WO2012153814A1 - 耐繰返し酸化特性に優れた耐熱オーステナイト系ステンレス鋼 - Google Patents

耐繰返し酸化特性に優れた耐熱オーステナイト系ステンレス鋼 Download PDF

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WO2012153814A1
WO2012153814A1 PCT/JP2012/062039 JP2012062039W WO2012153814A1 WO 2012153814 A1 WO2012153814 A1 WO 2012153814A1 JP 2012062039 W JP2012062039 W JP 2012062039W WO 2012153814 A1 WO2012153814 A1 WO 2012153814A1
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stainless steel
austenitic stainless
steel
heat
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PCT/JP2012/062039
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English (en)
French (fr)
Japanese (ja)
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剛夫 宮村
難波 茂信
和基 古屋
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株式会社神戸製鋼所
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Priority to ES12782655.0T priority Critical patent/ES2590465T3/es
Priority to US14/115,570 priority patent/US20140154128A1/en
Priority to KR1020137029415A priority patent/KR20130137705A/ko
Priority to CN201280022304.7A priority patent/CN103517998B/zh
Priority to EP12782655.0A priority patent/EP2708611B1/en
Publication of WO2012153814A1 publication Critical patent/WO2012153814A1/ja

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/004Heat treatment of ferrous alloys containing Cr and Ni
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/005Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron

Definitions

  • the present invention relates to a heat-resistant austenitic stainless steel suitably used as a heat transfer tube material such as a boiler, and more particularly to a heat-resistant austenitic stainless steel excellent in cyclic oxidation resistance.
  • 25Cr-20Ni austenitic stainless steel (SUS310S) is known as a heat resistant material having excellent oxidation resistance in a broad sense including characteristics other than cyclic oxidation resistance.
  • This stainless steel contains a large amount of expensive Ni. There is a problem that the cost is high. For this reason, it is important to use 18Cr-8Ni austenitic stainless steel (SUS304), which has a low Ni content and good high-temperature strength and corrosion resistance, as basic components for boiler heat transfer tube materials. It becomes.
  • Patent Documents 1 and 2 have been proposed as technologies related to austenitic stainless steel using a Ti compound as a precipitation strengthening mechanism. ing.
  • Patent Document 1 discloses that the oxidation resistance is improved by adding Al that contributes to the improvement of corrosion resistance and promoting the formation of a Cr 2 O 3 layer by surface polishing.
  • the total amount of Al and Si is increased to 4% or more, and in addition, REM such as Ce, Y, La, etc. or Ca is added to be resistant to oxidation. Has been shown to be improved.
  • the action of delaying the growth rate of the oxide formed on the steel pipe surface can be expected by the addition of Al and Si and the formation of the Cr 2 O 3 layer, the formation of the oxide itself is not completely prevented. Also, it cannot be expected to exhibit good cyclic oxidation resistance. Furthermore, the steel material to which Al is added has a problem that surface flaws are likely to occur during pipe making.
  • Patent Document 2 discloses that Ce, La, and Hf are added in order to improve the oxidation resistance. However, similar to the above technique, it is expected that the cyclic oxidation resistance is low, and the repetition resistance is also reduced. It was not made in recognition of the improvement in oxidation characteristics.
  • Patent Document 3 As a technique for improving the resistance to repeated oxidation, a technique such as Patent Document 3 has also been proposed. However, since this technique contains a large amount of Al and Si, there is a problem in that it causes embrittlement after a surface flaw on the steel pipe or a long-time heat treatment. Further, in this technique, it has been shown that adding REM such as La and Ce including Y exhibits an effect of improving the adhesion of the scale, but it does not have sufficient characteristics and is resistant to resistance. It was not made in recognition of the improvement of repeated oxidation characteristics.
  • REM such as La and Ce including Y
  • Patent Document 4 As a technique for improving the oxidation resistance of austenitic stainless steel for boilers, a technique such as Patent Document 4 has also been proposed.
  • This technology is a component system of “Take SUS304J1HTB” that uses Nb and N for precipitation strengthening and solid solution strengthening.
  • Ti is added in an amount of about 0.002 to 0.05% for the purpose of forming oxide inclusions, but a steel material using precipitation of Ti compounds such as fire SUS321J2HTB as a strengthening mechanism.
  • this technique is not made by recognizing an improvement in the resistance to repeated oxidation, and is expected to have a low resistance to repeated oxidation.
  • oxidation resistance is improved by adding REM and particle spray peening.
  • the peening process has another problem that the cost is increased due to an increase in the manufacturing process, and is not made in recognition of the improvement of the resistance to repeated oxidation, and is expected to have a low resistance to repeated oxidation.
  • the present invention has been made under such circumstances, and the object thereof is to have a chemical composition equivalent to that of 18Cr-8Ni austenitic stainless steel in which the contents of Ni and Cr are added, as well as the addition of Al and Si, and the surface.
  • An object of the present invention is to provide a heat-resistant austenitic stainless steel having excellent resistance to repeated oxidation, which is less dependent on treatment and has less oxide peeling in a repeated oxidation environment and is less likely to cause thinning.
  • the heat-resistant austenitic stainless steel of the present invention that has solved the above problems is C: 0.05-0.2% (meaning mass%, hereinafter the same for chemical composition), Si: 0.1-1%, Mn: 0.1 to 2.5%, Cu: 1 to 4%, Ni: 7 to 12%, Cr: 16 to 20%, Nb: 0.1 to 0.6%, Zr: 0.05 to 0 .4%, Ce: 0.005 to 0.1%, Ti: 0.1 to 0.6%, B: 0.0005 to 0.005%, N: 0.001 to 0.15%, S: It contains 0.005% or less (excluding 0%) and P: 0.05% or less (not including 0%), respectively, and the balance is made of iron and inevitable impurities.
  • the heat-resistant austenitic stainless steel of the present invention further contains Mo: 3% or less (not including 0%) and / or W: 5% or less (not including 0%) as necessary. Yes, the inclusion of these components further improves the high temperature strength.
  • the heat-resistant austenitic stainless steel of the present invention further contains Ca: 0.005% or less (not including 0%) and / or Mg: 0.005% or less (not including 0%) as necessary.
  • Ca 0.005% or less (not including 0%)
  • Mg 0.005% or less
  • the chemical component composition as described above By adjusting the chemical component composition as described above, a heat-resistant austenitic stainless steel with improved resistance to repeated oxidation can be obtained. Further, the crystal grain size of the metal structure is 6 or more and less than 12 in terms of ASTM grain size number. As a result, higher resistance to repeated oxidation can be obtained and the characteristics can be exhibited stably.
  • the heat-resistant austenitic stainless steel of the present invention is less susceptible to the progress of oxidation due to scale peeling and the accompanying thinning of the steel material even in a repetitive oxidation environment, so that it can be used as a heat transfer tube for coal-fired power generation. It is possible to improve the power generation efficiency by increasing the temperature of the tube, extending the life of the heat transfer tube compared to existing materials, and reducing the maintenance cost. Moreover, since there is little peeling of a scale, when it uses as a heat exchanger tube, scattering of the scale inside can be suppressed and damage to a turbine can also be reduced.
  • the present inventors have studied from various angles in order to realize an austenitic stainless steel having improved resistance to repeated oxidation while maintaining necessary high-temperature strength. As a result, if a predetermined amount of Zr and Ce is contained in a stainless steel having a chemical composition equal to that of 18Cr-8Ni austenitic stainless steel, the remarkably excellent resistance to repeated oxidation. The present invention was completed by discovering that the characteristics can be exhibited.
  • the heat resistant austenitic stainless steel of the present invention is characterized in that the contents of Ni and Cr contain a predetermined amount of Zr and Ce with respect to the chemical composition equivalent to that of 18Cr-8Ni austenitic stainless steel.
  • the reasons for setting the ranges of the contents of Zr and Ce are as follows.
  • Zr and Ce express the effect of suppressing the exfoliation of the oxide by these synergistic effects.
  • it is necessary to contain Zr at 0.05% or more.
  • the upper limit must be 0.4% or less.
  • Ce in order to exhibit the effect, it is necessary to contain 0.005% or more.
  • the Ce content exceeds 0.1% and becomes excessive, an economic cost increase is caused.
  • the preferable lower limit of the Zr content is 0.10% or more (more preferably 0.15% or more), and the preferable upper limit is 0.3% or less (more preferably 0.25% or less).
  • the preferable minimum of Ce content is 0.01% or more (more preferably 0.015% or more), and a preferable upper limit is 0.05% or less (more preferably 0.03% or less).
  • pure Ce may be added as a raw material of Ce, but it is also possible to add the necessary pure Ce using a separately prepared Ce-containing mother alloy or Ce-containing misch metal. There is no problem even if La, Nd, Pr, etc. contained are contained in steel as impurities at a lower concentration than Ce, respectively, and melting work is performed by using a mother alloy or misch metal compared to pure Ce that is easily oxidized It is possible to simplify the handling of time.
  • Patent Documents 1, 3, and 5 among the prior arts disclose that the adhesion of oxides is improved by adding REM containing Y, La, and Ce. , REM is assumed to be added alone, and no synergistic effect by adding Ce together with Zr is disclosed.
  • Patent Document 2 discloses that Zr and Ce can be used in combination, but in this technique, none of them is an essential component, and it is added as necessary including non-addition.
  • Zr is contained in an amount less than the range specified in the present invention in view of strengthening grain boundaries and improving creep ductility.
  • the heat-resistant austenitic stainless steel of the present invention has a chemical composition equivalent to that of 18Cr-8Ni austenitic stainless steel in the contents of Ni and Cr, but the chemical composition of each element other than Zr and Ce ( C, Si, Mn, Cu, Ni, Cr, Nb, Ti, B, N, S, and P) need to be appropriately adjusted.
  • the effects of these components and the reasons for setting the range are as follows.
  • C is an element that has the effect of forming carbides in a high-temperature use environment and improving the high-temperature strength and creep strength necessary as a heat transfer tube.
  • C is 0.05. % Or more must be contained.
  • the preferable lower limit of the C content is 0.07% or more (more preferably 0.09% or more), and the preferable upper limit is 0.18% or less (more preferably 0.15% or less).
  • Si 0.1 to 1%
  • Si is an element having a deoxidizing action in molten steel. Even if it is contained in a very small amount, it effectively works to improve oxidation resistance. In order to exert these effects, the Si content needs to be 0.1% or more. However, if the Si content is excessive and exceeds 1%, the formation of the ⁇ phase is caused and the steel material becomes brittle ( ⁇ brittle).
  • the preferable lower limit of the Si content is 0.2% or more (more preferably 0.3% or more), and the preferable upper limit is 0.9% or less (more preferably 0.8% or less).
  • Mn 0.1 to 2.5%
  • Mn is an element having a deoxidizing action in molten steel, and also has an action of stabilizing austenite.
  • the Mn content needs to be 0.1% or more. However, if the Mn content is excessive and exceeds 2.5%, hot workability is impaired.
  • the preferable lower limit of the Mn content is 0.2% or more (more preferably 0.3% or more), and the preferable upper limit is 2.0% or less (more preferably 1.8% or less).
  • Cu 1 to 4%
  • Cu is an element that forms consistent precipitates in the steel (precipitates whose atomic arrangement is continuous with the base metal) and significantly improves the high-temperature creep strength, and is one of the main strengthening mechanisms in stainless steel. It is. In order to exert this effect, the Cu content needs to be 1% or more. However, even if the Cu content is excessive and exceeds 4%, the effect is saturated.
  • the preferable lower limit of the Cu content is 2.0% or more (more preferably 2.5% or more), and the preferable upper limit is 3.7% or less (more preferably 3.5% or less).
  • Ni has an effect of stabilizing austenite, and it is necessary to contain 7% or more in order to maintain the austenite phase. However, if the Ni content becomes excessive and exceeds 12%, the cost will increase.
  • the preferable lower limit of the Ni content is 7.5% or more (more preferably 8.0% or more), and the preferable upper limit is 11.5% or less (more preferably 11.0% or less).
  • Cr 16-20%
  • Cr is an essential element in order to develop corrosion resistance as stainless steel. In order to exert such effects, it is necessary to contain 16% or more of Cr. However, if the Cr content becomes excessive and exceeds 20%, the ferrite phase that causes a decrease in high-temperature strength increases.
  • the preferable lower limit of the Cr content is 16.5% or more (more preferably 17.0% or more), and the preferable upper limit is 19.5% or less (more preferably 19.0% or less).
  • Nb is an element effective for improving the high-temperature strength by precipitating carbonitride (carbide, nitride, or carbonitride), and this precipitate suppresses the coarsening of crystal grains and diffuses Cr. By promoting the above, a secondary effect of improving corrosion resistance is exhibited.
  • Nb needs to be contained by 0.1% or more. However, if the Nb content exceeds 0.6% and becomes excessive, the precipitates become coarse and the toughness is reduced.
  • a preferable lower limit of the Nb content is 0.12% or more (more preferably 0.15% or more), and a preferable upper limit is 0.5% or less (more preferably 0.3% or less).
  • Ti 0.1 to 0.6%
  • Ti exhibits the same effect as Nb, but by adding it in combination with Nb and Zr, the precipitates are further stabilized and effective in maintaining high-temperature strength for a long period of time.
  • the Ti content needs to be 0.1% or more.
  • the preferable lower limit of the Ti content is 0.12% or more (more preferably 0.15% or more), and the preferable upper limit is 0.5% or less (more preferably 0.3% or less).
  • B has the effect of promoting the formation of M 23 C 6 type carbide (M is a carbide forming element), which is one of the main strengthening mechanisms, by forming a solid solution in steel.
  • M is a carbide forming element
  • the B content needs to be 0.0005% or more.
  • a preferable lower limit of the B content is 0.001% or more (more preferably 0.0012% or more), and a preferable upper limit is 0.004% or less (more preferably 0.003% or less).
  • N has the effect of improving high temperature strength by solid solution strengthening by dissolving in steel, and is effective in improving high temperature strength by forming nitrides with Cr and Nb under a long-term high temperature load. It is an element. In order to exhibit these effects effectively, the N content needs to be 0.001% or more. However, if the N content becomes excessive and exceeds 0.15%, the formation of coarse Ti nitrides and Nb nitrides is caused, and the toughness is deteriorated.
  • the preferable lower limit of the N content is 0.002% or more (more preferably 0.003% or more), and the preferable upper limit is 0.10% or less (more preferably 0.08% or less, still more preferably 0.02%). The following).
  • S 0.005% or less (excluding 0%)
  • S is an unavoidable impurity, but when its content increases, hot workability deteriorates, so it is necessary to make it 0.005% or less. Further, S impairs the action of adding Ce by fixing Ce as a sulfide, so S is preferably suppressed to 0.002% or less (more preferably 0.001% or less).
  • P 0.05% or less (excluding 0%)
  • P is an inevitable impurity, but if its content increases, weldability is impaired, so it is necessary to make it 0.05% or less. Preferably it is good to suppress to 0.04% or less (more preferably 0.03% or less).
  • the contained elements specified in the present invention are as described above, and the balance is iron and inevitable impurities, and in addition to La, Nd, Pr, etc. contained at a lower concentration than Ce when adding Ce raw material with misch metal Furthermore, mixing of elements brought in depending on the situation of raw materials, materials, manufacturing equipment, etc. can be allowed. However, low melting point impurities such as Sn, Pb, Sb, As, and Zn derived from scrap raw materials reduce the strength of grain boundaries during hot working or when used in a high temperature environment. In order to improve the resistance to embrittlement cracking after use, it is desirable to keep the concentration low. Moreover, the steel material of this invention may contain Mo, W, Ca, Mg, etc. as needed, and the characteristic of steel materials is further improved according to the kind of element contained.
  • Mo and W have the effect of improving the high temperature strength by solid solution strengthening, and the high temperature strength can be further increased by inclusion if necessary.
  • Mo content is excessive, hot workability is hindered. More preferably, it is 2.5% or less (more preferably 2.0% or less).
  • W content is excessive, a coarse intermetallic compound is formed and the high temperature ductility is lowered. More preferably, it is 4.5% or less (more preferably 4.0% or less).
  • the preferable minimum for exhibiting the above effects effectively is 0.1% or more (more preferably 0.5% or more) in Mo, and 0.1% or more (more preferably 1) in W. 0.0% or more).
  • the contents may be set according to the required amount of reinforcement and the allowable cost.
  • Ca and Mg function as desulfurization / deoxidation elements, formation of Ce sulfide and Ce oxide can be suppressed, and Ce yield can be improved, and reduction in toughness due to inclusion formation can be suppressed.
  • a preferable lower limit for effectively exhibiting such an effect is 0.0002% or more, and more preferably 0.0005% or more.
  • the upper limit value is set to 0.005% or less because there are restrictions on work such as bumping of molten steel during melting work. More preferably, both are 0.002% or less.
  • the heat-resistant austenitic stainless steel of the present invention can improve the resistance to repeated oxidation by containing a predetermined amount of Zr and Ce. However, in order to further improve the characteristics, the crystal grain size of the metal structure is controlled. It is effective. From such a viewpoint, it is preferable that the crystal grain size of the metal structure of the heat-resistant austenitic stainless steel is a microstructure having an ASTM (American Society for Testing and Materials) grain size number of 6 or more and less than 12.
  • the grain size number (crystal grain size number) is determined by ASTM, and means a grain size number calculated by a counting method (Planimetric method).
  • the crystal grain size of the metal structure is less than 6 in terms of ASTM grain size number, the effect of improving the repeated oxidation resistance by containing Zr and Ce can be obtained, but the improvement effect cannot be sufficiently enhanced.
  • the particle size number is more preferably 7 or more, and still more preferably 9 or more.
  • the upper limit of the crystal grain size is preferably less than 12. In consideration of production cost and productivity, it is more preferably 10 or less.
  • the crystal grain size range as described above can be obtained by adjusting the amount of components contributing to pinning of grain boundaries and the conditions of hot and cold working and heat treatment such as drawing and extrusion during the pipe making process. . Although each optimum condition varies depending on these three factors, in order to make the crystal grain size fine, it is necessary to add a large amount of precipitated elements, to increase the degree of processing, and to lower the heat treatment temperature.
  • Cold / hot working is aimed at adjusting the thickness and adjusting the grain structure by heat treatment after processing by introducing strain, and is usually carried out at a cross-section reduction rate of 30% or more.
  • the heat treatment is intended to remove strain, and is generally performed in a temperature range of 1000 ° C. or higher and lower than 1300 ° C.
  • the prescribed particle size range can be obtained by setting the heat treatment temperature to 1250 ° C. or less, preferably 1225 ° C. or less, particularly preferably 1150 ° C. or less. It is not limited to this condition depending on the balance between processing and heat treatment.
  • Example 1 Various steel materials having the chemical composition shown in Table 1 below were melted, and a 20 kg ingot melted in a vacuum melting furnace (VIF) was hot forged into a dimension of width: 120 mm ⁇ thickness: 20 mm, at 1250 ° C. After heat treatment, it was processed to a thickness of 13 mm by cold rolling. Thereafter, heat treatment was again performed at 1150 ° C. for 5 minutes, and this was used as a base material. A 20 mm ⁇ 30 mm ⁇ 2 mm steel material was cut out from the base material by machining, and a test piece was prepared by smoothing and mirror-finishing the surface of the steel material by polishing using emery paper and buffing using diamond abrasive grains.
  • VIF vacuum melting furnace
  • test No. Nos. 1 to 10 are steel materials (invention steels) satisfying the requirements specified in the present invention.
  • Nos. 11 to 16 are steel materials (comparative steels) that do not satisfy the requirements defined in the present invention.
  • Reference numerals 14, 15, and 16 are “fire SUS304J1HTB equivalent steel”, “SUS304L equivalent steel”, and “SUS310S equivalent steel”, which are existing steels, respectively.
  • Test No. 7 and 8 are steel materials to which Ce is added by misch metal, and include La, Pr, Nd and the like as impurities.
  • Test No. 9 and 10 are steel materials to which Mg and Ca are added, respectively.
  • fire SUS304J1HTB equivalent steel belongs to 18Cr-8Ni austenitic stainless steel and is a steel type that has been used as a boiler heat transfer tube (for example, “Materia” Vol. 46, No. 2). No. 2007, P99-101).
  • SUS310S equivalent steel belongs to 25Cr-20Ni austenitic stainless steel and is more expensive because it contains more Ni than 18Cr-8Ni austenitic stainless steel, but essentially in terms of chemical composition. It is a steel type that has better corrosion resistance than 18Cr-8Ni austenitic stainless steel.
  • the production and peeling of the scale does not occur because the steel of the present invention has a smoother scale surface.
  • the steel according to the present invention exhibits the same properties as the existing steel SUS310S equivalent to 25Cr-20Ni (test No. 16), which has a high Ni content and is excellent in corrosion resistance, and is an 18Cr-8Ni austenitic stainless steel. It can be seen that, despite the low cost, the repeated oxidation resistance can be improved to the same level as the 25Cr-20Ni austenitic stainless steel.
  • Example 2 Test No. shown in Tables 1 and 2 Inventive steels 1 to 6 and test no.
  • the heat treatment temperature was changed in the temperature range of 1125 to 1275 ° C. after cold working with a cross-section reduction rate of 35%, and samples with crystal grain numbers of 4.5 to 10.0 were prepared for each steel material.
  • the repeated oxidation test is a temperature cycle of 25 minutes for heating in the furnace and 5 minutes for cooling to the atmosphere. The sample is taken in and out of the atmospheric furnace at 1100 ° C., and the specimen mass after 40 cycles is compared with the specimen mass in the initial state The mass loss (thickness loss: mg ⁇ cm ⁇ 2 ) was determined.
  • the amount of thinning was significantly improved in some steels with added Zr and Ce, and the amount of thinning after 20 cycles was an error depending on the particle size. Repeated. For the calculation of the crystal grain size, three visual fields were observed per steel type.
  • the addition of Zr and Ce itself improves the resistance to repeated oxidation, and the chemical composition is within the range specified in the present invention. It can be seen that the finer the grain size, the better the characteristics.
  • the heat-resistant austenitic stainless steel of the present invention is suitably used as a heat transfer tube material such as a boiler.

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PCT/JP2012/062039 2011-05-11 2012-05-10 耐繰返し酸化特性に優れた耐熱オーステナイト系ステンレス鋼 WO2012153814A1 (ja)

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KR1020137029415A KR20130137705A (ko) 2011-05-11 2012-05-10 내반복 산화 특성이 우수한 내열 오스테나이트계 스테인리스강
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ES2590465T3 (es) 2016-11-22
CN103517998B (zh) 2016-08-17
JP2013076156A (ja) 2013-04-25
CN103517998A (zh) 2014-01-15
KR20130137705A (ko) 2013-12-17
JP5143960B1 (ja) 2013-02-13
EP2708611A1 (en) 2014-03-19
EP2708611B1 (en) 2016-08-24
US20140154128A1 (en) 2014-06-05

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