workability decreases. Therefore, the V content is 0 to 0.2%.
  • the minimum with preferable V content is 0.005%, More preferably, it is 0.01%.
  • the upper limit with preferable V content is 0.15%, More preferably, it is 0.1%.
  • the chemical composition of the austenitic stainless steel described above may further contain B instead of a part of Fe.
  • B 0 to 0.01% Boron (B) is an optional element and may not be contained. When contained, B segregates at the grain boundary and promotes precipitation of intermetallic compounds at the grain boundary. This increases the creep strength of the steel. On the other hand, if the B content is too high, the weldability and hot workability of the steel deteriorate. Therefore, the B content is 0 to 0.01%.
  • the minimum with preferable B content is 0.0001%, More preferably, it is 0.0005%.
  • the upper limit with preferable B content is 0.008%, More preferably, it is 0.006%.
  • the austenitic stainless steel of this embodiment further satisfies the formula (1). 0.40 ⁇ (C Cr ′ / C Al ′) / (C Cr / C Al ) ⁇ 0.80 (1)
  • the Cr concentration (% by mass) in the surface layer of the austenitic stainless steel is substituted for C Cr ′ in the formula (1).
  • Al concentration (% by mass) in the surface layer of austenitic stainless steel is substituted for C Al '.
  • the C Cr Cr concentration than the surface layer of austenitic stainless steel (mass%) is substituted.
  • Al concentration (mass%) other than the surface layer of austenitic stainless steel is substituted for C Al .
  • the surface layer of austenitic stainless steel means a range from the surface of austenitic stainless steel to a depth of 2 ⁇ m.
  • 2 ⁇ m depth from the surface means 2 ⁇ m depth from the surface of the base material.
  • the depth of 2 ⁇ m from the surface of the base material is 2 ⁇ m from the surface of the base material after removing the Al 2 O 3 coating by descaling.
  • the surface of the austenitic stainless steel in the case where the austenitic stainless steel has an Al 2 O 3 coating on the surface, the Al 2 O 3 coating is removed by descaling treatment) in C Cr ′ in the formula (1).
  • C Al ′ in formula (1) is the surface of austenitic stainless steel (if the austenitic stainless steel has an Al 2 O 3 coating on the surface, the mother after removing the Al 2 O 3 coating by descaling treatment) Al concentration (mass%) in a range from the surface of the material to a depth of 2 ⁇ m is substituted.
  • the Cr concentration (% by mass) other than the surface layer means the average Cr concentration (% by mass) of the base material in the region other than the surface layer.
  • the Al concentration (mass%) other than the surface layer means the average Al concentration (mass%) of the base material in the region other than the surface layer.
  • the ratio of the Cr concentration of the surface layer to the Al concentration of the surface layer is more appropriate than the ratio of the Cr concentration of the base material to the Al concentration of the base material. small.
  • the formation of the Al 2 O 3 film is promoted.
  • carburization resistance is enhanced in a high-temperature carburizing environment.
  • F1 (C Cr '/ C Al ') / (C Cr / C Al ).
  • F1 is an index of Cr behavior.
  • the ratio between the Cr concentration in the surface layer and the Al concentration in the surface layer is too large than the ratio between the Cr concentration in the base material and the Al concentration in the base material. That is, the surface layer Cr concentration C Cr ′ is too high.
  • Cr carbide is formed on the steel surface in a high-temperature carburizing environment, and the formation of a uniform Al 2 O 3 film is physically hindered.
  • the ratio between the Cr concentration in the surface layer and the Al concentration in the surface layer is too small than the ratio between the Cr concentration in the base material and the Al concentration in the base material. That is, the Cr concentration C Cr ′ of the surface layer is too small. In this case, the TEE effect of Cr cannot be obtained in a high-temperature carburizing environment. Therefore, uniform Al 2 O 3 film on the steel surface is not formed.
  • F1 is 0.40 to 0.80.
  • the minimum with preferable F1 is 0.42, More preferably, it is 0.44.
  • the upper limit with preferable F1 is 0.79, More preferably, it is 0.78.
  • the surface layer Cr concentration C Cr ′ and the surface layer Al concentration C Al ′ are determined by the following method.
  • Austenitic stainless steel is cut perpendicular to the surface. From the surface of the cut austenitic stainless steel (when the austenitic stainless steel has an Al 2 O 3 coating on the surface, the surface of the base material after removing the Al 2 O 3 coating by descaling) to a depth of 2 ⁇ m In the range, arbitrary 5 points (measurement points) are selected.
  • the Cr concentration and the Al concentration at each measurement point are measured by EDX (energy dispersive X-ray spectroscopy). Values obtained by averaging the measured values are defined as C Cr ′ (%) and C Al ′ (%).
  • the surface layer Cr concentration C Cr ′ and the surface layer Al concentration C Al ′ are measured.
  • the conditions for descaling austenitic stainless steel conform to JIS Z 2290 (2004).
  • Analysis of the Cr concentration C Cr other than the surface layer and the Al concentration C Al other than the surface layer can be obtained by a well-known component analysis method. Specifically, the following method is used. An austenitic stainless steel is cut perpendicularly to the longitudinal direction (in the axial direction in the case of a steel pipe) to prepare a measurement surface. Drill the center of thickness of the measurement surface with a drill. Chips are generated by drilling and collected. Collect chips from four locations on the same measurement surface. When the austenitic stainless steel is a steel pipe, chips are collected from four locations at a 45 ° pitch. The collected chips are subjected to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry) to perform elemental analysis of chemical composition. The analysis procedure by ICP-OES conforms to JIS G 1258 (2007). The average of the four measured values is defined as the Cr concentration C Cr (%) other than the surface layer and the Al concentration C Al (%) other than the surface layer.
  • ICP-OES Inductive
  • the austenitic stainless steel of this embodiment is provided with an Al 2 O 3 coating on the surface after the heat treatment step described later. Therefore, the austenitic stainless steel of this embodiment may have an Al 2 O 3 coating on the surface.
  • the Al 2 O 3 film can be removed by a known method such as pickling after the heat treatment step or shot peening. Therefore, the austenitic stainless steel of this embodiment may be in a state where the surface Al 2 O 3 film is removed.
  • the austenitic stainless steel of this embodiment has a crystal grain size of 30 to 80 ⁇ m. If the crystal grain size is 30 ⁇ m or more, the creep strength of the steel is further increased. If the crystal grain size is 80 ⁇ m or less, the grain boundary diffusion of Al is promoted and the formation of the Al 2 O 3 film is further promoted.
  • the crystal grain size is determined by a microscopic test method for crystal grain size specified in JIS G 0551 (2013).
  • the shape of the austenitic stainless steel according to the present embodiment is not particularly limited.
  • Austenitic stainless steel is, for example, a steel pipe.
  • Austenitic stainless steel pipes are used as reaction tubes for chemical plants.
  • the austenitic stainless steel may be a plate, rod, wire, or the like.
  • a steel pipe manufacturing method will be described as an example of a method for manufacturing the austenitic stainless steel according to the present embodiment.
  • 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.
  • you may manufacture a pipe-shaped casting by the centrifugal casting method.
  • Hot forging process You may manufacture a cylindrical raw material by implementing hot forging with respect to the manufactured raw material. If hot forging is carried out, the internal structure of the molten steel produced in the preparation process can be changed from a solidified structure to a uniform sized structure.
  • the temperature of hot forging is 900 to 1200 ° C., for example.
  • a steel base tube is manufactured by performing hot working on the material manufactured in the preparation process or the material that has been hot forged (cylindrical material). For example, a through hole is formed in the center of a cylindrical material by machining.
  • a steel base tube is manufactured by performing hot extrusion on a cylindrical material in which a through hole is formed. The processing temperature for hot extrusion is, for example, 900 to 1200 ° C.
  • a steel blank may be manufactured by piercing and rolling a cylindrical material (Mannesmann method or the like).
  • Cold work is performed on the steel base tube after hot working to produce an intermediate material.
  • the cold working is, for example, cold drawing or the like. If strain is applied to the steel surface in the cold working process, elements such as Al and Cr easily move to the steel surface. In this case, the TEE effect can be sufficiently obtained. Thereby, Cr of a steel surface layer is lacking moderately, and the austenitic stainless steel which satisfy
  • the heat treatment temperature is 900-1100 ° C., and the heat treatment time is 3.0-30.0 minutes.
  • the heat treatment temperature is less than 900 ° C. or the heat treatment time is less than 3.0 minutes, the TEE effect cannot be sufficiently obtained.
  • the Cr concentration C Cr ′ of the steel surface layer becomes too high and does not satisfy the formula (1).
  • Cr carbide is formed on the steel surface in a high-temperature carburizing environment, and a uniform Al 2 O 3 film is not sufficiently formed.
  • the heat treatment temperature is 900 ° C. or higher, and the heat treatment time is 3.0 minutes or longer. If the heat treatment temperature is 900 ° C. or more and the heat treatment time is 3.0 minutes or more, the crystal grains are 30 ⁇ m or more.
  • the Al concentration C Al ′ of the steel surface layer becomes too low and does not satisfy the formula (1). Therefore, a uniform Al 2 O 3 film is not sufficiently formed in a high-temperature carburizing environment. As a result, carburization resistance is reduced. Therefore, the heat treatment temperature is less than 1100 ° C. and the heat treatment time is 30.0 minutes or less. If the heat treatment temperature is less than 1100 ° C. and the heat treatment time is 30.0 minutes or less, the crystal grains will be 80 ⁇ m or less.
  • the heat treatment temperature is 900 to less than 1100 ° C. and the heat treatment time is 3.0 to 30.0 minutes, a TEE effect can be obtained sufficiently and appropriately, and a steel having a chemical composition satisfying the formula (1) can be obtained. As a result, carburization resistance in a high-temperature carburizing environment is enhanced.
  • ⁇ Pickling treatment may be applied to the intermediate material after heat treatment 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 minutes to 60 minutes.
  • shot processing may be performed on the steel surface for the purpose of descaling the steel surface and imparting strain to the steel surface with respect to the pickled intermediate material.
  • the material, shape, and processing conditions of the shot grains in the shot processing are not specified, but the material, shape, and processing conditions are sufficient for exfoliating the scale of the steel surface or imparting strain to the steel surface.
  • the scale is, for example, Al 2 O 3 .
  • the Al 2 O 3 film can be removed by known methods such as pickling and shot processing.
  • the austenitic stainless steel of this embodiment is manufactured by the above manufacturing method.
  • the manufacturing method of the steel pipe was demonstrated above.
  • the austenitic stainless steel of this embodiment is particularly preferably applied to a steel pipe. Therefore, Preferably, the austenitic stainless steel of this embodiment is an austenitic stainless steel pipe.
  • a cylindrical ingot (30 kg) having an outer diameter of 120 mm was manufactured using the molten steel. Hot forging and hot rolling were performed on the ingot. After hot rolling, cold rolling was performed under the conditions shown in Table 2 to produce an intermediate material having a thickness of 15 mm. From the obtained intermediate material, a plate material of 8 mm ⁇ 20 mm ⁇ 30 mm was manufactured by machining for two steel types. The plate material was heat-treated at the temperature and time shown in Table 2. After the heat treatment, the plate was cooled with water to produce a test steel plate.
  • a test piece for microscopic observation was produced from the central part of the cross section perpendicular to the rolling direction of the steel plate of each test number.
  • the microscopic test method defined in ASTM E 112 was performed, and the crystal grain size was measured.
  • the observation surface was mechanically polished and then corroded using a corrosive solution, and the crystal grain boundary on the observation surface was revealed.
  • the average grain size of each field was determined. The area of each visual field is about 0.75 mm 2 .
  • Test results The test results are shown in Table 2.
  • test number 13 the processing rate during cold rolling was too low. Therefore, F1 was 0.35 and did not satisfy Formula (1). As a result, the amount of intrusion C was 0.51%, and the carburization resistance was low.
  • test number 14 the heat treatment temperature was too low. Therefore, F1 was 1.00 and did not satisfy the formula (1). As a result, the amount of intrusion C was 0.65%, and the carburization resistance was low. In Test No. 14, the crystal grain size was 21 ⁇ m.
  • test number 15 the heat treatment temperature was too high. Therefore, F1 was 0.39, and the formula (1) was not satisfied. As a result, the amount of intrusion C was 0.58%, and the carburization resistance was low. In Test No. 15, the crystal grain size was 131 ⁇ m.
  • test number 16 the heat treatment time was too short. Therefore, F1 was 1.06 and did not satisfy Formula (1). As a result, the amount of intrusion C was 0.69%, and the carburization resistance was low. In Test No. 16, the crystal grain size was 22 ⁇ m.
  • test number 17 the heat treatment time was too long. Therefore, F1 was 0.95 and did not satisfy the formula (1). As a result, the amount of intrusion C was 0.54%, and the carburization resistance was low. In Test No. 17, the crystal grain size was 95 ⁇ m.
  • test number 19 the Cr content was too high. Therefore, formation of the Al 2 O 3 film was inhibited by Cr carbide. As a result, the amount of intrusion C was 0.60%, and the carburization resistance was low.
  • test number 20 the Al content was too low. Therefore, the Al 2 O 3 film was not sufficiently formed. As a result, the amount of intrusion C was 0.83%, and the carburization resistance was low.
  • test number 21 the Ni content was too low. Therefore, the amount of intrusion C was 0.52%, and the carburization resistance was low.
  • test number 23 the Mg content was too high. Therefore, the drawing value was less than 60% and the hot workability was low.
  • the austenitic stainless steel of the present invention can be used even in a high-temperature carburizing environment where carburization and coking are a concern, such as a hydrocarbon gas atmosphere. It is particularly suitable for use as a reaction tube steel in chemical industrial plants such as ethylene production plants.

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Abstract

L'invention concerne un acier inoxydable austénitique qui présente une excellente résistance à la carburation même dans un environnement de carburation à haute température et qui présente également une excellente aptitude à l'ouvrabilité à chaud pendant la production. Un acier inoxydable austénitique selon un mode de réalisation de la présente invention présente une composition chimique qui contient, en % en masse, 0,03 % ou plus mais moins de 0,25 % de C, 0,01 % à 2,0 % de Si, 2,0 % ou moins de Mn, 10 % ou plus mais moins de 22 % de Cr, plus de 30,0 % mais 40,0 % ou moins de Ni, plus de 2,5 % mais moins de 4,5 % d'Al, 0,01 % à 3,5 % de Nb, 0,0005 % à 0,05 % de Ca, 0,0005 % à 0,05 % de Mg et 0,03 % ou moins de N, le reste étant constitué de Fe et d'impuretés. La concentration en Cr CCr' de la couche superficielle de cet acier inoxydable austénitique et la concentration en Al CAl' de la couche superficielle de cet acier inoxydable austénitique satisfont à la formule (1) par rapport à la concentration en Cr CCr de portions autres que la couche superficielle et la concentration en Al CAl de portions autres que la couche superficielle. 0,40 ≤ (CCr'/CAl')/(CCr/CAl) ≤ 0,80 (1)
PCT/JP2017/023657 2016-06-29 2017-06-28 Acier inoxydable austénitique WO2018003823A1 (fr)

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US20190127832A1 (en) 2019-05-02
JPWO2018003823A1 (ja) 2019-04-25
KR20190022723A (ko) 2019-03-06
JP6614347B2 (ja) 2019-12-04
KR102124914B1 (ko) 2020-06-19
EP3480330A1 (fr) 2019-05-08
EP3480330A4 (fr) 2020-01-08
CN109415786A (zh) 2019-03-01

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