US20020110476A1 - Heat and corrosion resistant cast stainless steels with improved high temperature strength and ductility - Google Patents
Heat and corrosion resistant cast stainless steels with improved high temperature strength and ductility Download PDFInfo
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- US20020110476A1 US20020110476A1 US09/736,741 US73674100A US2002110476A1 US 20020110476 A1 US20020110476 A1 US 20020110476A1 US 73674100 A US73674100 A US 73674100A US 2002110476 A1 US2002110476 A1 US 2002110476A1
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- 229910001220 stainless steel Inorganic materials 0.000 title description 11
- 230000007797 corrosion Effects 0.000 title description 5
- 238000005260 corrosion Methods 0.000 title description 5
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 54
- 239000000956 alloy Substances 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000010955 niobium Substances 0.000 claims description 30
- 229910052758 niobium Inorganic materials 0.000 claims description 29
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims 2
- 229910001566 austenite Inorganic materials 0.000 abstract description 7
- 230000001965 increasing effect Effects 0.000 abstract description 7
- 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 abstract description 6
- 239000002244 precipitate Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000006104 solid solution Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 150000001247 metal acetylides Chemical class 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract 3
- 238000005266 casting Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 150000004763 sulfides Chemical class 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- -1 niobium carbides Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005382 thermal cycling Methods 0.000 description 4
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- 229910001141 Ductile iron Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- QISGROBHHFQWKS-UHFFFAOYSA-N [C].[Nb] Chemical compound [C].[Nb] QISGROBHHFQWKS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- VCTOKJRTAUILIH-UHFFFAOYSA-N manganese(2+);sulfide Chemical class [S-2].[Mn+2] VCTOKJRTAUILIH-UHFFFAOYSA-N 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- SAOHCOFTVLEOCB-UHFFFAOYSA-K tris(2,4,6-tribromophenoxy)bismuthane Chemical compound [Bi+3].[O-]C1=C(Br)C=C(Br)C=C1Br.[O-]C1=C(Br)C=C(Br)C=C1Br.[O-]C1=C(Br)C=C(Br)C=C1Br SAOHCOFTVLEOCB-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- 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
- This invention relates generally to cast steel alloys of the CF8C and CN-12 types with improved strength and ductility at high temperatures. More particularly, this invention relates to CN-12 and CF8C stainless steel alloys and articles made therefrom having excellent high temperature strength, creep resistance and aging resistance, with reduced niobium carbides, manganese sulfides, and chrome carbides along grain and substructure boundaries.
- CN-12 cast austenitic stainless steel
- CN-12 provides adequate strength and aesthetics for automobiles for the anticipated life in comparison to cast iron, but lacks the improved creep resistance that is optimal when mounting turbo chargers (70 lbs.) onto diesel exhaust manifolds.
- CN-12 austenitic stainless steel includes about 25 wt. % chromium, 13 wt. % nickel, smaller amounts of carbon, nitrogen, niobium, silicon, manganese, molybdenum and sulfur.
- the addition of sulfur is considered essential or desirable for machineability from the cast material.
- the amount of added sulfur ranges from 0.11 wt. % to 0.15 wt. %.
- Currently-available cast austenitic stainless CF8C steels include from 18 wt. % to 21 wt. % chromium, 9 wt. % to 12 wt. % nickel and smaller amounts of carbon, silicon, manganese, phosphorous, sulfur and niobium.
- CF8C typically includes about 2 wt. % silicon, about 1.5 wt. % manganese and about 0.04 wt. % sulfur.
- CF8C is a niobium stabilized grade of austentic stainless steel most suitable for aqueous corrosion resistance at temperatures below 500° C. In the standard form CF8C has inferior strength compared to CN12 at temperatures above 600° C.
- a stainless steel alloy contains from about 0.5 wt. % to about 10 wt. % manganese and less than about 0.10 wt. % sulfur.
- a stainless steel alloy contains from about 0.03 wt. % sulfur or less, from about 2 wt. % to about 5 wt. % manganese and niobium and carbon in a niobium:carbon wt. % ratio ranging from about 3.5 to about 5.0.
- a stainless steel that contains from about 2 wt. % to about 5 wt. % manganese, less than about 0.03 wt. % sulfur and about 0.8 wt. % silicon or less.
- the present invention is directed toward alloys of both the CN-12 and CF8C types.
- Table 1 presents the optimal and permissible minimum and maximum ranges for the compositional elements of CN-12 and CF8C stainless steel alloys made in accordance with the present invention. Boron, aluminum and copper may also be added.
- allowable ranges for cobalt, vanadium, tungsten and titanium may not significantly alter the performance of the resulting material. Specifically, based on current information, that cobalt may range from 0 to 5 wt. %, vanadium may range from 0 to 3 wt. %, tungsten may range from 0 to 3 wt. % and titanium may range from 0 to 0.2 wt.
- Table 2 includes the compositions of ten experimental alloys A-J in comparison with a standard CN-12 and CF8C alloys TABLE 2 Composition by Weight Percent Element CN-12 A B C D E F G H CF8C I J Chromium 24 53 24.87 23 84 23.92 23.84 24.28 23.9 24.00 23.96 19.16 19.14 19.08 Nickel 12.91 13.43 15.34 15.33 15.32 15.67 15.83 15.69 15.90 12.19 12.24 12.36 Carbon 0 40 0.43 0.31 0.31 0.20 0.41 0.37 0.40 0.29 0.08 0.09 0.08 Silicon 0 9 0.82 0.7 0.7 0.68 0.66 0.66 0.66 0.66 0.62 0.67 Manganese 0.82 0.90 1.83 1.85 1.84 1.86 4.87 4.86 4.82 1.89 1.80 4.55 Phosphorous 0.019 0.036 0.037 0.038 0.040 0.035 0.033 0.032 0.032 0.004 0.004 0.005 Sulfur 0.139 0.002 0.002 0.003 0.003 0.003
- the critical testing conditions for CN-12 of 850° C. and 110 MPa were chosen because 850° C. is approximately the highest exhaust temperature observed currently and this is the temperature at which the most harmful precipitates like sigma form rapidly.
- the stress, 110 MPa was chosen to provide an accelerated test lasting from 10 to 100 hours that would equate to much longer durability at lower stresses and temperatures during engine service. Removing the sulfur improved the room and elevated temperature ductility, tensile strength, yield strength, creep life and creep ductility for the same carbon content. By lowering the carbon content to 0.30 wt. %, creep life and tensile strength were only slightly lowered while creep ductility was improved significantly. By lowering the carbon content further to 0.20 wt. %, room or elevated temperature strength did not decrease significantly, but creep life was reduced by 60 percent.
- a solution annealing treatment was applied to each alloy to analyze the effect of a more uniform distribution of carbon.
- the alloys were held at 1200° C. for one hour. They were then air cooled rather than quenched to allow the small niobium carbide and chromium carbide precipitates to nucleate in the matrix during cooling.
- the resulting microstructure was found to be very similar to the as-cast (AS) structure except for the formation of small precipitates.
- AS as-cast
- the solution annealing treatment lowered creep life significantly while increasing creep ductility, therefore proving that the strategy to optimize the as-cast microstructures was best as well as most cost effective.
- Alloys A-H and the unmodified CN-12 base alloy were aged at 850° C. for 1,000 hours to study the effects of aging on the microstructure and mechanical properties which are summarized in Table 5.
- the alloys with 0.3 wt. % carbon (alloys B and C) showed the presence of platelets near the grain boundary structure.
- the 0.2 wt. % carbon alloy (D) showed an even higher amount of the platelets.
- the platelets are identified as sigma in the ASM Handbook, Vol. 9, 9 th Ed. (1986). SEM/XEDS/TEM analysis confirmed that the platelets had a concentration consistent with sigma. (FeCr).
- Manganese is an effective austenite stabilizer, like nickel, but is about one tenth the cost of nickel.
- the positive austenite stabilizing potential of manganese must be balanced with its possible affects on oxidation resistance at a given chromium level relative to nickel, which nears maximum effectiveness around 5 wt. % and therefore addition of manganese in excess of 10 wt. % is not recommended.
- Manganese in an amount of less than 2 wt. % may not provide the desired stabilizing effect.
- Manganese also dramatically increases the solubility of carbon and nitrogen in austenite. This effect is especially beneficial because dissolved nitrogen is an austenite stabilizer and also improves strength of the alloy when in solid solution without decreasing ductility or toughness.
- Manganese also improves strength ductility and toughness, and manganese and nitrogen have synergistic effects.
- niobium:carbon ratio reduces excessive and continuous networks of coarse niobium carbides (NbC) or finer chrome carbides (M 23 C 6 ) along the grain or substructure boundaries (interdentritic boundaries and cast material) that are detrimental to the mechanical performance of the material at high temperatures.
- niobium and carbon are present in amounts necessary to provide high-temperature strength (both in the matrix and at the grain boundaries), but without reducing ductility due to cracking along boundaries with continuous or nearly-continuous carbides.
- Carbon can be present in CN-12 alloys in an amount ranging from 0.2 wt. % to about 0.5 wt. % and niobium can be present in CN-12 alloys in an amount ranging from about 1.0 wt. % to about 2.5 wt. %.
- Nitrogen can be present in an amount ranging from 0.1 wt. % to about 0.5 wt. % in CN-12 alloys.
- the presence of nitride precipitates is reduced by adjusting the levels and enhancing the solubility of nitrogen while lowering the chromium:nickel ratio.
- the niobium to carbon ratio can range from about 3 to about 5, the nitrogen content can range from about 0.10 wt. % to about 0.5 wt. %, the carbon content can range from about 0.2 wt. % to about 0.5 wt. %, the niobium content can range from about 1.0 wt. % to about 2.5wt. %, the silicon content can range from about 0.2 wt. % to about 3.0 wt. %, the chromium content can range from about 18 wt. % to about 25 wt. %, the molybdenum content can be limited to about 0.5 wt.
- the manganese content can range from about 0.5 wt. % to about 1.0 wt. %
- the sulfur content can range from about 0 wt. % to about 0.1 wt. %
- the sum of the carbon and nitrogen content can range from 0.4 wt. % to 1.0 wt. %
- the nickel content can range from about 12 wt. % to about 20 wt. %.
- the nitrogen content can range from 0.02 wt. % to about 0.5 wt. %
- the silicon content can be limited to about 3.0 wt. % or less
- the molybdenum content can be limited to about 1.0 wt. % or less
- the niobium content can range from 0.0 wt. % to about 1.5 wt. %
- the carbon content can range from 0.05 wt. % to about 0.15 wt. %
- the chromium content can range from about 18 wt. % to about 25 wt. %
- the nickel content can range from about 8.0 wt. % to about 20.0 wt.
- the manganese content can range from about 0.5 wt. % to about 1.0 wt. %
- the sulfur content can range from about 0 wt. % to about 0.1 wt. %
- the niobium carbon ratio can range from about 8 to about 11
- the sum of the niobium and carbon contents can range from about 0.1 wt. % to about 0.5 wt. %.
- the phosphorous content can be limited to about 0.04 wt. % or less
- the copper content can be limited to about 3.0 wt. % or less
- the tungsten content can be limited to about 3.0 wt. % or less
- the vanadium content can be limited to about 3.0 wt. % or less
- the titanium content can be limited to about 0.20 wt. % or less
- the cobalt content can be limited to about 5.0 wt. % or less
- the aluminum content can be limited to about 3.0 wt. % or less
- the boron content can be limited to about 0.01 wt. % or less.
- the present invention is specifically directed toward a cast stainless steel alloy for the production of articles exposed to high temperatures and extreme thermal cycling such as air/exhaust-handling equipment for diesel and gasoline engines and gas-turbine engine components.
- the present invention is not limited to these applications as other applications will become apparent to those skilled in the art that require an austenitic stainless steel alloy for manufacturing reliable and durable high temperature cast components with any one or more of the following qualities: sufficient tensile and creep strength at temperatures in excess of 600° C.; adequate cyclic oxidation resistance at temperatures at or above 700° C.; sufficient room temperature ductility either as-cast or after exposure; sufficient long term stability of the original microstructure and sufficient long-term resistance to cracking during severe thermal cycling.
- stainless steel alloys of the present invention By employing the stainless steel alloys of the present invention, manufacturers can provide a more reliable and durable high temperature component. Engine and turbine manufacturers can increase power density by allowing engines and turbines to run at higher temperatures thereby providing possible increased fuel efficiency. Engine manufacturers may also reduce the weight of engines as a result of the increased power density by thinner section designs allowed by increased high temperature strength and oxidation and corrosion resistance compared to conventional high-silicon molybdenum ductile irons. Further, the stainless steel alloys of the present invention provide superior performance over other cast stainless steels for a comparable cost. Finally, stainless steel alloys made in accordance with the present invention will assist manufacturers in meeting emission regulations for diesel, turbine and gasoline engine applications.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Exhaust Silencers (AREA)
Abstract
A cast stainless steel alloy and articles formed therefrom containing about 0.5 wt. % to about 10 wt. % manganese, 0.02 wt. % to 0.50 wt. % N, and less than 0.15 wt. % sulfur provides high temperature strength both in the matrix and at the grain boundaries without reducing ductility due to cracking along boundaries with continuous or nearly-continuous carbides. Alloys of the present invention also have increased nitrogen solubility thereby enhancing strength at all temperatures because nitride precipitates or nitrogen porosity during casting are not observed. The solubility of nitrogen is dramatically enhanced by the presence of manganese, which also retains or improves the solubility of carbon thereby providing additional solid solution strengthening due to the presence of manganese and nitrogen, and combined carbon. Such solution strengthening enhances the high temperature precipitation-strengthening benefits of fine dispersions of NbC. Such solid solution effects also enhance the stability of the austenite matrix from resistance to excess sigma phase or chrome carbide formation at higher service temperatures. The presence of sulfides is substantially eliminated.
Description
- [0001] This invention was made with U.S. Government support under U.S. Department of Energy Contract No.: DE-AC05-960R2264 awarded by the U.S. Department of Energy. The U.S. Government has certain rights in this invention.
- This invention relates generally to cast steel alloys of the CF8C and CN-12 types with improved strength and ductility at high temperatures. More particularly, this invention relates to CN-12 and CF8C stainless steel alloys and articles made therefrom having excellent high temperature strength, creep resistance and aging resistance, with reduced niobium carbides, manganese sulfides, and chrome carbides along grain and substructure boundaries.
- There is a need for high strength, oxidation resistant and crack resistant cast alloys for use in internal combustion engine components such as exhaust manifolds and turbo-charger housings and gas-turbine engine components such as combustor housings as well as other components that must function in extreme environments for prolonged periods of time. The need for improved high strength, oxidation resistant, crack resistant cast alloys arises from the desire to increase operating temperatures of diesel engines, gasoline engines, and gas-turbine engines in effort of increasing fuel efficiency and the desire to increase the warranted operating hours or miles for diesel engines, gasoline engines and gas-turbine engines.
- Current materials used for applications such as exhaust manifolds, turbo-charger housings and combustor housings are limited by oxidation and corrosion resistance as well as by strength at high temperatures and detrimental effects of aging. Specifically, current exhaust manifold materials, such as high silicon and molybdenum cast ductile iron (Hi—Si—Mo) and austenitic ductile iron (Ni-resist) must be replaced by cast stainless steels when used for more severe applications such as higher operating temperatures or when longer operating lifetimes are demanded due to increased warranty coverage. The currently commercially available cast stainless steels include ferritic stainless steels such as NHSR-F5N or austenitic stainless steels such as NHSR-A3N, CF8C and CN-12. However, these currently-available cast stainless steels are deficient in terms of tensile and creep strength at temperatures exceeding 600° C., do not provide adequate cyclic oxidation resistance for temperatures exceeding 700° C., do not provide sufficient room temperature ductility either as-cast or after service exposure and aging, do not have the requisite long-term stability of the original microstructure and lack long-term resistance to cracking during severe thermal cycling.
- Currently, the corrosion-resistant grade of cast austenitic stainless steel, CN-12, is in commercial use for automotive applications but is not optimized for extended service applications (e.g. diesel applications). CN-12 provides adequate strength and aesthetics for automobiles for the anticipated life in comparison to cast iron, but lacks the improved creep resistance that is optimal when mounting turbo chargers (70 lbs.) onto diesel exhaust manifolds. Currently commercially available CN-12 austenitic stainless steel includes about 25 wt. % chromium, 13 wt. % nickel, smaller amounts of carbon, nitrogen, niobium, silicon, manganese, molybdenum and sulfur. The addition of sulfur is considered essential or desirable for machineability from the cast material. The amount of added sulfur ranges from 0.11 wt. % to 0.15 wt. %.
- Currently-available cast austenitic stainless CF8C steels include from 18 wt. % to 21 wt. % chromium, 9 wt. % to 12 wt. % nickel and smaller amounts of carbon, silicon, manganese, phosphorous, sulfur and niobium. CF8C typically includes about 2 wt. % silicon, about 1.5 wt. % manganese and about 0.04 wt. % sulfur. CF8C is a niobium stabilized grade of austentic stainless steel most suitable for aqueous corrosion resistance at temperatures below 500° C. In the standard form CF8C has inferior strength compared to CN12 at temperatures above 600° C.
- It is therefore desirable to have a steel alloy and articles made from a steel alloy that have improved strength-at high temperatures and improved ductility for engine component applications requiring severe thermal cycling, high operation temperatures and extended warranty coverage.
- In accordance with one example of the present invention, a stainless steel alloy is provided that contains from about 0.5 wt. % to about 10 wt. % manganese and less than about 0.10 wt. % sulfur.
- In accordance with another example of the present invention, a stainless steel alloy is provided that contains from about 0.03 wt. % sulfur or less, from about 2 wt. % to about 5 wt. % manganese and niobium and carbon in a niobium:carbon wt. % ratio ranging from about 3.5 to about 5.0.
- In accordance with another example of the present invention, a stainless steel is provided that contains from about 2 wt. % to about 5 wt. % manganese, less than about 0.03 wt. % sulfur and about 0.8 wt. % silicon or less.
- Various advantages of the present invention will become apparent upon reading the following detailed description and appended claims.
- The present invention is directed toward alloys of both the CN-12 and CF8C types. Table 1 presents the optimal and permissible minimum and maximum ranges for the compositional elements of CN-12 and CF8C stainless steel alloys made in accordance with the present invention. Boron, aluminum and copper may also be added. However, it will be noted that allowable ranges for cobalt, vanadium, tungsten and titanium may not significantly alter the performance of the resulting material. Specifically, based on current information, that cobalt may range from 0 to 5 wt. %, vanadium may range from 0 to 3 wt. %, tungsten may range from 0 to 3 wt. % and titanium may range from 0 to 0.2 wt. % without significantly altering the performances of the alloys. Accordingly, it is anticipated that the inclusion of these elements in amounts that fall outside of the ranges of Table 1 would still provide advantageous alloys and would fall within the spirit and scope of the present invention.
TABLE 1 Composition by Weight Percent OPTIMAL PERMISSIBLE PERMIS- CN- CN- CN- CN- OPTIMAL SIBLE 12 12 12 12 CF8C CF8C CF8C CF8C Element MIN MAX MIN MAX MIN MAX MIN MAX Chromium 22.0 25.0 18.0 25.0 18.0 21.0 18.0 25.0 Nickel 12.0 16.0 12.0 20.0 12.0 15.0 8.0 20.0 Carbon 0.30 0.45 0.2 0.5 0.07 0.1 0.05 0.15 Silicon 0.50 0.75 0.2 3.0 0.5 0.75 0.20 3.0 Manganese 2 5.0 0.5 10.0 2.0 5.0 0.5 10.0 Phosphorous 0 0.04 0 0.04 0 0.04 0 0.04 Sulfur 0 0.03 0 0.10 0 0.03 0 0.1 Molybdenum 0 0.3 0 0.5 0 0.5 0 1.0 Copper 0 0.3 0 3.0 0 0.3 0 3.0 Niobium 1.5 2.0 1.0 2.5 0.3 1.0 0 1.5 Nitrogen 0.1 0.5 0.1 0.5 0.1 0.3 0.02 0.5 Titanium 0 0.03 0 0.2 0 0.03 0 0.2 Cobalt 0 0.5 0 5.0 0 0.5 0 5.0 Aluminum 0 0.05 0 3.0 0 0.05 0 3.0 Boron 0 0.01 0 0.01 0 0.01 0 0.01 Vanadium 0 0.01 0 3.0 0 0.01 0 3.0 Tungsten 0 0.6 0 3.0 0 0.1 0 3.0 Niobium: 3.5 5.0 3 5.0 9 11 8 11 Carbon Carbon + 0.5 0.75 0.4 1.0 0.15 0.4 0.1 0.5 Nitrogen - Unexpectely, the inventors have found that substantially reducing the sulfur content of austenitic stainless steels increases the creep properties. The inventors believe machineability is not significantly altered as they believe the carbide morphology controls machining characteristics in this alloy system. While sulfur may be an important component of cast stainless steels for other applications because it contributes significantly to the machineability of such steels, it severely limits the high temperature creep-life and ductility and low temperature ductility after service at elevated temperatures.
- The inventors have found that removing or substantially reducing the presence of sulfur alone provides a four-fold improvement in creep life at 850° C. at a stress load of 110 MPa.
- Further, the inventors have found that reducing the maximum carbon content in the alloys of the present invention reduces the coarse NbC and possibly some of the coarse Cr 23C6 constituents from the total carbide content (VF Carbide) in a near linear manner as shown in Table 2. Table 2 includes the compositions of ten experimental alloys A-J in comparison with a standard CN-12 and CF8C alloys
TABLE 2 Composition by Weight Percent Element CN-12 A B C D E F G H CF8C I J Chromium 24 53 24.87 23 84 23.92 23.84 24.28 23.9 24.00 23.96 19.16 19.14 19.08 Nickel 12.91 13.43 15.34 15.33 15.32 15.67 15.83 15.69 15.90 12.19 12.24 12.36 Carbon 0 40 0.43 0.31 0.31 0.20 0.41 0.37 0.40 0.29 0.08 0.09 0.08 Silicon 0 9 0.82 0.7 0.7 0.68 0.66 0.66 0.66 0.66 0.66 0.62 0.67 Manganese 0.82 0.90 1.83 1.85 1.84 1.86 4.87 4.86 4.82 1.89 1.80 4.55 Phosphorous 0.019 0.036 0.037 0.038 0.040 0.035 0.033 0.032 0.032 0.004 0.004 0.005 Sulfur 0.139 0.002 0.002 0.003 0.003 0.001 0.001 0.001 0.001 0.002 0.002 0.004 Molybdenum 0.49 0.26 0.52 0.52 0.52 0.31 0 31 0.30 0.30 0.31 0.31 0.31 Copper 0.15 0.01 0.01 0.01 0.00 0.01 0 01 0.01 0.01 0.01 0.01 0.01 Niobium 1.92 1.41 1.26 1.06 1.05 1.78 1 72 1.31 1.22 0.68 0.68 0.68 Nitrogen 0.27 0.25 0.13 0.2 0.17 0.28 0.44 0.31 0.34 0.02 0.11 0.23 Titanium 0 0.005 0.004 0 005 0.004 0.004 0.005 0.006 0.005 0.008 0.006 0.006 Cobalt 0.019 0.02 0.02 0.02 0.02 0.02 0 02 0.02 0.02 0.01 0.01 0.01 Aluminum 0 0.01 0.01 0.01 0.01 0 0 0 0 0.01 0.01 0.01 Boron 0 0.001 0.001 0.001 0.001 0 0 0 0 0 001 0 001 0.001 Vanadium 0 0.01 0.008 0.008 0.008 0.011 0.012 0.012 0.011 0.004 0.007 0.001 Niobium: 4.8 3 28 4 06 3.42 5.25 4.34 4.64 3.28 4.21 8.40 7.82 8.52 Carbon Carbon + 0.67 0.68 0.44 0.51 0.37 0.69 0.81 0.71 0.63 0.10 0.20 0.31 Nitrogen VF Carbide 11.4 8.0 7.5 3.7 - The volume fraction of carbide shown in Table 2 was measured with a Clemex Image Analysis System. A near linear correlation is observed between carbon content and carbide content. However, by lowering the carbon content below 0.20 wt. %, δ ferrite is allowed to form. δ ferrite will eventually form sigma at operating temperatures, presumably causing premature failure. Sigma, is a hard brittle Fe—Cr intermetallic, which greatly reduces both strength and ductility when present. These observations did form the basis for further strategy of designing optimum high temperature microstructures based on smaller specific reductions in as-cast carbide content (mainly CR 23C6 rather than NbC) and maximum stability of the austenite matrix against the formation of sigma phase during prolonged aging at 700° C. to 900° C. This improved austenite stability resulted in CN-12 alloys with more nickel, manganese and nitrogen while keeping carbon in the range of 0.30 wt. % to 0.45 wt. %.
- The elevated tensile properties for alloys A-J, CN-12, and CF8C were measured at 850° C. and are displayed in Tables 3. Creep properties of alloys A-J, CN-12, and CF8C were measured at 850° C. and are displayed in Table 4.
TABLE 3 Strain Temp Rate YS UTS Elong Alloy Condition (° C.) (1/sec) (ksi) (ksi) (%) CN-12 As-Cast 850 1E−05 19.1 21.7 8.4 A As-Cast 850 1E−05 21.2 24.5 9.6 B As-Cast 850 1E−05 19.1 20.75 14.2 C As-Cast 850 1E−05 22.6 23.9 37.2 D As-Cast 850 1E−05 20 21.9 29.5 E As-Cast 850 1E−05 20.8 24.8 10.8 F As-Cast 850 1E−05 24.5 27.5 6.10 G As-Cast 850 1E−05 23.1 26.0 30.3 H As-Cast 850 1E−05 22.9 25.8 30.0 CF8C As-Cast 850 1E−05 11.7 12.6 31.2 I As-Cast 850 1E−05 17.1 18.1 45.9 J As-Cast 850 1E−05 21.5 22.1 35 -
TABLE 4 Temp Stress Life Elong Heat Condition (° C.) (ksi) (Hours) (%) CN-12 As-Cast 850 110 10.7 6.5 A As-Cast 850 110 53.5 6.2 B As-Cast 850 110 51.3 37.7 C As-Cast 850 110 26.7 26.7 D As-Cast 850 110 17.5 25.1 E As-Cast 850 110 93.9 11.6 F As-Cast 850 110 113 9.6 G As-Cast 850 110 103 15.5 H As-Cast 850 110 72.5 18 CF8C As-Cast 850 35 1824 7.2 I As-Cast 850 35 5252* 2 J As-Cast 850 35 6045* 0.4 - The critical testing conditions for CN-12 of 850° C. and 110 MPa were chosen because 850° C. is approximately the highest exhaust temperature observed currently and this is the temperature at which the most harmful precipitates like sigma form rapidly. The stress, 110 MPa, was chosen to provide an accelerated test lasting from 10 to 100 hours that would equate to much longer durability at lower stresses and temperatures during engine service. Removing the sulfur improved the room and elevated temperature ductility, tensile strength, yield strength, creep life and creep ductility for the same carbon content. By lowering the carbon content to 0.30 wt. %, creep life and tensile strength were only slightly lowered while creep ductility was improved significantly. By lowering the carbon content further to 0.20 wt. %, room or elevated temperature strength did not decrease significantly, but creep life was reduced by 60 percent.
- The critical test conditions for the CF8C of 850° C. and 35Mpa were again chosen because of expected operating temperatures and the harmful precipitates, which form readily. The stress of 35 MPa was chosen for accelerated test conditions that would again equate to much longer durability at lower stress levels during engine service. The increase in nitrogen results in a dramatic increase in room and elevated temperature strength and ductility with at least a three-fold improvement in creep life at 850° C.
- A solution annealing treatment (SA) was applied to each alloy to analyze the effect of a more uniform distribution of carbon. The alloys were held at 1200° C. for one hour. They were then air cooled rather than quenched to allow the small niobium carbide and chromium carbide precipitates to nucleate in the matrix during cooling. The resulting microstructure was found to be very similar to the as-cast (AS) structure except for the formation of small precipitates. Unfortunately, the solution annealing treatment lowered creep life significantly while increasing creep ductility, therefore proving that the strategy to optimize the as-cast microstructures was best as well as most cost effective.
- Alloys A-H and the unmodified CN-12 base alloy were aged at 850° C. for 1,000 hours to study the effects of aging on the microstructure and mechanical properties which are summarized in Table 5. The alloys with 0.3 wt. % carbon (alloys B and C) showed the presence of platelets near the grain boundary structure. The 0.2 wt. % carbon alloy (D) showed an even higher amount of the platelets. The platelets are identified as sigma in the ASM Handbook, Vol. 9, 9 th Ed. (1986). SEM/XEDS/TEM analysis confirmed that the platelets had a concentration consistent with sigma. (FeCr). Alloys E, F, and G with more carbon and Nb showed good resistance to sigma phase embrittlement. Alloys I and J aged at 850° C. for 1000 hours showed improved strength compared to the commercially available CF8C.
TABLE 5 Strain Temp Rate YS UTS Elong Alloy Condition (° C.) (1/sec) (ksi) (ksi) (%) CN-12 Aged 1000 hr at 850° C. 22 1E−05 42.4 79.45 5.5 A Aged 1000 hr at 850° C. 22 1E−05 46.7 76.1 3.6 B Aged 1000 hr at 850° C. 22 1E−05 37.9 58.4 2.9 C Aged 1000 hr at 850° C. 22 1E−05 46.5 81 4.6 D Aged 1000 hr at 850° C. 22 1E−05 44.4 76.4 3 E Aged 1000 hr at 850° C. 22 1E−05 55.3 81.6 3.1 F Aged 1000 hr at 850° C. 22 1E−05 56 84.8 2.2 G Aged 1000 hr at 850° C. 22 1E−05 53.3 85.2 2.6 H Aged 1000 hr at 850° C. 22 1E−05 43 80.7 1.7 CF8C Aged 1000 hr at 850° C. 22 1E−05 28.3 67.5 27 I Aged 1000 hr at 850° C. 22 1E−05 34.4 82 25 J Aged 1000 hr at 850° C. 22 1E−05 42.3 79.4 11.3 - In order to improve upon the performance of alloys A-D, the inventors utilized a unique combination of higher manganese, higher nitrogen, combined with a reduced sulfur content, all in an alloy also containing substantial amounts of carbon and niobium.
- Manganese is an effective austenite stabilizer, like nickel, but is about one tenth the cost of nickel. The positive austenite stabilizing potential of manganese must be balanced with its possible affects on oxidation resistance at a given chromium level relative to nickel, which nears maximum effectiveness around 5 wt. % and therefore addition of manganese in excess of 10 wt. % is not recommended.
- Manganese in an amount of less than 2 wt. % may not provide the desired stabilizing effect. Manganese also dramatically increases the solubility of carbon and nitrogen in austenite. This effect is especially beneficial because dissolved nitrogen is an austenite stabilizer and also improves strength of the alloy when in solid solution without decreasing ductility or toughness. Manganese also improves strength ductility and toughness, and manganese and nitrogen have synergistic effects.
- The dramatic reduction in the sulfur content to 0.1 wt. % or less proposed by the present invention substantially eliminates the segregation of free sulfur to grain boundaries and further eliminates MnS particles found in conventional CN-12 and CF8C alloys, both of which are believed to be detrimental at high temperatures.
- With respect to the CN-12 alloys, the inventors have found that an appropriate niobium:carbon ratio reduces excessive and continuous networks of coarse niobium carbides (NbC) or finer chrome carbides (M 23C6) along the grain or substructure boundaries (interdentritic boundaries and cast material) that are detrimental to the mechanical performance of the material at high temperatures. Accordingly, by providing an optimum level of the niobium and carbon ratio ranging from about 3.5 to about 5 for CN-12 alloys and from about 9 to about 11 for CF8C alloys, niobium and carbon are present in amounts necessary to provide high-temperature strength (both in the matrix and at the grain boundaries), but without reducing ductility due to cracking along boundaries with continuous or nearly-continuous carbides. Carbon can be present in CN-12 alloys in an amount ranging from 0.2 wt. % to about 0.5 wt. % and niobium can be present in CN-12 alloys in an amount ranging from about 1.0 wt. % to about 2.5 wt. %.
- Strength at all temperatures is also enhanced by the improved solubility of nitrogen which is a function of manganese. Nitrogen can be present in an amount ranging from 0.1 wt. % to about 0.5 wt. % in CN-12 alloys. The presence of nitride precipitates is reduced by adjusting the levels and enhancing the solubility of nitrogen while lowering the chromium:nickel ratio.
- For alloys of the CN-12 type, the niobium to carbon ratio can range from about 3 to about 5, the nitrogen content can range from about 0.10 wt. % to about 0.5 wt. %, the carbon content can range from about 0.2 wt. % to about 0.5 wt. %, the niobium content can range from about 1.0 wt. % to about 2.5wt. %, the silicon content can range from about 0.2 wt. % to about 3.0 wt. %, the chromium content can range from about 18 wt. % to about 25 wt. %, the molybdenum content can be limited to about 0.5 wt. % or less, the manganese content can range from about 0.5 wt. % to about 1.0 wt. %, the sulfur content can range from about 0 wt. % to about 0.1 wt. %, the sum of the carbon and nitrogen content can range from 0.4 wt. % to 1.0 wt. %, and the nickel content can range from about 12 wt. % to about 20 wt. %.
- For alloys of the CF8C type, the nitrogen content can range from 0.02 wt. % to about 0.5 wt. %, the silicon content can be limited to about 3.0 wt. % or less, the molybdenum content can be limited to about 1.0 wt. % or less, the niobium content can range from 0.0 wt. % to about 1.5 wt. %, the carbon content can range from 0.05 wt. % to about 0.15 wt. %, the chromium content can range from about 18 wt. % to about 25 wt. %, the nickel content can range from about 8.0 wt. % to about 20.0 wt. %, the manganese content can range from about 0.5 wt. % to about 1.0 wt. %, the sulfur content can range from about 0 wt. % to about 0.1 wt. %, the niobium carbon ratio can range from about 8 to about 11, and the sum of the niobium and carbon contents can range from about 0.1 wt. % to about 0.5 wt. %.
- For both CN-12 and CF8C alloys, the phosphorous content can be limited to about 0.04 wt. % or less, the copper content can be limited to about 3.0 wt. % or less, the tungsten content can be limited to about 3.0 wt. % or less, the vanadium content can be limited to about 3.0 wt. % or less, the titanium content can be limited to about 0.20 wt. % or less, the cobalt content can be limited to about 5.0 wt. % or less, the aluminum content can be limited to about 3.0 wt. % or less and the boron content can be limited to about 0.01 wt. % or less.
- Because nickel is an expensive component, stainless steel alloys made in accordance with the present invention are more economical if the nickel content is reduced.
- Industrial Applicability
- The present invention is specifically directed toward a cast stainless steel alloy for the production of articles exposed to high temperatures and extreme thermal cycling such as air/exhaust-handling equipment for diesel and gasoline engines and gas-turbine engine components. However, the present invention is not limited to these applications as other applications will become apparent to those skilled in the art that require an austenitic stainless steel alloy for manufacturing reliable and durable high temperature cast components with any one or more of the following qualities: sufficient tensile and creep strength at temperatures in excess of 600° C.; adequate cyclic oxidation resistance at temperatures at or above 700° C.; sufficient room temperature ductility either as-cast or after exposure; sufficient long term stability of the original microstructure and sufficient long-term resistance to cracking during severe thermal cycling.
- By employing the stainless steel alloys of the present invention, manufacturers can provide a more reliable and durable high temperature component. Engine and turbine manufacturers can increase power density by allowing engines and turbines to run at higher temperatures thereby providing possible increased fuel efficiency. Engine manufacturers may also reduce the weight of engines as a result of the increased power density by thinner section designs allowed by increased high temperature strength and oxidation and corrosion resistance compared to conventional high-silicon molybdenum ductile irons. Further, the stainless steel alloys of the present invention provide superior performance over other cast stainless steels for a comparable cost. Finally, stainless steel alloys made in accordance with the present invention will assist manufacturers in meeting emission regulations for diesel, turbine and gasoline engine applications.
- While only certain embodiments have been set forth, alternative embodiments and various modifications will be apparent from the above description to those skilled in the art. These and other alternatives are considered equivalents and within the spirit and scope of the present invention.
Claims (36)
1. A stainless steel alloy comprising:
from about 0.5 wt. % to about 10 wt. % manganese; and
less than about 0.15 wt. % sulfur.
2. The stainless steel alloy of claim 1 wherein the alloy is a CN-12 alloy or a CF8C alloy.
3. The stainless steel alloy of claim 1 further comprising from about 0.2 wt. % to about 0.5 wt. % carbon and from about 1 wt. % to about 2.5 wt. % niobium.
4. The stainless steel alloy of claim 3 wherein the alloy is a CN-12 alloy wherein niobium and carbon are present in a weight ratio of niobium to carbon ranging from about 3 to about 5.
5. The stainless steel alloy of claim 1 wherein the alloy is a CF8C alloy wherein niobium and carbon are present in a weight ratio of niobium to carbon ranging from about 8 to about 11.
6. The stainless steel alloy of claim 3 further comprising from about 0.10 wt. % to about 0.5 wt. % nitrogen.
7. The stainless steel alloy of claim 3 further comprising less than about 0.04 wt. % phosphorous.
8. The stainless steel alloy of claim 3 further comprising from about 0.2 wt. % to about 3.0 wt. % silicon.
9. The stainless steel alloy of claim 3 further comprising from about 8 wt. % to about 25 wt. % nickel.
10. The stainless steel alloy of claim 3 further comprising from about 18 wt. % to about 25 wt. % chromium.
11. The stainless steel alloy of claim 3 further comprising about 0.5 wt. % molybdenum or less.
12. The stainless steel alloy of claim 3 further comprising about 3.0 wt. % tungsten or less.
13. The stainless steel alloy of claim 3 further comprising about 3.0 wt. % copper or less.
14. The stainless steel alloy of claim 1 further comprising from about 0.02 wt. % to about 0.5 wt. % nitrogen.
15. The stainless steel alloy of claim 1 further comprising from about 0.8 wt. % silicon or less.
16. The stainless steel alloy of claim 1 further comprising from about 3.0 wt. % copper or less.
17. The stainless steel alloy of claim 1 further comprising from about 0.3 wt. % to about 1 wt. % niobium.
18. The stainless steel alloy of claim 1 further comprising from about 0.2 wt. % titanium or less.
19. The stainless steel alloy of claim 1 further comprising from about 5.0 wt. % cobalt or less.
20. The stainless steel alloy of claim 1 further comprising from about 3.0 wt. % aluminum or less.
21. The stainless steel alloy of claim 1 further comprising from about 0.01 wt. % boron or less.
22. The stainless steel alloy of claim 1 further comprising from about 3.0 wt. % tungsten or less.
23. The stainless steel alloy of claim 3 further comprising about 3.0 wt. % vanadium or less.
24. The stainless steel alloy of claim 1 wherein the alloy is a CN-12 alloy and wherein nitrogen and carbon are present in a cumulative amount ranging from 0.4 wt. % to 1.0 wt. %.
25. The stainless steel alloy of claim 1 wherein the alloy is a CF8C alloy and wherein nitrogen and carbon are present in a cumulative amount ranging from 0.1 wt. % to 0.5 wt. %.
26. A CN-12 stainless steel alloy comprising:
about 0.03% sulfur or less;
from about 2 wt. % to about 5 wt. % manganese;
niobium and carbon in a niobium:carbon wt. % ratio ranging from about 3.5 to 5.0.
27. The CN-12 alloy of claim 26 wherein niobium is present in an amount ranging from about 1.5 wt. % to about 2.0 wt. %.
28. The CN-12 alloy of claim 26 further comprising about 0.04 wt. % phosphorous or less.
29. The CN-12 alloy of claim 26 further comprising from about 0.2 wt. % to about 1.4 wt. % silicon.
30. The CN-12 alloy of claim 26 further comprising from about 12 wt. % to about 25 wt. % nickel.
31. The CN-12 alloy of claim 26 further comprising from about 22 wt. % to about 25 wt. % chromium.
32. The CN-12 alloy of claim 26 further comprising less than about 0.3 wt. % molybdenum or less.
33. The CN-12 alloy of claim 26 further comprising about 3 wt. % copper or less.
34. An article formed from the stainless steel alloy of claim 1 .
35. An article formed from the stainless steel alloy of claim 26 .
36. A stainless steel alloy comprising:
from about 2 wt. % to about 5 wt. % manganese;
less than about 0.03 wt. % sulfur; and
about 0.5 wt. % nitrogen or less.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/736,741 US20020110476A1 (en) | 2000-12-14 | 2000-12-14 | Heat and corrosion resistant cast stainless steels with improved high temperature strength and ductility |
| EP01124942.2A EP1219720B1 (en) | 2000-12-14 | 2001-10-19 | Heat and corrosion resistant cast stainless steels with improved high temperature strength and ductility |
| ES01124942.2T ES2503715T3 (en) | 2000-12-14 | 2001-10-19 | Cast stainless steels resistant to heat and corrosion, with improved resistance and ductility at high temperature |
| EP09002293A EP2113581B1 (en) | 2000-12-14 | 2001-10-19 | Heat and corrosion resistant cast stainless steels with improved high temperature strength and ductility |
| ES09002293T ES2369392T3 (en) | 2000-12-14 | 2001-10-19 | STAINLESS STEEL COLORS RESISTANT TO HEAT AND CORROSION PROVIDED WITH IMPROVED RESISTANCE AND DUCTILITY TO HIGH TEMPERATURE. |
| AT09002293T ATE523610T1 (en) | 2000-12-14 | 2001-10-19 | HEAT AND CORROSION RESISTANT STAINLESS CAST STEELS WITH IMPROVED HEAT STRENGTH AND MALLABILITY |
| JP2001378786A JP2002194511A (en) | 2000-12-14 | 2001-12-12 | Heat resistant and corrosion resistant cast stainless steel having superior high temperature strength and ductility |
| KR1020010078726A KR100856659B1 (en) | 2000-12-14 | 2001-12-13 | Heat and corrosion resistant cast stainless steels with improved high temperature strength and ductility |
| US10/195,724 US7153373B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility |
| US10/195,703 US7255755B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility |
| US12/230,179 USRE41504E1 (en) | 2000-12-14 | 2008-08-25 | Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility |
| US12/230,257 USRE41100E1 (en) | 2000-12-14 | 2008-08-26 | Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility |
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| US09/736,741 US20020110476A1 (en) | 2000-12-14 | 2000-12-14 | Heat and corrosion resistant cast stainless steels with improved high temperature strength and ductility |
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| US10/195,724 Continuation-In-Part US7153373B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility |
| US10/195,724 Continuation US7153373B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility |
| US10/195,703 Continuation-In-Part US7255755B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility |
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| US09/736,741 Abandoned US20020110476A1 (en) | 2000-12-14 | 2000-12-14 | Heat and corrosion resistant cast stainless steels with improved high temperature strength and ductility |
| US10/195,724 Ceased US7153373B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility |
| US10/195,703 Ceased US7255755B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility |
| US12/230,179 Expired - Lifetime USRE41504E1 (en) | 2000-12-14 | 2008-08-25 | Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility |
| US12/230,257 Expired - Lifetime USRE41100E1 (en) | 2000-12-14 | 2008-08-26 | Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility |
Family Applications After (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/195,724 Ceased US7153373B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility |
| US10/195,703 Ceased US7255755B2 (en) | 2000-12-14 | 2002-07-15 | Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility |
| US12/230,179 Expired - Lifetime USRE41504E1 (en) | 2000-12-14 | 2008-08-25 | Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility |
| US12/230,257 Expired - Lifetime USRE41100E1 (en) | 2000-12-14 | 2008-08-26 | Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility |
Country Status (6)
| Country | Link |
|---|---|
| US (5) | US20020110476A1 (en) |
| EP (2) | EP2113581B1 (en) |
| JP (1) | JP2002194511A (en) |
| KR (1) | KR100856659B1 (en) |
| AT (1) | ATE523610T1 (en) |
| ES (2) | ES2503715T3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060266439A1 (en) * | 2002-07-15 | 2006-11-30 | Maziasz Philip J | Heat and corrosion resistant cast austenitic stainless steel alloy with improved high temperature strength |
| US20070217941A1 (en) * | 2004-04-19 | 2007-09-20 | Hitachi Metals, Ltd | HIGH-Cr HIGH-Ni, HEAT-RESISTANT, AUSTENITIC CAST STEEL AND EXHAUST EQUIPMENT MEMBERS FORMED THEREBY |
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| CN103290332B (en) * | 2013-06-18 | 2015-09-09 | 浙江和园装饰有限公司 | A kind of abrasion-resistant metal pipeline with inner anticorrosioning coating |
| CN103290332A (en) * | 2013-06-18 | 2013-09-11 | 张康 | Wear-resistant metal pipeline with inner corrosion-resistant coating |
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| CN114341389A (en) * | 2019-11-18 | 2022-04-12 | 韩国科学技术院 | Austenitic stainless steel with a large number of uniformly distributed nano-sized precipitates and method of making the same |
| US12110578B2 (en) | 2019-11-18 | 2024-10-08 | Korea Advanced Institute Of Science And Technology | Austenitic stainless steel having a large amount of unifromly distributed nanometer-sized precipitates and preparing method of the same |
| US11873547B2 (en) * | 2020-10-15 | 2024-01-16 | Cummins Inc. | Fuel system components |
| CN113862573A (en) * | 2021-06-30 | 2021-12-31 | 青岛科技大学 | Nanocrystalline stainless steel for paper pulp millstone and preparation method thereof |
| CN113943904A (en) * | 2021-10-18 | 2022-01-18 | 华能国际电力股份有限公司 | A heat treatment process for improving high temperature tensile plasticity of heat-resistant alloys |
| CN113943904B (en) * | 2021-10-18 | 2022-04-22 | 华能国际电力股份有限公司 | Heat treatment process for improving high-temperature tensile plasticity of heat-resistant alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| US20030056860A1 (en) | 2003-03-27 |
| ES2503715T3 (en) | 2014-10-07 |
| US20030084967A1 (en) | 2003-05-08 |
| US7153373B2 (en) | 2006-12-26 |
| EP1219720A2 (en) | 2002-07-03 |
| ATE523610T1 (en) | 2011-09-15 |
| EP1219720A3 (en) | 2003-04-16 |
| EP2113581B1 (en) | 2011-09-07 |
| USRE41100E1 (en) | 2010-02-09 |
| KR100856659B1 (en) | 2008-09-04 |
| JP2002194511A (en) | 2002-07-10 |
| ES2369392T3 (en) | 2011-11-30 |
| US7255755B2 (en) | 2007-08-14 |
| KR20020046988A (en) | 2002-06-21 |
| USRE41504E1 (en) | 2010-08-17 |
| EP2113581A1 (en) | 2009-11-04 |
| EP1219720B1 (en) | 2014-09-10 |
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