WO2008041961A2 - Austenitic stainless steel - Google Patents
Austenitic stainless steel Download PDFInfo
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- WO2008041961A2 WO2008041961A2 PCT/US2006/013175 US2006013175W WO2008041961A2 WO 2008041961 A2 WO2008041961 A2 WO 2008041961A2 US 2006013175 W US2006013175 W US 2006013175W WO 2008041961 A2 WO2008041961 A2 WO 2008041961A2
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- WIPO (PCT)
- Prior art keywords
- steel
- austenitic stainless
- manganese
- article
- manufacture
- Prior art date
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- 229910000963 austenitic stainless steel Inorganic materials 0.000 title claims abstract description 42
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 87
- 239000011572 manganese Substances 0.000 claims abstract description 87
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 62
- 239000010959 steel Substances 0.000 claims abstract description 62
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011651 chromium Substances 0.000 claims abstract description 43
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 42
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010936 titanium Substances 0.000 claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 31
- 239000010955 niobium Substances 0.000 claims abstract description 31
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 22
- 239000011733 molybdenum Substances 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- LPXDKRZWFWKMST-UHFFFAOYSA-N aluminum;iron Chemical compound [Al+3].[Fe].[Fe].[Fe] LPXDKRZWFWKMST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 69
- 239000000956 alloy Substances 0.000 claims description 69
- 229910052782 aluminium Inorganic materials 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 33
- 238000012545 processing Methods 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 239000011574 phosphorus Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052726 zirconium Inorganic materials 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- 239000000446 fuel Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 229910001220 stainless steel Inorganic materials 0.000 description 25
- 239000000463 material Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 230000008859 change Effects 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 208000021017 Weight Gain Diseases 0.000 description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 230000004584 weight gain Effects 0.000 description 6
- 235000019786 weight gain Nutrition 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910000914 Mn alloy Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- -1 chromium oxyhydroxides Chemical class 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
Definitions
- the present disclosure relates to austenitic stainless steels. More specifically, the present disclosure relates to austenitic stainless steels having improved creep resistance and/or improved corrosion resistance when subjected to high temperature environments.
- High temperature air presents a particularly corrosive environment. Even more aggressive corrosion conditions can occur if significant water vapor is present.
- energy generation devices such as, for example, gas turbines, steam turbines, and fuel cells, and in heat exchangers and recuperators handling the gas streams used or generated by such energy generation devices, as well as in equipment for treating, processing, or extracting chemicals or minerals at high temperatures. Accordingly, parts of such devices subjected to these conditions have been fabricated from a variety of austenitic stainless steels.
- austenitic stainless steels include various combinations of chromium, nickel, manganese, and other alloying additions. Nevertheless, stainless steels and certain other chromium-bearing heat-resistant alloys are susceptible to attack in high temperature air and in high temperature air containing water vapor. This attack takes two distinct forms. Low-alloy content stainless steels such as, for example, AISI Type 304 (nominally 18 weight percent chromium and 8 weight percent nickel, balance iron), suffer from accelerated oxidation in the presence of water vapor. The slow-growing chromium oxide film is displaced by a thick scale comprised of rapidly growing mixed iron and chromium oxides. The result is rapid metal wastage by conversion to oxide.
- AISI Type 304 nominally 18 weight percent chromium and 8 weight percent nickel, balance iron
- High-alloy content materials such as, for example, superferritic iron-chromium stainless steels and nickel-chromium superalloys, appear to be immune to this form of attack, but have been observed to suffer from weight loss during exposure to water vapor.
- the oxide that forms on certain of the high-alloy content materials is very pure chromium oxide and is susceptible to evaporation through the formation of volatile chromium oxyhydroxides.
- the result of this evaporative loss of chromium to the atmosphere is an abnormally high level of chromium depletion in the metal substrate, and this can lead to a loss of high temperature oxidation resistance.
- the transition between the foregoing corrosion states is relatively complex, with aspects of both states noted in some alloys.
- creep is the undesirable plastic deformation of alloys held for long periods of time at stresses lower than the normal yield strength.
- creep may affect certain structural parts and other parts subject to high stresses and high temperatures in, for example, energy generation devices and related devices, and in equipment and parts for high temperature processing, treating, or extracting chemicals or minerals, or for high temperature treating or processing alloys.
- it is often desirable that parts are formed from a material that has substantial resistance to corrosion in high temperature environments, and that also has substantial creep resistance.
- the alloying element manganese has been shown play a role in mitigating the effects of chromium oxide vaporization.
- Many stainless steel specifications include manganese at levels limited to 2 weight percent or less, with no required minimum level.
- the manganese in these steels is not an intentional alloying addition but, instead, is included in the steel as an incidental ingredient derived from the scrap starting materials.
- One austenitic stainless steel adapted for use in high temperature, high water vapor content environments that includes an appreciable allowance for incidental manganese is NF709 alloy.
- NF709 alloy has been available from Nippon Steel Corporation in forms including of seamless tubing for boiler applications.
- the composition of NF709 alloy which is provided in the Nippon Steel publication "Quality and Properties of NF709 Austenitic Stainless Steel for Boiler Tubing Applications," is shown in Table 1. The published composition specifies a manganese limit of 1.5 weight percent, with no specified minimum.
- the typical commercial manganese content is approximately 1 weight percent.
- Certain other austenitic stainless steels are also shown in Table 1. Elemental concentrations throughout the present description are weight percentages based on total alloy weight unless otherwise indicated. "NS" in Table 1 indicates that the particular UNS specification does not specify a concentration for the element.
- Type 201 stainless steel is similar to standard 18 chromium-8 nickel stainless steels, but with a fraction of nickel replaced with manganese to lower alloy cost.
- Type 201 alloy does not possess sufficient creep and oxidation resistance for use at elevated temperatures.
- Higher- alloyed materials such as the NITRONIC ® family of alloys, Esshete 1250 alloy, and 21-6-9 alloy (UNS S21900), include low nickel levels (about 11 weight percent maximum) and significant manganese levels (5-10 weight percent), and are typically designed for high creep strength and moderate environmental resistance.
- Commercially available heat-resistant stainless steels such as AISI Types 309S and 310S generally include manganese at levels up to about 2 weight percent. These alloys are somewhat deficient in terms of metallurgical stability, which may be tied to their basic compositions inasmuch as the nickel-to-chromium ratio for these two grades results in the formation of significant amounts of brittle phases at typical use temperatures.
- austenitic stainless steels having improved high temperature creep resistance and/or resistance to corrosive attack in high temperature air and/or in high temperature air containing appreciable levels of water vapor.
- stainless steels exhibiting substantial corrosion resistance in high temperature air including water vapor could be advantageously employed in, for example, parts of energy generation devices including, for example, gas turbines, steam turbines, and fuel cells, which are subjected to highly corrosive high temperature-high water vapor content environments.
- Such parts include heat exchangers, recuperators, tubing, pipe, and certain structural parts.
- Alloys exhibiting substantial corrosion resistance in high temperature air also may be advantageously applied in certain devices for high temperature processing, treatment, or extraction of chemicals or minerals, or for high temperature processing or treatment of alloys.
- Stainless steels exhibiting both substantial high temperature creep resistance as well as significant corrosion resistance could be advantageously adapted for use in parts of the foregoing devices that are subjected to high stresses.
- austenitic stainless steels having improved high temperature creep resistance and/or improved resistance to corrosion when exposed to a high temperature air environment.
- high temperature refers to temperatures in excess of about 100 0 F (about 37.8°C).
- an austenitic stainless steel is provided including: 0.05 to 0.2 carbon; 0.08 to 0.2 nitrogen; 20 to 23 chromium; 25 to 27 nickel; 1 to 2 molybdenum; greater than 1.5 to 4.0 manganese; 0.20 to 0.75 niobium; up to 0.1 titanium; iron; and incidental impurities.
- the manganese content of the steel is at least 1.6 up to 4.0 weight percent.
- the austenitic stainless steel further includes one or more of the following elements: greater than 0 to 0.50 silicon; greater than 0 to 0.30 aluminum; greater than 0 to 0.02 sulfur; greater than 0 to 0.05 phosphorus; greater than 0 to 0.1 zirconium; and greater than 0 to 0.1 vanadium.
- the titanium and/or aluminum content of the steel is no greater than 0.1 weight percent.
- an austenitic stainless steel includes: 0.05 to 0.2 carbon; 0.08 to 0.2 nitrogen; 20 to 23 chromium; 25 to 27 nickel; 1 to 2 molybdenum; greater than 1.5 to 4.0 manganese; 0.20 to 0.75 niobium; up to 0.1 titanium; up to 0.50 silicon; up to 0.30 aluminum; up to 0.02 sulfur; up to 0.05 phosphorus; up to 0.1 zirconium; up to 0.1 vanadium; iron; and incidental impurities.
- the manganese content of the steel is at least 1.6 up to 4.0 weight percent.
- the titanium and/or aluminum content of the steel is no greater than 0.1 weight percent.
- an austenitic stainless steel is provided that consists essentially of the following: 0.05 to 0.2 carbon; 0.08 to 0.2 nitrogen; 20 to 23 chromium; 25 to 27 nickel; 1 to 2 molybdenum; greater than 1.5 to 4.0 manganese; 0.20 to 0.75 niobium; up to 0.1 titanium; up to 0.50 silicon; up to 0.30 aluminum; up to 0.02 sulfur; up to 0.05 phosphorus; up to 0.1 zirconium; up to 0.1 vanadium; iron; and incidental impurities.
- the manganese content of the steel is at least 1.6 up to 4.0 weight percent.
- an austenitic stainless steel that consists of: 0.05 to 0.2 carbon; 0.08 to 0.2 nitrogen; 20 to 23 chromium; 25 to 27 nickel; 1 to 2 molybdenum; greater than 1.5 to 4.0 manganese; 0.20 to 0.75 niobium; up to 0.1 titanium; up to 0.50 silicon; up to 0.30 aluminum; up to 0.02 sulfur; up to 0.05 phosphorus; up to 0.1 zirconium; up to 0.1 vanadium; iron; and incidental impurities.
- the manganese content of the steel is at least 1.6 up to 4.0 weight percent.
- Another aspect of the present disclosure is directed to an austenitic stainless steel including, in weight percentages based on total weight of the steel: 0.05 to 0.2 carbon; 0.08 to 0.2 nitrogen; 20 to 23 chromium; 25 to 27 nickel; 1 to 2 molybdenum; up 4.0 manganese; 0.20 to 0.75 niobium; at least one of no greater than 0.1 titanium and no greater than 0.1 aluminum; iron; and incidental impurities.
- a further aspect of the present disclosure is directed to an austenitic stainless steel consisting essentially of, in weight percentages based on total weight of the steel: 0.05 to 0.2 carbon; 0.08 to 0.2 nitrogen; 20 to 23 chromium; 25 to 27 nickel; 1 to 2 molybdenum; up to 4.0 manganese; 0.20 to 0.75 niobium; at least one of no greater than 0.1 titanium and no greater than 0.1 aluminum; up to 0.50 silicon; up to 0.02 sulfur; up to 0.05 phosphorus; up to 0.1 zirconium; up to 0.1 vanadium; iron; and incidental impurities.
- the steel includes at least 1.5 up to 4.0 weight percent manganese, while in other embodiments the steel includes 1.6 up to 4.0 weight percent manganese.
- an austenitic stainless consisting of, in weight percentages based on total weight of the steel: 0.05 to 0.2 carbon; 0.08 to 0.2 nitrogen; 20 to 23 chromium; 25 to 27 nickel; 1 to 2 molybdenum; up to 4.0 manganese; 0.20 to 0.75 niobium; at least one of no greater than 0.1 titanium and no greater than 0.1 aluminum; up to 0.50 silicon; up to 0.02 sulfur; up to 0.05 phosphorus; up to 0.1 zirconium; up to 0.1 vanadium; iron; and incidental impurities.
- the steel includes at least 1.5 up to 4.0 weight percent manganese, while in other embodiments the steel includes 1.6 up to 4.0 weight percent manganese.
- an article of manufacture including an austenitic stainless steel having a composition according to the present disclosure.
- the article of manufacture include, for example, energy generation devices and parts of such devices.
- the article of manufacture may be selected from a gas turbine, a steam turbine, a fuel cell, a heat exchanger, a recuperator, a tube, a pipe, a structural part, and other parts for any of those devices.
- Other examples of the article of manufacture include equipment or piping, tubing, and other parts for equipment for high temperature processing, treatment, or extraction of chemicals and minerals, or for high temperature processing or treatment of alloys
- Figure 1 is a plot of weight change over time for alloy samples exposed at 1300 0 F (704 0 C) in air containing 10% water vapor
- Figure 2 is a plot of weight change over time for alloy samples exposed at 1400 0 F (76O 0 C) in air containing 7% water vapor;
- Figure 3 is a plot of weight change over time for alloy samples exposed at 1500 0 F (815°C) in air containing 7% water vapor;
- Figure 4(a) and 4(b) are micrographs of oxide scale formed on alloy samples exposed to high temperature environments including water vapor;
- Figure 5 is a graph of oxide composition, measured as a molar ratio of MnO to O 2 O 3 , for several alloys subjected to high temperature environments including water vapor;
- Figure 6 is a plot of chromium content of two alloy samples as a function of depth into the sample;
- Figure 7 is a plot of chromium content of two alloy samples as a function of depth into the sample
- Figure 8 is a graph of oxide composition, measured as a molar ratio of MnO to Cr 2 ⁇ 3, for high manganese and low manganese samples subjected to high temperature environments including 7% water vapor;
- Figure 9 is a plot of weight change over time for alloy samples exposed at 1400°F (760 0 C) in air containing 10% water vapor.
- any numerical range recited herein is intended to include the range boundaries and all sub-ranges subsumed therein.
- a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
- certain austenitic stainless steels have been used in articles and parts exposed to high temperature air or to high temperature air containing significant water vapor.
- Parts subjected to such conditions include, for example, affected parts of energy generation devices, such as gas turbines, steam turbines, and fuel cells, and heat exchangers and recuperators, and in equipment and parts for high temperature processing, treatment, or extraction of chemicals or minerals, or high temperature processing or treatment of alloys.
- energy generation devices such as gas turbines, steam turbines, and fuel cells, and heat exchangers and recuperators
- These steels still suffer from a level of corrosive attack when subjected over time to these conditions. Accordingly, the present inventors undertook to determine whether certain modified austenitic stainless steel chemistries further improved corrosion resistance in high temperature environments.
- the inventors determined that alloys containing 1.5 weight percent or less manganese are subject to oxide scale evaporation and subsequent degradation in air containing water vapor.
- the inventors' work focused on certain novel austenitic stainless steel chemistries including more than 1.5 weight percent manganese, along with appreciable levels of chromium and nickel.
- the present inventors concluded that an austenitic stainless steel having the broad composition and, more preferably, the nominal composition listed in Table 2 would have substantial resistance to chromium oxide scale evaporation in high temperature air environments and in high temperature air environments including water vapor.
- the proposed alloy's manganese content is controlled at a minimum level, which was found to significantly improve resistance to high temperature corrosive attack.
- Table 3 provides information on several alloys evaluated during the testing. All heats were melted and subsequently rolled to foil gauge. Heats 1 and 3 were lab heats, heat 2 was prepared as a pilot coil, and heat 4 was a plant heat prepared as a production coil. Heats 1 , 3, and 4 were prepared with an aim of 1.0 weight percent manganese, and heat 2 was prepared with an aim of 1.6 weight percent manganese. Table 3
- Figure 2 shows weight change over time for samples of high manganese (heat 2) and the low manganese (heat 4) alloys when the samples were exposed at 1400°F (76O 0 C) in air containing 7% water vapor.
- the samples exhibited significantly different oxidation kinetics under these conditions.
- the high manganese sample gained weight rapidly during the initial portion of the test, but then the weight gain slowed significantly. After completion of the 5,000 hour test, the two samples exhibited essentially identical weight gain.
- Figure 3 shows weight change over time for samples of high manganese (heat 2) and the low manganese (heat 4) alloys when the samples were exposed at 1500 0 F (815°C) in air containing 7% water vapor.
- the curve shows that the lower manganese sample exhibited significant oxide scale evaporation during the test period.
- the higher manganese alloy did not exhibit the same weight change over the limited test exposure.
- the low manganese material did not exhibit manganese saturation (i.e., a MnO/Cr 2 O 3 ratio of 1.0) at the scale/gas interface at 1300 0 F (704 0 C) and was borderline saturated at 1400 0 F (760 0 C). Achieving manganese saturation in the spinel is believed to be important in providing resistance to evaporation.
- FIG. 6 plots the chromium concentration as a function of depth into the sample surface for high manganese and low manganese samples, from heats 2 and 4, respectively, exposed for 5,000 hours at 1300 0 F (704 0 C) in air containing 10% water vapor.
- the depletion observed for the low manganese sample is significantly greater in terms of chromium concentration directly adjacent the scale/metal interface Depth of depletion between the samples does not appear to be noticeably different.
- FIG. 7 is a plot of chromium concentration as a function of depth into the sample surface for high manganese and low manganese samples, heats 2 and 4, respectively, exposed for 5,000 hours at 1400 0 F (760 0 C) in air containing 7% water vapor.
- chromium depletion for the low manganese sample was significantly greater than for the high manganese sample at the scale/metal interface.
- Figure 8 is a graph showing oxide composition, measured as a molar ratio of MnO to Cr 2 O 3 , using XEDS in the SEM (semi-quantitative) for high manganese and low manganese samples, derived from heats 2 and 4, respectively, subjected to high temperature air containing 7% water vapor. The measurements were taken at the scale/alloy interface and the scale/gas interface. The evaluations conducted after exposure to 1300 0 F (704 0 C) and to 1400 0 F (760°C) air were conducted after about 5,000 hours of exposure time. Those conducted after exposure at 1500 0 F (815°C) were performed after about 3,000 hours of exposure time.
- the low manganese material did not exhibit manganese saturation ⁇ i.e., a MnO/Cr 2 O 3 ratio of 1.0) at the scale/gas interface at 1300°F (704°C) and at 1500 0 F (815 0 C), and was borderline saturated at 1400°F (760 0 C).
- Figure 9 is a plot of sample weight change over time for samples of the alloys of heat 2 (1.61 weight percent manganese), heat 5 (2.04 weight percent manganese), and heat 6 (3.82 weight percent manganese) exposed at 1400 0 F (760 0 C) in air containing 7% water vapor.
- the results indicate that higher manganese levels produce higher initial weight gain through oxide scale formation. While the weight gains shown in Figure 9 did not appear to be problematic, it is believed that higher manganese levels, above about 4 weight percent, would result in further scale formation and weight gains, and the consequent undesirable result of spallation of the material.
- Additional heats 7 through 11 in Table 5 were prepared. The heats included less than 0.1 weight percent titanium. Heats 7, 8 and 11 also included less than 0.1 weight percent aluminum.
- austenitic stainless steels subjected to stress at high temperature for prolonged periods can be subject to creep.
- Most austenitic stainless steels include relatively minor levels of titanium and aluminum to facilitate deoxidation of the molten metal during melting and casting. These elements also are precipitated as nitrides and, possibly, intermetallic phases in the solid state. These precipitated phases are very difficult or impractical to dissolve during processing. Excessive nitride formation will have the effect of reducing the level of nitrogen in solid solution, which will reduce the creep strength of the alloy. Nitrides and intermetallic phases also can make processing more difficult, particularly when the steel is formed by being folded or stamped into part shapes.
- a preferred chemistry for the austenitic stainless steels of the present disclosure includes at least one of no greater than 0.1 weight percent titanium and no greater than 0.1 weight percent aluminum. More preferably, to better enhance creep resistance and formability, the austenitic stainless steels of the present disclosure includes no greater than 0.1 weight percent titanium and no greater than 0.1 weight percent aluminum.
- an austenitic stainless having the investigated chemistries and including manganese at levels greater than 1.5 weight percent and up to about 4 weight percent should exhibit advantageous resistance to high temperature attack in air, which may include significant water vapor, and without suffering from excessive scale formation and spallation. More specifically, the broad and nominal alloy compositions shown in Table 2 are proposed as austenitic stainless steels with substantial resistance to corrosive attack in high temperature air and in high temperature air including water vapor.
- a preferred manganese level is at least 1.6 up to about 4 weight percent, and a more preferred manganese level is at least 1.6 up to about 2.0 weight percent manganese.
- An additional proposed alloy chemistry having improved creep resistance and improved formability has the general chemistry shown in Table 2, but includes no greater than 0.1 weight percent titanium and/or no greater than 0.1 weight percent aluminum.
- the expected improvement in creep resistance resulting from the limits on titanium and/or aluminum content is not necessarily tied to the improved high temperature corrosion resistance provided by controlling the manganese content to the range of greater than 1.5 weight percent up to about 4 weight percent.
- the manganese content of the alloy proposed herein having improved creep resistance and formability may be any level up to about 4.0 weight percent. Accordingly, the alloy in the following Table 6 should exhibit advantageous creep resistance and formability properties, and a preferred chemistry includes no greater than 0.1 weight percent titanium and no greater than 0.1 weight percent aluminum.
- At least one of Ti and Al is no greater than 0.1.
- An alloy exhibiting advantageous high temperature creep resistance, improved formability, and advantageous resistance to corrosive attack in high temperature air including water vapor would have the composition shown in Table 6 and wherein the composition is further controlled such that the manganese content is greater then 1.5 up to about 4.0 weight percent, preferably is at least 1.6 up to about 4.0 weight percent, and more preferably is at least 1.6 up to about 2.0 weight percent.
- Such an alloy could be advantageously applied in making, for example, structural parts and other parts of the previously mentioned energy generation devices and processing, treatment, or extraction devices that are both subjected to stress and exposed to high temperature air including water vapor.
- niobium to carbon ratio in the alloys satisfies the following formula: 0.7 ⁇ 0.13(niobium/carbon) ⁇ 1.0, wherein the niobium and carbon contents in the formula are expressed in atom percentages.
- Heats of the novel corrosion resistant austenitic stainless steels disclosed herein may be made by conventional means, such as by the conventional technique of vacuum melting scrap and other feed materials.
- the resulting heats may be processed by conventional techniques into billets, slabs, plates, coils, sheets, and other intermediate articles, and then further processed into final articles of manufacture.
- the enhanced formability of embodiments of alloys within the present disclosure including no greater than 0.1 weight percent of titanium and/or no greater than 0.1 weight percent aluminum allows flat mill products (such as strip, sheet, plate, coil, and the like) formed from the alloys to be further processed into articles having relatively complicated shapes. This characteristic of the alloys is an advantage relative to NF709 alloy, which has more limited formability and has commonly only been processed by extrusion into seamless pipe.
- novel austenitic stainless steels according to the present disclosure may be used in any suitable application and environment, but the alloys are particularly suited for use in equipment and parts subjected for extended periods to high temperature, or to both high temperature and significant water vapor.
- the creep resistance and/or high temperature corrosion resistance of the alloys disclosed herein makes them particularly suitable for use in: tubing, piping, structural parts, and other parts of equipment adapted for high temperature processing, treatment, or extraction of chemicals or minerals, or high temperature processing or treatment of alloys; tubing, piping, structural parts, and other parts of energy generation devices such as, for example, gas turbines, steam turbines, and fuel cells; and parts of heat exchangers, recuperators, and other equipment handling gas streams used or generated by energy generation devices.
- Other applications for the alloys disclosed herein will be apparent to those of ordinary skill upon considering the present description of the alloys.
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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EP06851605.3A EP1941070B1 (de) | 2005-06-03 | 2006-04-07 | Austenitischer edelstahl |
JP2008537684A JP5068760B2 (ja) | 2005-06-03 | 2006-04-07 | オーステナイト系ステンレス鋼 |
BRPI0607922-9A BRPI0607922B1 (pt) | 2005-06-03 | 2006-04-07 | Austenetic stainless steel and austenetic stainless steel product |
CN2006800183434A CN101218365B (zh) | 2005-06-03 | 2006-04-07 | 奥氏体不锈钢 |
CA2603526A CA2603526C (en) | 2005-06-03 | 2006-04-07 | Austenitic stainless steel |
KR1020137008688A KR101412893B1 (ko) | 2005-06-03 | 2006-04-07 | 오스테나이트 스테인리스 스틸 |
ES06851605.3T ES2551868T3 (es) | 2005-06-03 | 2006-04-07 | Acero inoxidable austenítico |
AU2006344097A AU2006344097B2 (en) | 2005-06-03 | 2006-04-07 | Austenitic stainless steel |
DK06851605.3T DK1941070T3 (en) | 2005-06-03 | 2006-04-07 | Austenitisk rustfrit stål |
NO20076693A NO20076693L (no) | 2005-06-03 | 2007-12-28 | Austenittisk rustfritt stal |
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US68740005P | 2005-06-03 | 2005-06-03 | |
US60/687,400 | 2005-06-03 | ||
US11/270,279 | 2005-11-09 | ||
US11/270,279 US20060275168A1 (en) | 2005-06-03 | 2005-11-09 | Austenitic stainless steel |
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WO2008041961A2 true WO2008041961A2 (en) | 2008-04-10 |
WO2008041961A3 WO2008041961A3 (en) | 2008-05-29 |
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PCT/US2006/013175 WO2008041961A2 (en) | 2005-06-03 | 2006-04-07 | Austenitic stainless steel |
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US (1) | US20060275168A1 (de) |
EP (1) | EP1941070B1 (de) |
JP (1) | JP5068760B2 (de) |
KR (2) | KR20080053437A (de) |
AU (1) | AU2006344097B2 (de) |
BR (1) | BRPI0607922B1 (de) |
DK (1) | DK1941070T3 (de) |
ES (1) | ES2551868T3 (de) |
NO (1) | NO20076693L (de) |
RU (1) | RU2429308C2 (de) |
WO (1) | WO2008041961A2 (de) |
Families Citing this family (9)
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EP1612395A4 (de) * | 2003-03-31 | 2010-08-04 | Hitachi Metals Ltd | Kolben für einen verbrennungsmotor |
JP2010116622A (ja) * | 2008-11-14 | 2010-05-27 | Nisshin Steel Co Ltd | ヒートパイプ用フェライト系ステンレス鋼および鋼板並びにヒートパイプおよび高温排熱回収装置 |
ES2351281B1 (es) * | 2009-02-03 | 2011-09-28 | Valeo Termico, S.A. | Intercambiador de calor para gases, en especial de los gases de escape de un motor. |
US8182963B2 (en) * | 2009-07-10 | 2012-05-22 | GM Global Technology Operations LLC | Low-cost manganese-stabilized austenitic stainless steel alloys, bipolar plates comprising the alloys, and fuel cell systems comprising the bipolar plates |
KR101614622B1 (ko) * | 2014-12-26 | 2016-04-22 | 주식회사 포스코 | 연료전지용 오스테나이트계 스테인리스강 |
EP3208029B1 (de) * | 2016-02-17 | 2021-01-27 | General Electric Technology GmbH | Innengehäusekomponente einer dampfturbine und reparaturverfahren dafür |
US20210292876A1 (en) * | 2016-10-03 | 2021-09-23 | Nippon Steel Corporation | Austenitic Heat Resistant Alloy and Welded Joint Including the Same |
EP3682156A1 (de) * | 2017-09-14 | 2020-07-22 | Sandvik Materials Technology Deutschland GmbH | System zur übertragung von flüssigem wasserstoff |
DE102021211652A1 (de) * | 2021-10-15 | 2023-04-20 | Siemens Energy Global GmbH & Co. KG | Austenitlegierung, Rohteil und Bauteil sowie Verfahren |
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DE3018537A1 (de) * | 1979-05-17 | 1980-11-27 | Daido Steel Co Ltd | Kontrollierte einschluesse enthaltender automatenstahl und verfahren zu seiner herstellung |
JPS59173249A (ja) * | 1983-03-19 | 1984-10-01 | Nippon Steel Corp | オ−ステナイト系耐熱合金 |
JPS60230966A (ja) * | 1984-04-27 | 1985-11-16 | Sumitomo Metal Ind Ltd | 塩化物の存在する高温乾食環境用鋼 |
JPS61183452A (ja) * | 1985-02-09 | 1986-08-16 | Sumitomo Metal Ind Ltd | 耐CaSO↓4付着高温腐食性高マンガン鋼 |
JPS6254067A (ja) * | 1985-09-02 | 1987-03-09 | Sumitomo Metal Ind Ltd | 流動床ボイラ−部材用Si含有鋼 |
US4853185A (en) * | 1988-02-10 | 1989-08-01 | Haynes International, Imc. | Nitrogen strengthened Fe-Ni-Cr alloy |
JPH01252757A (ja) * | 1988-03-31 | 1989-10-09 | Nkk Corp | 耐溶融炭酸塩腐食性に優れたFe基合金 |
DE3825634C2 (de) * | 1988-07-28 | 1994-06-30 | Thyssen Stahl Ag | Verfahren zur Erzeugung von Warmbad oder Grobblechen |
JPH05148587A (ja) * | 1991-11-26 | 1993-06-15 | Sumitomo Metal Ind Ltd | ごみ焼却ボイラ伝熱管用高耐食合金 |
JPH0826439B2 (ja) * | 1991-07-05 | 1996-03-13 | 新日本製鐵株式会社 | 高温腐食特性に優れたオーステナイト系ステンレス鋼 |
JPH06330226A (ja) * | 1993-05-19 | 1994-11-29 | Nippon Steel Corp | 耐高温腐食特性に優れた複層鋼材およびその製造方法 |
JP4190617B2 (ja) * | 1998-06-23 | 2008-12-03 | 大平洋金属株式会社 | ステンレス鋼の熱間圧延板を製造する方法 |
JP2000129403A (ja) * | 1998-10-26 | 2000-05-09 | Hitachi Ltd | 高温強度と耐食性に優れたオーステナイト系耐熱合金及び用途 |
SE516137C2 (sv) * | 1999-02-16 | 2001-11-19 | Sandvik Ab | Värmebeständigt austenitiskt stål |
US6352670B1 (en) * | 2000-08-18 | 2002-03-05 | Ati Properties, Inc. | Oxidation and corrosion resistant austenitic stainless steel including molybdenum |
JP3689009B2 (ja) * | 2001-02-27 | 2005-08-31 | 株式会社日立製作所 | 高耐食性高強度オーステナイト系ステンレス鋼とその製法 |
JP2003041349A (ja) * | 2001-08-01 | 2003-02-13 | Nisshin Steel Co Ltd | 電気抵抗材料 |
US7258752B2 (en) * | 2003-03-26 | 2007-08-21 | Ut-Battelle Llc | Wrought stainless steel compositions having engineered microstructures for improved heat resistance |
JP2005023353A (ja) * | 2003-06-30 | 2005-01-27 | Sumitomo Metal Ind Ltd | 高温水環境用オーステナイトステンレス鋼 |
-
2005
- 2005-11-09 US US11/270,279 patent/US20060275168A1/en not_active Abandoned
-
2006
- 2006-04-07 JP JP2008537684A patent/JP5068760B2/ja not_active Expired - Fee Related
- 2006-04-07 KR KR1020077026082A patent/KR20080053437A/ko active Application Filing
- 2006-04-07 AU AU2006344097A patent/AU2006344097B2/en not_active Ceased
- 2006-04-07 EP EP06851605.3A patent/EP1941070B1/de not_active Not-in-force
- 2006-04-07 WO PCT/US2006/013175 patent/WO2008041961A2/en active Application Filing
- 2006-04-07 ES ES06851605.3T patent/ES2551868T3/es active Active
- 2006-04-07 BR BRPI0607922-9A patent/BRPI0607922B1/pt not_active IP Right Cessation
- 2006-04-07 KR KR1020137008688A patent/KR101412893B1/ko active IP Right Grant
- 2006-04-07 RU RU2007149031/02A patent/RU2429308C2/ru not_active IP Right Cessation
- 2006-04-07 DK DK06851605.3T patent/DK1941070T3/en active
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2007
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Also Published As
Publication number | Publication date |
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KR101412893B1 (ko) | 2014-06-26 |
KR20080053437A (ko) | 2008-06-13 |
BRPI0607922B1 (pt) | 2017-09-12 |
WO2008041961A3 (en) | 2008-05-29 |
BRPI0607922A2 (pt) | 2009-10-20 |
JP5068760B2 (ja) | 2012-11-07 |
EP1941070A2 (de) | 2008-07-09 |
US20060275168A1 (en) | 2006-12-07 |
AU2006344097B2 (en) | 2011-07-07 |
EP1941070B1 (de) | 2015-09-30 |
RU2429308C2 (ru) | 2011-09-20 |
JP2008545889A (ja) | 2008-12-18 |
KR20130043247A (ko) | 2013-04-29 |
ES2551868T3 (es) | 2015-11-24 |
AU2006344097A1 (en) | 2008-04-10 |
DK1941070T3 (en) | 2016-01-11 |
NO20076693L (no) | 2008-02-29 |
RU2007149031A (ru) | 2009-07-20 |
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