EP3995599A1 - Austenitischer rostfreier stahl - Google Patents
Austenitischer rostfreier stahl Download PDFInfo
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- EP3995599A1 EP3995599A1 EP20206232.9A EP20206232A EP3995599A1 EP 3995599 A1 EP3995599 A1 EP 3995599A1 EP 20206232 A EP20206232 A EP 20206232A EP 3995599 A1 EP3995599 A1 EP 3995599A1
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- stainless steel
- austenitic stainless
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- 229910000963 austenitic stainless steel Inorganic materials 0.000 title claims abstract description 80
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 20
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 11
- 239000010959 steel Substances 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 229910001220 stainless steel Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 239000011651 chromium Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- -1 cerium and lanthanum Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 description 39
- 238000007254 oxidation reaction Methods 0.000 description 39
- 238000012360 testing method Methods 0.000 description 34
- 125000004122 cyclic group Chemical group 0.000 description 11
- 239000000155 melt Substances 0.000 description 10
- 229910001566 austenite Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 6
- 230000001464 adherent effect Effects 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005255 carburizing Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 238000000641 cold extrusion Methods 0.000 description 1
- 238000010273 cold forging Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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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
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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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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
Definitions
- the present invention relates to an austenitic heat and creep resistant stainless steel. It also relates to the use of this austenitic stainless steel, especially in oxidizing and carburizing environments. Further, the present invention relates to products made of this austenitic heat and creep resistant stainless steel.
- S31008 is the most commonly used high temperature stainless steel for applications in the temperature range of 800 - 1050°C. It is however outperformed by S30815 both in regards to creep resistance and oxidation resistance in cyclic temperatures. It is however so that S31008 performs better in reducing or carburizing environments.
- the present invention relates to an austenitic heat resistant stainless steel, intended to replace the existing heat resistant stainless grades S30815 and S31008 for special high temperature applications like muffle and heat treatment furnaces where both oxidizing and reducing environments exist.
- an austenitic heat resistance stainles steel is provided having even better high temperature corrosion resistance and creep properties, being cost effective and easy to produce.
- the austenitic stainless steel according to embodiments provides high temperature corrosion resistance and creep properties and is particularly suitable for high temperature applications in aggressive environments such as heat treatment equipment e.g. muffle furnaces.
- the austenitic stainless steel according to embodiments can be economically manufactured in a practical and environmentally sound manner.
- an austenitic stainless steel has a composition utilizing the benefits of several alloying elements in order to combine good oxidation resistance through the formation of a tight and adhesive oxide layer and to, at the same time, be alloyed in a way to resist carburizing. Furthermore, it is designed in a way to have excellent creep resistance.
- a well-defined and balanced alloying with carbon and nitrogen increases the creep strength through the formation of intra- and to some extent intergranular carbides and nitrides; so-called precipitation strengthening.
- Chromium and silicon are added in order to have a high oxidation resistance.
- the amount is carefully balanced in order to not have a negative influence on the structure stability, since both these elements promote the formation of intermetallic and brittle phases such as sigma phases.
- Rare earth metals e.g. cerium has in earlier micro alloyed (MA) grades shown to have an excellent effect on the cyclic oxidation resistance.
- MA micro alloyed
- rare earth metals are added in an amount optimized to get the benefits of a more elastic and adhesive oxide layer. The amount, however, is limited since it has been shown that a surplus amount of rare earth metals is no longer beneficial for oxidation resistance and that it might cause clusters of oxide inclusions having a negative effect on mechanical properties and formability.
- the nickel content is at a level known from other well-known commercially-available high temperature stainless steels but different from other high temperature grades micro alloyed with rare earth metals. Thus, the combination of the elements is utilized in a novel way.
- the nickel in combination with silicon promotes resistance to carburization.
- the melts 1-8 are produced using a Mullite crucible and heated up to melt in an Ar protection atmosphere using a high frequency coil. The melt process takes about 10 to 15 min. Each melt is weighed about 600 grams. The melts are forged by using the hydraulic press Interlaken. An in-house software program has been developed that presses the ingot in short bursts to the desired thickness over a predetermined number of steps. The melt is heated to about 1250°C between each step. The thickness of the final piece is 8 mm.
- the test melts 9-15 are produced using a Leybold-Heraeus vacuum induction furnace having minimum pressure of 4 x 10-4 bar. The melts are tapped to metal mound in vacuum for producing 65 kg ingots. Heating up to 1250°C, the Frohling rolling mill with furnaces on both sides is used to hot roll 38 mm thick slab to 10 and 6 mm thick plates, respectively. The rolling speed is 45 m/min. The rolling passes are 7 and 9 for 10 mm thick plate and for 6 mm thick plate, respectively.
- Annealing temperature and holding time have been chosen to bring about a fully recrystallized austenite, proper hardness and grain size. Annealing temperature and holding time cover from 1100°C to 1200°C and from 0 min to 30 min, respectively.
- melts listed in Table 1 fulfill the basic idea behind this austenitic stainless steel to chemically combine main elements like chromium, nickel, silicon, nitrogen and REM of S31008 and S30815. Therefore, the chemical compositions obtained in above test melts result in a target and preferred chemical composition as described below in Table 2.
- the microstructure investigation, oxidation and carburisation tests, as well as creep test are performed in the most cases using the melts 7, 8, 14 and 15.
- Table 2 Proposed chemical composition of austenitic stainless steel (wt%).
- Main target composition Broad range Preferred range Carbon 0.03 - 0.20 0.05 - 0.10 Chromium 20.00 - 26.00 24.00 - 26.00 Nickel 10.00 - 22.00 19.00 - 22.00 Silicon 0.50 - 2.50 1.20 - 2.50 Mangness 0.50 - 2.00 0.50 - 2.00 Nitrogen 0.10 - 0.40 0.12-0.20 Sulphur ⁇ 0.015 ⁇ 0.010 Phosphous ⁇ 0.040 ⁇ 0.040 Cerium 0.00 - 0.10* 0.03 - 0.08* *Sum of rare earth metals, mainly Cerium and Lanthanum
- the austenitic stainless heat resistant steel as defined hereinabove and herinafter is intended to be used for manufacturing of objects such as semis, plate, sheet, coil, strip, par, pipe, tube and/or wire.
- the methods used for manufacturing these products include conventional manufacturing processes such as, but not limited to, melting, refining, casting, hot rolling, cold rolling, forging, extrusion and drawing.
- pCH4 is the CH4 partial pressure, in the present case content of CH4 in the gas mixture.
- p2H2 is assumed to be very low, i.e. 0,00001, since the running gas flow and constant supply of CH4 will minimize H2 in the reaction.
- K is the equilibrium constant and is calculated using standard free energy of formation for the reaction ⁇ G at temperature T (K) of 1273K (1000°C).
- the austenitic stainless steel is provided with improved heat resistance and corrosion resistance.
- the austenitic stainless steel has finer grain size which improves oxidation and corrosion resistance as well as ductiliy.
- the austenitic stainless steel has superior cyclic oxidation reistance.
- the steel has superior isothermal oxidation reistance.
- the steel has superior carburization resistance.
- the steel has a creep resistance comparable with commercial grades.
- the steel contains in weight % carbon ⁇ 0.20, chromium 20.00 - 26.00, nickel 10.00 - 22.00, silicon 0.50 - 2.50, manganese ⁇ 2.00, nitrogen 0.10 - 0.40, sulphur ⁇ 0.015, phosphous ⁇ 0.040, rare earth metals 0.00 - 0.10, and the rest being iron (Fe) and inevitable impurities.
- the austenitic stainless steel contains ⁇ 0.20 carbon in weight %. Keeping the carbon content ⁇ 0.20%, preferably at least 0.05% but not more than 0.10% provides an optimization between austenite, mechnical strength and intergranullar corrosion resistance.
- Chromium is the most important alloying element for the stainless steels. Chromium gives stainless steels their fundmental oxidation and corrosion resistance. All stainless steels have a Cr-content of at least 10.5% and the oxidation and corrosion resistance increases with increasing chromium content. In addition, chromium carbide and nitride improve mechanical strength. On the other hand, chromium promotes a ferritic microstructure. High chromium also contributes to intermetallic sigma phase formation. In a preferred embodiment the chromium content is at least 24.0 but not more than 26.0% for the austenitic stainless steel.
- Nickel is present in all of the austenitic stainless steels since nickel promotes an austenitic microstructure. When added to a mix of iron and chromium, nickel increases ductility, high temperature strength, and resistance to both carburization and nitriding because nickel decreases the solubility of both carbon and nitrogen in austenite. On the other hand, high nickel is bad for sulphidation resistance.
- the chromium content is at least 19.0 but not more than 22.0 w-% for the austenitic stainless steel.
- Silicon improves both carburization and oxidation resistance, as well as resistance to absorbing nitrogen at high temperature. On the other hand, silicon tends to make the alloy ferritic, and promotes to intermetallic sigma phase formation.
- the amount of silicon in the austenitic stainless steel is further controlled so that the silicon content is at least 1.20 but not more than 2.50 w-%.
- Manganese is usually considered an austenitizing element and can also replace some of the nickel in the stainless steel. Manganese improves hot workability, weldability, and increases solubility for nitrogen to permit a substantial nitrogen addition. On the other hand, manganese is mildly detrimental to oxidation resistance, so it is limited to 2 w-% maximum in most heat resistant alloys. In a preferred embodiment the amount of manganese in the austenitic stainless steel is at least 0.50 but not more than 2.00 w-%.
- Nitrogen is a very strong austenite former that also significantly increases the mechanical strength. Nitrogen tends to retard or prevent ferrite and sigma formation. On the other hand, high content nitrigen impairs toughness and causes embrittlement. In a preferred embodiment the amount of nitrogen in the austenitic stainless steel is at least 0.12 but not more than 0.20 w-%.
- Sulphur and phosphorus are normally regarded as impurities. Sulphur is commonly below 0.010 w-%, while phosphorus is usually not specified. In a preferred embodiment the sulphur and phosphorus content in the austenitic stainless steel is not more than 0.010 w-% and 0.040 w-%, respectively.
- the rare earth elements are used singly or in combination to increase oxidation resistance by forming a thinner, tighter and more protective oxide scale in austenitic stainless alloys. Residual REM oxides in the metal may also contribute to creep-rupture strength. On the other hand, a surplus amount of rare earth metals might cause clusters of oxide inclusions having a negative effect on mechanical properties and formability.
- the REM content in the austenitic stainless steel, maninly cerium and lanthanum is at least 0.03 w-% but not more than 0.08 w-%. In a particularly preferred embodiment the REM is cerium and is present in the range of 0.03% to 0.08 w-%
- the N, C and rare earth metal (REM) contents in the austenitic stainless steel satisfy the relationship: 0.40 % ⁇ N + 3 ⁇ C + 3 ⁇ REM ⁇ 0.60 %
- the austenitic stainless steel comprises one or more of the inevitable impurities contains in weight %:
- the stainless steel according to embodiments of the present invention has a diverse range of uses.
- the object formed and/or used according to embodiments is selected from the group consisting of plate, sheet, strip, tube, pipe, bar and wire.
- Further embodiments relates to uses of objects formed in heat treatment applications. Such object are apt for use in difficult environments.
- the object may be used in aggressive high temperature environments, which have oxidazing and reducing carburizing atomspheres, like in muffle funace and in metal manufacturing process applications.
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20206232.9A EP3995599A1 (de) | 2020-11-06 | 2020-11-06 | Austenitischer rostfreier stahl |
MX2023005403A MX2023005403A (es) | 2020-11-06 | 2021-11-05 | Acero inoxidable austenitico. |
KR1020237018520A KR20230100735A (ko) | 2020-11-06 | 2021-11-05 | 오스테나이트계 스테인리스 강 |
AU2021374827A AU2021374827A1 (en) | 2020-11-06 | 2021-11-05 | Austenitic stainless steel |
JP2023527394A JP2023553258A (ja) | 2020-11-06 | 2021-11-05 | オーステナイト系ステンレス鋼 |
US18/035,878 US20230416889A1 (en) | 2020-11-06 | 2021-11-05 | Austenitic Stainless Steel |
CN202180080895.2A CN116601324A (zh) | 2020-11-06 | 2021-11-05 | 奥氏体不锈钢 |
TW110141345A TW202219290A (zh) | 2020-11-06 | 2021-11-05 | 奧氏體不鏽鋼 |
PCT/EP2021/080791 WO2022096656A1 (en) | 2020-11-06 | 2021-11-05 | Austenitic stainless steel |
Applications Claiming Priority (1)
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EP20206232.9A EP3995599A1 (de) | 2020-11-06 | 2020-11-06 | Austenitischer rostfreier stahl |
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EP20206232.9A Pending EP3995599A1 (de) | 2020-11-06 | 2020-11-06 | Austenitischer rostfreier stahl |
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US (1) | US20230416889A1 (de) |
EP (1) | EP3995599A1 (de) |
JP (1) | JP2023553258A (de) |
KR (1) | KR20230100735A (de) |
CN (1) | CN116601324A (de) |
AU (1) | AU2021374827A1 (de) |
MX (1) | MX2023005403A (de) |
TW (1) | TW202219290A (de) |
WO (1) | WO2022096656A1 (de) |
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CN115261730B (zh) * | 2022-08-12 | 2023-10-20 | 安徽富凯特材有限公司 | 一种炼镁还原罐用耐热不锈钢及其制备方法 |
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-
2020
- 2020-11-06 EP EP20206232.9A patent/EP3995599A1/de active Pending
-
2021
- 2021-11-05 MX MX2023005403A patent/MX2023005403A/es unknown
- 2021-11-05 TW TW110141345A patent/TW202219290A/zh unknown
- 2021-11-05 WO PCT/EP2021/080791 patent/WO2022096656A1/en active Application Filing
- 2021-11-05 CN CN202180080895.2A patent/CN116601324A/zh active Pending
- 2021-11-05 AU AU2021374827A patent/AU2021374827A1/en active Pending
- 2021-11-05 KR KR1020237018520A patent/KR20230100735A/ko unknown
- 2021-11-05 JP JP2023527394A patent/JP2023553258A/ja active Pending
- 2021-11-05 US US18/035,878 patent/US20230416889A1/en active Pending
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US5824264A (en) * | 1994-10-25 | 1998-10-20 | Sumitomo Metal Industries, Ltd. | High-temperature stainless steel and method for its production |
JPH08239737A (ja) * | 1995-02-28 | 1996-09-17 | Nisshin Steel Co Ltd | 熱間加工性および耐σ脆化性に優れた耐熱用オーステナイト系ステンレス鋼 |
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JP2023553258A (ja) | 2023-12-21 |
US20230416889A1 (en) | 2023-12-28 |
AU2021374827A1 (en) | 2023-06-15 |
TW202219290A (zh) | 2022-05-16 |
WO2022096656A1 (en) | 2022-05-12 |
CN116601324A (zh) | 2023-08-15 |
MX2023005403A (es) | 2023-09-05 |
KR20230100735A (ko) | 2023-07-05 |
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