EP2890825B1 - Ferritic stainless steel with excellent oxidation resistance, good high temperature strength, and good formability - Google Patents
Ferritic stainless steel with excellent oxidation resistance, good high temperature strength, and good formability Download PDFInfo
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- EP2890825B1 EP2890825B1 EP13759947.8A EP13759947A EP2890825B1 EP 2890825 B1 EP2890825 B1 EP 2890825B1 EP 13759947 A EP13759947 A EP 13759947A EP 2890825 B1 EP2890825 B1 EP 2890825B1
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- ferritic stainless
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- 229910001220 stainless steel Inorganic materials 0.000 title claims description 36
- 230000003647 oxidation Effects 0.000 title description 13
- 238000007254 oxidation reaction Methods 0.000 title description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000010936 titanium Substances 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 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
- 229910052742 iron Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 description 30
- 239000000155 melt Substances 0.000 description 25
- 229910000831 Steel Inorganic materials 0.000 description 19
- 239000010959 steel Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000000137 annealing Methods 0.000 description 9
- 238000005266 casting Methods 0.000 description 9
- MNEIJGDSFRHGMS-UHFFFAOYSA-N 1-(phenylmethyl)benzimidazole Chemical compound C1=NC2=CC=CC=C2N1CC1=CC=CC=C1 MNEIJGDSFRHGMS-UHFFFAOYSA-N 0.000 description 7
- 238000005261 decarburization Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 6
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 238000004901 spalling Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910006639 Si—Mn Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- -1 e.g. Chemical compound 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000161 steel melt Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
-
- 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
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- 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
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- 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
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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
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
-
- 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
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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
- C22C38/04—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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
Definitions
- ferritic stainless steel with oxidation resistance, high temperature strength, and good formability characteristics. Columbium and copper are added in amounts to provide high temperature strength, and silicon and manganese are added in amounts to provide oxidation resistance.
- the present ferritic stainless steel provides better oxidation resistance than known stainless steels such as 18Cr-2Mo and 15Cr-Cb-Ti-Si-Mn. In addition, the present ferritic stainless steel is less expensive to manufacture than other stainless steels such as 18Cr-2Mo and can be produced without a hot band annealing step.
- WO2012/036313 A1 discloses a heat-resistant ferrite-type stainless steel plate used in exhaust system components.
- the present ferritic stainless steel are produced with titanium additions and low aluminum concentration to provide room temperature formability from equiaxed as-cast grain structures, as disclosed in U.S. Patent Nos. 6,855,213 and 5,868, 875 .
- Columbium and copper are added to the ferritic stainless steel for high temperature strength and silicon and manganese are added to improve oxidation resistance.
- the ferritic stainless steel is produced using process conditions known in the art for use in manufacturing ferritic stainless steels, such as the processes described in U.S. Patent Nos. 6,855,213 and 5,868,875 .
- Columbium and copper are added to the ferritic stainless steel for high temperature strength and silicon and manganese are added to improve oxidation resistance. It can be produced from material having an as-cast structure of fine equiaxed grains.
- a ferrous melt for the ferritic stainless steel is provided in a melting furnace such as an electric arc furnace.
- This ferrous melt may be formed in the melting furnace from solid iron bearing scrap, carbon steel scrap, stainless steel scrap, solid iron containing materials including iron oxides, iron carbide, direct reduced iron, hot briquetted iron, or the melt may be produced upstream of the melting furnace in a blast furnace or any other iron smelting unit capable of providing a ferrous melt.
- the ferrous melt then will be refined in the melting furnace or transferred to a refining vessel such as an argon-oxygen-decarburization vessel or a vacuum-oxygen-decarburization vessel, followed by a trim station such as a ladle metallurgy furnace or a wire feed station.
- the steel is cast from a melt containing sufficient titanium and nitrogen but a controlled amount of aluminum for forming small titanium oxide inclusions to provide the necessary nuclei for forming the as-cast equiaxed grain structure so that an annealed sheet produced from this steel also has enhanced ridging characteristics and formability.
- titanium is added to the melt for deoxidation prior to casting.
- Deoxidation of the melt with titanium forms small titanium oxide inclusions that provide the nuclei that result in an as-cast equiaxed fine grain structure.
- aluminum may not be added to this refined melt as a deoxidant and in other embodiments aluminum may be added to this refined melt in a small fraction.
- titanium and nitrogen are present in the melt prior to casting so that the ratio of the product of titanium and nitrogen divided by residual aluminum is at least 0.14.
- the steel is to be stabilized, sufficient amount of the titanium beyond that required for deoxidation can be added for combining with carbon and nitrogen in the melt but preferably less than that required for saturation with nitrogen, i.e ., in a sub-equilibrium amount, thereby avoiding or at least minimizing precipitation of large titanium nitride inclusions before solidification.
- the maximum amount of titanium for "sub-equilibrium" is generally illustrated in FIG. 4 of U.S. Pat. No. 4,964,926 ,
- one or more stabilizing elements such as columbium, zirconium, tantalum and vanadium can be added to the melt as well.
- the cast steel is hot processed into a sheet.
- sheet is meant to include continuous strip or cut lengths formed from continuous strip and the term “hot processed” means the as-cast steel will be reheated, if necessary, and then reduced to a predetermined thickness such as by hot rolling. If hot rolled, a steel slab is reheated to 2000° to 2350°F (1093°-1288°C), hot rolled using a finishing temperature of 1500 - 1800°F (816 - 982°C) and coiled at a temperature of 1000 - 1400°F (538 - 760°C).
- the hot rolled sheet is also known as the "hot band.”
- the hot band may be annealed at a peak metal temperature of 1700 - 2100°F (926 - 1149°C). In other embodiments, the sheet does not undergo a hot band annealing step.
- the hot band may be descaled and cold reduced at least 40% to a desired final sheet thickness. In other embodiments, the hot band may be descaled and cold reduced at least 50% to a desired final sheet thickness. Thereafter, the cold reduced sheet can be final annealed at a peak metal temperature of 1800 - 2100°F (982-1149°C).
- the ferritic stainless steel can be produced from a hot processed sheet made by a number of methods.
- the sheet can be produced from slabs formed from ingots or continuous cast slabs of 50-200 mm thickness which are reheated to 2000° to 2350°F (1093°-1288°C) followed by hot rolling to provide a starting hot processed sheet of 1 - 7 mm thickness or the sheet can be hot processed from strip continuously cast into thicknesses of 2 - 52 mm.
- the present process is applicable to sheet produced by methods wherein continuous cast slabs or slabs produced from ingots are fed directly to a hot rolling mill with or without significant reheating, or ingots hot reduced into slabs of sufficient temperature to be hot rolled in to sheet with or without further reheating.
- Titanium is used for deoxidation of the ferritic stainless steel melt prior to casting.
- the amount of titanium in the melt is 0.30% or less. Unless otherwise expressly stated, all concentrations stated as “%" are percent by weight.
- titanium can be present in a sub-equilibrium amount.
- the term "sub-equilibrium” means the amount of titanium is controlled so that the solubility product of the titanium compounds formed are below the saturation level at the steel liquidus temperature thereby avoiding excessive titanium nitride precipitation in the melt.
- Excessive nitrogen is not a problem for those manufacturers that refine ferritic stainless steel melts in an argon oxygen decarburization vessel. Nitrogen substantially below 0.010% can be obtained when refining the stainless steel in an argon oxygen decarburization vessel thereby allowing increased amount of titanium to be tolerated and still be at sub-equilibrium.
- sufficient time after adding the titanium to the melt should elapse to allow the titanium oxide inclusions to form before casting the melt. If the melt is cast immediately after adding titanium, the as-cast structure of the casting can include larger columnar grains. The amount of time that should elapse can be determined by one of ordinary skill in the art without undue experimentation. Ingots cast in the laboratory less than 5 minutes after adding the titanium to the melt had large as-cast columnar grains even when the product of titanium and nitrogen divided by residual aluminum was at least 0.14.
- Sufficient nitrogen should be present in the steel prior to casting so that the ratio of the product of titanium and nitrogen divided by aluminum is at least 0.14.
- the amount of nitrogen present in the melt is ⁇ 0.020%.
- nitrogen concentrations after melting in an electric arc furnace may be as high as 0.05%
- the amount of dissolved N can be reduced during argon gas refining in an argon oxygen decarburization vessel to less than 0.02%. Precipitation of excessive TiN can be avoided by reducing the sub-equilibrium amount of Ti to be added to the melt for any given nitrogen content.
- the amount of nitrogen in the melt can be reduced in an argon oxygen decarburization vessel for an anticipated amount of Ti contained in the melt.
- Total residual aluminum can be controlled or minimized relative to the amounts of titanium and nitrogen.
- Minimum amounts of titanium and nitrogen must be present in the melt relative to the aluminum.
- the ratio of the product of titanium and nitrogen divided by residual aluminum at least 0.14 and at least 0.23 in some embodiments.
- the amount of aluminum is ⁇ 0.020%. In some embodiments, the amount of aluminum is ⁇ 0.013% and in other embodiments, it is reduced to ⁇ 0.010%. If aluminum is not purposefully alloyed with the melt during refining or casting such as for deoxidation immediately prior to casting, total aluminum should be controlled or reduced to less than 0.020%.
- Titanium alloys may contain as much as 20% Al which may contribute total Al to the melt.
- stabilizing elements may also include columbium, vanadium or mixtures thereof.
- this second stabilizing element may be limited to ⁇ 0.50% when deep formability is required.
- the invention includes columbium in concentrations of 0.5% or less. Some embodiments include columbium in concentrations of 0.28 - 0.43%. Vanadium can be present in amounts less than 0.5%. Some embodiments of the ferritic stainless steels include 0.008 - 0.098% vanadium.
- the ferritic stainless steels contain 1.0 - 2.0% copper. Some embodiments include 1.16-1.31% copper.
- Silicon is generally present in the ferritic stainless steels in an amount of 1.0 - 1.7%. In some embodiments, silicon is present in an amount of 1.27 - 1.35%. A small amount of silicon generally is present in a ferritic stainless steel to promote formation of the ferrite phase. Silicon also enhances high temperature oxidation resistance and provides high temperature strength. In most embodiments, silicon does not exceed about 1.7% because the steel can become too hard and the elongation can be adversely affected.
- Manganese is present in the ferritic stainless steel in an amount of 0.4 - 1.5%. In some embodiments, manganese is present in an amount of 0.97 - 1.00%. Manganese improves oxidation resistance and spalling resistance at high temperatures. Accordingly, some embodiments include manganese in amounts of at least 0.4%. However, manganese is an austenite former and affects the stabilization of the ferrite phase. If the amount of manganese exceeds about 1.5%, the stabilization and formability of the steel can be affected.
- Carbon is present in the ferritic stainless steel in an amount of up to 0.02%. In some embodiments, the carbon content is ⁇ 0.02%. In still other embodiments, it is 0.0054-0.0133%.
- Chromium is present in some embodiments of the ferritic stainless steels in an amount of 15-20%. If chromium is greater than about 25%, the formability of the steel can be reduced.
- oxygen is present in the steel in an amount ⁇ 100 ppm.
- oxygen in the melt can be within the range of 10-60 ppm thereby providing a very clean steel having small titanium oxide inclusions that aid in forming the nucleation sites responsible for the fine as-cast equiaxed grain structure.
- Sulfur is present in the ferritic stainless steel in an amount of ⁇ 0.01%.
- Phosphorus can deteriorate formability in hot rolling and can cause pitting. It is present in the ferritic stainless steel in an amount of ⁇ 0.05%.
- nickel is an austenite former and affects the stabilization of the ferrite phase. Accordingly, in some embodiments, nickel is limited to ⁇ 1.0%. In some embodiments, nickel is present in amounts of 0.13- 0.19%.
- Molybdenum also improves corrosion resistance. Some embodiments include 3.0% or less molybdenum. Some embodiments include 0.03 - 0.049% molybdenum.
- boron in the steels of the present invention in an amount of ⁇ 0.010%. In some embodiments, boron is present in an amount of 0.0001 - 0.002%. Boron can improve the resistance to secondary work embrittlement of steel so that the steel sheet will be less likely to split during deep drawing applications and multi-step forming applications.
- the ferritic stainless steels may also include other elements known in the art of steelmaking that can be present as residual elements, i.e ., impurities from steelmaking process.
- Embodiments of the ferritic stainless steels and comparative reference steels were made with the compositions set forth in Table 1 below.
- HT #831187 is Type 444 stainless steel
- HT #830843 is 15 CrCb stainless steel, which is a product of AK Steel Corporation, West Chester, Ohio.
- the oxidation resistance of several of several of the steel compositions described in Example 1 and Table 1 above was tested at 930°C for 200 hours in air.
- the results of the tests are set forth in Table 2 below.
- the individual compositions are each identified by their respective ID number.
- the oxidation resistance was evaluated using two factors. One was the amount of weight gain, and the other was degree of spalling. For each material, except HT #920097, the reported weight gain value is an average of two tests. For HT #920097, eight samples were tested and the minimum, average, and maximum of these eight tests has been reported. Table 2 Oxidation resistance test results at 930°C for 200 hours in air.
- HT #930354 One plant produced hot band coil with the composition set forth in Table 1 (HT #930354, CL #681158-03) was finish-processed without hot band annealing to 1.5 mm gauge.
- a hot band annealing step was included, the plant-produced coils of HT#930354 resulted in r-bar values of 1.34, 1.31, 1.38, and 1.34, as shown in Table 5.
- the hot band annealing step was not included, it resulted in higher r-bar of 1.46, as shown by Table 7 below.
- Table 7 -Longitudinal tensile properties (ASTM E8/E8M), stretch r-values, and ridging resistances.
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PL13759947T PL2890825T3 (pl) | 2012-08-31 | 2013-08-28 | Ferrytyczne stale nierdzewne o doskonałej odporności na utlenianie z dobrą wytrzymałością na wysokie temperatury i dobrą odkształcalnością |
SI201331448T SI2890825T1 (sl) | 2012-08-31 | 2013-08-28 | Feritno nerjavno jeklo z odlično odpornostjo proti oksidaciji, dobro trdnostjo pri visokih temperaturah in dobro oblikovalnostjo |
RS20190532A RS58807B1 (sr) | 2012-08-31 | 2013-08-28 | Feritni nerđajući čelik sa odličnom otpornošću na oksidaciju, dobrom izdržljivošću na visoku temperaturu, i dobre obradivosti |
HRP20190864TT HRP20190864T1 (hr) | 2012-08-31 | 2019-05-09 | Feritni nehrđajući čelik s odličnom otpornošću na oksidaciju, dobrom otpornošću na visoke temperature i dobrom formabilnošću |
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US201261695771P | 2012-08-31 | 2012-08-31 | |
US13/837,500 US20140065005A1 (en) | 2012-08-31 | 2013-03-15 | Ferritic Stainless Steel with Excellent Oxidation Resistance, Good High Temperature Strength, and Good Formability |
PCT/US2013/056999 WO2014036091A1 (en) | 2012-08-31 | 2013-08-28 | Ferritic stainless steel with excellent oxidation resistance, good high temperature strength, and good formability |
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US (2) | US20140065005A1 (ru) |
EP (1) | EP2890825B1 (ru) |
JP (1) | JP6194956B2 (ru) |
KR (2) | KR20150080485A (ru) |
CN (2) | CN104769147A (ru) |
AU (1) | AU2013308922B2 (ru) |
BR (1) | BR112015004228A2 (ru) |
CA (1) | CA2882361C (ru) |
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HR (1) | HRP20190864T1 (ru) |
HU (1) | HUE043997T2 (ru) |
MX (1) | MX2015002677A (ru) |
MY (1) | MY172722A (ru) |
PL (1) | PL2890825T3 (ru) |
RS (1) | RS58807B1 (ru) |
RU (1) | RU2650467C2 (ru) |
SI (1) | SI2890825T1 (ru) |
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US20140065005A1 (en) * | 2012-08-31 | 2014-03-06 | Eizo Yoshitake | Ferritic Stainless Steel with Excellent Oxidation Resistance, Good High Temperature Strength, and Good Formability |
EP3333277B1 (en) | 2015-08-05 | 2019-04-24 | Sidenor Investigación y Desarrollo, S.A. | High-strength low-alloy steel with high resistance to high-temperature oxidation |
CN107675075A (zh) * | 2017-09-05 | 2018-02-09 | 王业双 | 一种高性能耐高温铁素体不锈钢及其制备方法 |
JP6420893B1 (ja) * | 2017-12-26 | 2018-11-07 | 日新製鋼株式会社 | フェライト系ステンレス鋼 |
WO2021126518A1 (en) * | 2019-12-18 | 2021-06-24 | Oerlikon Metco (Us) Inc. | Iron-based high corrosion and wear resistance alloys |
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CA899A (en) * | 1871-03-24 | D. Cameron | Composition of matter for making fire brick, and in the art of burning the same | |
JPH01165752A (ja) * | 1987-12-22 | 1989-06-29 | Kawasaki Steel Corp | 高濃度ハロゲン化物中で優れた耐食性を有するフェライト系ステンレス鋼 |
JPH02115346A (ja) * | 1988-10-21 | 1990-04-27 | Kawasaki Steel Corp | 高濃度ハロゲン化物中で優れた耐食性を有するフェライト系ステンレス鋼 |
US5426039A (en) * | 1993-09-08 | 1995-06-20 | Bio-Rad Laboratories, Inc. | Direct molecular cloning of primer extended DNA containing an alkane diol |
FR2720410B1 (fr) * | 1994-05-31 | 1996-06-28 | Ugine Savoie Sa | Acier inoxydable ferritique à usinabilité améliorée. |
JP3439866B2 (ja) * | 1995-03-08 | 2003-08-25 | 日本冶金工業株式会社 | 耐食性および溶接性に優れるフェライト系ステンレス鋼 |
US6426039B2 (en) * | 2000-07-04 | 2002-07-30 | Kawasaki Steel Corporation | Ferritic stainless steel |
JP3886785B2 (ja) * | 2001-11-22 | 2007-02-28 | 日新製鋼株式会社 | 石油系燃料改質器用フェライト系ステンレス鋼 |
JP3942876B2 (ja) * | 2001-11-22 | 2007-07-11 | 日新製鋼株式会社 | 炭化水素系燃料改質器用フェライト系ステンレス鋼 |
JP3989790B2 (ja) * | 2002-07-30 | 2007-10-10 | 新日鐵住金ステンレス株式会社 | プレス成形性に優れたフェライト系ステンレス鋼板及びその製造方法 |
JP3920185B2 (ja) * | 2002-09-27 | 2007-05-30 | 日新製鋼株式会社 | 耐たわみ性に優れたステンレス鋼製の二輪車用タイヤリム材および二輪車用フレーム材 |
JP4463663B2 (ja) * | 2004-11-04 | 2010-05-19 | 日新製鋼株式会社 | 耐高温水蒸気酸化性に優れたフェライト系鋼材およびその使用方法 |
JP5236158B2 (ja) * | 2005-01-26 | 2013-07-17 | 日本ウエルディング・ロッド株式会社 | フェライト系ステンレス鋼溶接ワイヤ及びその製造方法 |
US7732733B2 (en) * | 2005-01-26 | 2010-06-08 | Nippon Welding Rod Co., Ltd. | Ferritic stainless steel welding wire and manufacturing method thereof |
JP4302678B2 (ja) * | 2005-09-01 | 2009-07-29 | 日新製鋼株式会社 | 燃料タンク用フェライト系ステンレス鋼板 |
JP4761993B2 (ja) * | 2006-02-14 | 2011-08-31 | 日新製鋼株式会社 | スピニング加工用フェライト系ステンレス鋼溶接管の製造法 |
JP4948998B2 (ja) * | 2006-12-07 | 2012-06-06 | 日新製鋼株式会社 | 自動車排ガス流路部材用フェライト系ステンレス鋼および溶接鋼管 |
JP5349153B2 (ja) * | 2009-06-15 | 2013-11-20 | 日新製鋼株式会社 | ろう付け用フェライト系ステンレス鋼材および熱交換器部材 |
RU2415963C2 (ru) * | 2009-07-13 | 2011-04-10 | Открытое акционерное общество "Научно-производственное объединение "Центральный научно-исследовательский институт технологии машиностроения", ОАО НПО "ЦНИИТМАШ" | Жаростойкая сталь |
KR20180017220A (ko) * | 2010-09-16 | 2018-02-20 | 닛폰 스틸 앤드 스미킨 스테인레스 스틸 코포레이션 | 내산화성이 우수한 내열 페라이트계 스테인리스 강판 |
US20140065005A1 (en) * | 2012-08-31 | 2014-03-06 | Eizo Yoshitake | Ferritic Stainless Steel with Excellent Oxidation Resistance, Good High Temperature Strength, and Good Formability |
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2013
- 2013-03-15 US US13/837,500 patent/US20140065005A1/en not_active Abandoned
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- 2013-08-28 CN CN201380045477.5A patent/CN104769147A/zh active Pending
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- 2013-08-28 CN CN201810791340.9A patent/CN108823509A/zh active Pending
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US20140065005A1 (en) | 2014-03-06 |
KR20200028502A (ko) | 2020-03-16 |
JP6194956B2 (ja) | 2017-09-13 |
JP2015532684A (ja) | 2015-11-12 |
CN104769147A8 (zh) | 2018-10-09 |
CA2882361C (en) | 2019-06-18 |
CN108823509A (zh) | 2018-11-16 |
SI2890825T1 (sl) | 2019-06-28 |
CA2882361A1 (en) | 2014-03-06 |
EP2890825A1 (en) | 2015-07-08 |
CN104769147A (zh) | 2015-07-08 |
AU2013308922A1 (en) | 2015-03-05 |
KR20150080485A (ko) | 2015-07-09 |
BR112015004228A2 (pt) | 2017-07-04 |
MX2015002677A (es) | 2015-05-12 |
HRP20190864T1 (hr) | 2019-06-28 |
HUE043997T2 (hu) | 2019-09-30 |
US20140065006A1 (en) | 2014-03-06 |
RU2015108849A (ru) | 2016-10-20 |
RU2650467C2 (ru) | 2018-04-13 |
RS58807B1 (sr) | 2019-07-31 |
WO2014036091A1 (en) | 2014-03-06 |
MY172722A (en) | 2019-12-11 |
PL2890825T3 (pl) | 2019-09-30 |
ZA201502075B (en) | 2016-03-30 |
AU2013308922B2 (en) | 2016-08-04 |
ES2728229T3 (es) | 2019-10-23 |
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