EP3670692A1 - Ferritischer edelstahl - Google Patents
Ferritischer edelstahl Download PDFInfo
- Publication number
- EP3670692A1 EP3670692A1 EP18215480.7A EP18215480A EP3670692A1 EP 3670692 A1 EP3670692 A1 EP 3670692A1 EP 18215480 A EP18215480 A EP 18215480A EP 3670692 A1 EP3670692 A1 EP 3670692A1
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- EP
- European Patent Office
- Prior art keywords
- ferritic stainless
- stainless steel
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- weight
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 50
- 239000010936 titanium Substances 0.000 claims abstract description 84
- 239000010955 niobium Substances 0.000 claims abstract description 80
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 49
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 26
- 239000010959 steel Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 22
- 239000011651 chromium Substances 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011733 molybdenum Substances 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims 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 claims abstract description 7
- 238000005261 decarburization Methods 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 description 31
- 239000000956 alloy Substances 0.000 description 31
- 230000006641 stabilisation Effects 0.000 description 27
- 238000011105 stabilization Methods 0.000 description 26
- 229910001068 laves phase Inorganic materials 0.000 description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 238000005275 alloying Methods 0.000 description 8
- 238000003466 welding Methods 0.000 description 8
- 239000012925 reference material Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 titanium nitrides Chemical class 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000001247 metal acetylides Chemical group 0.000 description 2
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical group 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 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
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000001761 ethyl methyl cellulose Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VCTOKJRTAUILIH-UHFFFAOYSA-N manganese(2+);sulfide Chemical class [S-2].[Mn+2] VCTOKJRTAUILIH-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- UXIGZRQVLGFTOU-VQXQMPIVSA-N remikiren Chemical compound C([C@H](CS(=O)(=O)C(C)(C)C)C(=O)N[C@@H](CC=1NC=NC=1)C(=O)N[C@@H](CC1CCCCC1)[C@@H](O)[C@@H](O)C1CC1)C1=CC=CC=C1 UXIGZRQVLGFTOU-VQXQMPIVSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
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
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- 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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—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
- C22C38/40—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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- 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
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
-
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
Definitions
- This invention relates to a stabilized ferritic stainless steel having good corrosion resistance, good weldability and enhanced high temperature strength for use in high temperature service in components used in applications such as automotive exhaust systems, fuel cells and other energy sector applications, appliances, furnaces and other industrial high temperature systems.
- the most critical point in developing ferritic stainless steel is how to take care of carbon and nitrogen elements. These elements have to be bound to carbides, nitrides or carbonitrides.
- the elements used in this type of binding are called stabilizing elements.
- the common stabilizing elements are niobium and titanium.
- the requirements for stabilization of carbon and nitrogen can be diminished for ferritic stainless steels where for instance the carbon content is very low, less than 0.01 weight %. However, this low carbon content causes requirements for the manufacturing process.
- the common AOD (Argon-Oxygen-Decarburization) producing technology for stainless steels is not any more practical and, therefore, more expensive producing methods shall be used, such as the VOD (Vacuum-Oxygen-Decarburization) producing technology.
- Intermetallic Laves phase particles which may form in ferritic stainless steel, increase the high temperature strength of the steel provided that the particles remain small and stable in the operating temperatures. Additionally, Laves phase particles, precipitated inside grains and on grain boundaries, also inhibit grain growth. Alloying of a balanced combination of niobium, silicon and titanium in ferritic stainless steel promotes precipitation of intermetallic Laves phase and stabilizes the phase by increasing the dissolution temperature of precipitates.
- the microstructure formed in the weld depends on the chemical composition of weld metal.
- the compounds formed during the stabilization such as TiN, produce an equiaxed, fine grained structure in welds.
- the equiaxed, fine grained structure improves the ductility and toughness of the welds. Unwanted columnar grains can cause hot cracking as impurities may segregate to the weld centreline. Large columnar grains also decrease the toughness of the weld.
- the EP patent 1818422 describes a niobium stabilized ferritic stainless steel having, among others, less than 0.03 weight % carbon, 18 - 22 weight % chromium, less than 0.03 weight % nitrogen and 0.2 - 1.0 weight % niobium. In accordance with this EP patent the stabilization of carbon and nitrogen is carried out using only niobium.
- the EP patent application 2163658 describes a ferritic stainless steel with sulfate corrosion resistance containing less than 0.02 % carbon, 0.05-0.8 % silicon, less than 0.5 % manganese, 20-24 % chromium, less than 0.5 % nickel, 0.3-0.8 % copper, less than 0.02 % nitrogen, 0.20-0.55 % niobium, less than 0.1 % aluminium and the balance being iron and inevitable impurities. In this ferritic stainless only niobium is used in the stabilization of carbon and nitrogen.
- the WO publication 2012046879 relates to a ferritic stainless steel to be used for a separator of a proton-exchange membrane fuel cell.
- a passivation film is formed on the surface of the stainless steel by immersing the stainless steel in a solution containing mainly hydrofluoric acid or a liquid mixture of hydrofluoric acid and nitric acid.
- the ferritic stainless steel contains carbon, silicon, manganese, aluminium, nitrogen, chromium and molybdenum in addition to iron as the necessary alloying elements. All other alloying elements described in the reference WO 2012046879 are optional.
- the ferritic stainless steel having a low carbon content is produced by vacuum smelting, which is a very expensive manufacturing method.
- EP1083241 describes niobium stabilized ferritic chromium steel strip, produced from a steel having specified molybdenum, silicon and tin contents and containing a cubic iron-niobium phase as the sole intermetallic phase at high temperature.
- a niobium stabilized ferritic 14% chromium steel strip is produced from a steel of composition (by wt.) ⁇ 0.02% C, 0.002-0.02% N, 0.05-1% Si, greater than 0 to 1% Mn, 0.2-0.6% Nb, 13.5-16.5% Cr, 0.02-1.5% Mo, greater than 0 to 1.5% Cu, greater than 0 to 0.2% Ni, greater than 0 to 0.020% P, greater than 0 to 0.003% S, greater than 0.005 to 0.04% Sn, balance Fe and impurities, the Nb, C and N contents satisfying the relationship Nb/(C + N) ⁇ 9.5, by: (a) reheating before hot rolling at 1150-1250 (preferably 1175) degrees C; (b) coiling at 600-800 (preferably 600) degrees C; (c) cold rolling, optionally after pre-annealing; and (d) final annealing at 800-1100 (preferably 1050) degrees C for 1-5 (preferably 2) min.
- An independent claim
- EP1170392 describes ferritic stainless steel comprising all three of Co, V, and B, having a Co content of about 0.01 mass% to about 0.3 mass%, a V content of about 0.01 mass% to about 0.3 mass%, and a B content of about 0.0002 mass% to about 0.0050 mass%, and having superior secondary working embrittleness resistance and superior high temperature fatigue characteristics.
- Further components are (in mass%): 0.02% or less of C, 0.2 to 1.0% Si, 0.1 to 1.5% Mn, 0.04% or less of P, 0.01% or less of S, 11.0 to 20.0% of Cr, 0.1 to 1.0% Ni, 1.0 to 2.0% Mo, 1.0% or less of Al, 0.2 to 0.8% of Nb, 0.02% or less of N and optionally 0.05 to 0.5% Ti, Zr or Ta, 0.1 to 2.0% Cu, 0.05 to 1.0% W, 0.001 to 0.1% Mg and 0.0005 to 0.005% Ca.
- US patent 4726853 concerns a strip or sheet of ferritic stainless steel, usually in the annealed state, the final annealing operation then being followed in most cases by a finishing and cold-working pass or "skin pass", producing a degree of elongation of less than 1%, intended in particular for the production of exhaust pipes and manifolds.
- the composition of the strip or sheet is as follows (% by weight):
- EP2557189 describes ferritic stainless steel sheet for an exhaust part which has little deterioration in strength even if undergoing long term heat history and is low in cost, excellent in heat resistance and workability characterized by containing, characterized by containing, by mass%, C: less than 0.010%, N: 0.020% or less, Si: over 0.1% to 2.0%, Mn: 2.0% or less, Cr: 12.0 to 25.0%, Cu: over 0.9 to 2%, Ti: 0.05 to 0.3%, Nb: 0.001 to 0.1%, Al: 1.0% or less, and B: 0.0003 to 0.003%, having a Cu/(Ti+Nb) of 5 or more, and having a balance of Fe and unavoidable impurities.
- the object of the present invention is to eliminate some drawbacks of the prior art and to achieve a ferritic stainless steel having good corrosion resistance, improved weldability and enhanced high temperature strength, which steel is stabilized by niobium, titanium and vanadium and is produced using AOD (Argon-Oxygen-Decarburization) technology.
- AOD Aron-Oxygen-Decarburization
- the chemical composition of the ferritic stainless steel according to the invention consists of in weight % 0.003 - 0.035 % carbon, 0.05 - 1.0 % silicon, 0.10 - 0.8 % manganese, 18 - 24 % chromium, 0.05 - 0.8 % nickel, 0.003 - 2.5 % molybdenum, 0.2 - 0.8 % copper, 0.003 - 0.05 % nitrogen, 0.05 - 1.0 % titanium, 0.05 - 1.0 % niobium, 0.03 - 0.5 % vanadium, 0.01 - 0.04 % aluminium, and the sum C+N less than 0.06 %, the rest being iron and evitable impurities occupying in stainless steels, in such conditions that the sum of (C+N) is less than 0.06 % and the ratio (Ti+Nb)/(C+N) is higher or equal to 8, and less than 40, and the ratio (Ti + 0.515*Nb +0.940*V)
- Carbon (C) decreases elongation and r-value and, preferably, carbon is removed as much as possible during the steel making process.
- the solid-solution carbon is fixed as carbides by titanium, niobium and vanadium as described below.
- the carbon content is limited to 0.035 %, preferably to 0.03 %, but having at least of 0.003 % carbon.
- Silicon (Si) is used to reduce chromium from slag back to melt. Some silicon remainders in steel are necessary to make sure that reduction is done well. In the solid solution, silicon boosts formation of Laves phases and stabilizes Laves phase particles at higher temperatures. Therefore, the silicon content is less than 1.0 %, but at least 0.05 %.
- Manganese (Mn) degrades the corrosion resistance of ferritic stainless steel by forming manganese sulphides. With low sulphur (S) content the manganese content is less than 0.8 %, preferable less than 0.65 %, but at least 0.10 %.
- Chromium (Cr) enhances oxidation resistance and corrosion resistance.
- the chromium content must be 18 - 24 %, preferably 20 - 22 %.
- Nickel (Ni) is an element favourably contributing to the improvement of toughness, but nickel has sensitivity to stress corrosion cracking (SCC). In order to consider these effects the nickel content is less than 0.8 %, preferably less than 0.5 % so that the nickel content is at least 0.05 %.
- Molybdenum enhances corrosion resistance but reduces elongation to fracture.
- the molybdenum content is less than 2.5 %, but at least 0.003%.
- the molybdenum content is preferably less than 2.5% but at least 0.5%.
- the more preferable range is 0.003% - 0.5% molybdenum.
- Copper (Cu) improves corrosion resistance in acidic solutions, but high copper content can be harmful.
- the copper content is thus less than 0.8 %, preferably less than 0.5 %, but at least 0.2 %.
- Nitrogen (N) reduces elongation to fracture.
- the nitrogen content is less than 0.05 %, preferably less than 0.03 %, but at least 0.003 %.
- Aluminium is used to remove oxygen from melt.
- the aluminium content is less than 0.04 %.
- Titanium (Ti) is very useful because it forms titanium nitrides with nitrogen at very high temperatures. Titanium nitrides prevent grain growth during annealing and welding. In welds, titanium alloying promotes the formation of equiaxed, fine grained structure. Titanium is the cheapest element of chosen stabilization elements titanium, vanadium and niobium. Therefore, using titanium for stabilization is an economic choice.
- the titanium content is less than 1.0 %, but at least 0.05 %. The more preferable range is 0.07% - 0.40% titanium.
- Niobium (Nb) is used to some extent to bind carbon to niobium carbides. With niobium the recrystallization temperature can be controlled. Niobium stimulates precipitation of Laves phases particles and has positive effect their stability at high temperatures. Niobium is the most expensive element of chosen stabilization elements titanium, vanadium and niobium. The niobium content is less than 1.0 %, but at least 0.05 %.
- Vanadium (V) forms carbides and nitrides at lower temperatures. These precipitations are small and major part of them is usually inside grains. Amount of vanadium needed to carbon stabilization is only about half of amount of niobium needed to same carbon stabilization. This is because vanadium atomic weight is only about a half of niobium atomic weight. Vanadium is economic choice for stabilization element since vanadium is cheaper than niobium. Vanadium also improves toughness of steel. The vanadium content is less than 0.5 %, but at least 0.03 % preferably 0.03 - 0.20 %.
- the alloy A has smaller amount of niobium and silicon compared to the other alloys from B to H.
- the alloys B, C and D have the same amount of niobium, while the amount of silicon is increasing gradually from the alloy B to C and to alloy D.
- the alloy E has essentially the same chemical composition as the alloy D except for small variations in the amounts of silicon, titanium and niobium.
- the alloy F has essentially the same amount of silicon as the alloy C, while the niobium content of alloy F is the highest among all alloys from A to H.
- the alloys G and H contain also molybdenum in addition to silicon, titanium and niobium. All alloys A - H are triple stabilized with titanium, niobium and vanadium in accordance with the invention.
- the compounds which are generated during the stabilization are such as titanium carbide (TiC), titanium nitride (TiN), niobium carbide (NbC), niobium nitride (NbN), vanadium carbide (VC) and vanadium nitride (VN).
- TiC titanium carbide
- TiN titanium nitride
- NbC niobium carbide
- NbN niobium nitride
- VN vanadium carbide
- Ti eq Ti + 0.515 * Nb + 0.940 * V
- the ratio Ti eq /C eq is used as one factor for determining the disposition for sensitization, and the ratio Ti eq /C eq is higher or equal to 6 and the ratio (Ti+Nb)/(C+N) higher or equal to 8 for the ferritic stainless steel of the invention in order to avoid the sensitization.
- the EP patent EP292278B gives additional information regarding sensitization to grain boundary corrosion. In this document it is shown that stabilization against intergranular corrosion is successful if Ti eq /C eq is higher or equal to 6 and (Ti+Nb)/(C+N) higher or equal to 8.
- the enhanced high temperature strength of invented steel is ensured by fine dispersion of thermodynamically stable Laves phase particles.
- the alloying of Nb, Ti and Si must be carefully balanced in order to obtain an optimal microstructure for high service temperatures.
- the correct alloying promotes precipitation of Laves phase particles and raises their dissolution temperature.
- the Laves phase particles are formed quickly in exposure to temperatures in the range from 650 to 850°C.
- Figure 2 illustrates intergranular and intragranular precipitates observed in the alloys A to H when the material was exposed to the temperature of 800°C for 30 minutes. Chemical composition of precipitated particles was determined by means of by energy dispersive spectrometry (EDS). The results in table 2 reveal that particles formed in the steel of invention are Laves phase precipitates.
- EDS energy dispersive spectrometry
- the chemical composition of precipitated particles in the steel of invention follows the model A 2 B, where A is a combination of Fe and of Cr and B is a combination of Nb, Si and Ti.
- A is a combination of Fe and of Cr
- B is a combination of Nb, Si and Ti.
- the chemical formula of the Laves phase particles is (Fe 0.8 Cr 0.2 ) 2 (Nb 0.70 Si 0.25 Ti 0.05 ).
- the number of Fe, Cr, Nb, Si and Ti atoms in the molecule depend on alloying and on heat cycles experienced by the material.
- Table 2 Chemical composition of 10 Laves phase particles in the steel of the invention according to energy dispersive spectrometry (EDS).
- a balanced combination of silicon, niobium and titanium ensures that the steel contains sufficient amount Laves phase particles in high service temperatures above 900°C.
- Laves phase equivalent number L eq is higher or equal to 3.3 for the ferritic stainless steel of the invention in order to guarantee enhanced high temperature strength properties.
- Laves phase equivalent corresponds to the lower boundary of the region indicated order to guarantee enhanced high temperature strength properties.
- Laves phase equivalent number L eq is higher or equal to 4.5.
- the dissolution of precipitated Laves phase determines the upper limit for the service temperature for the ferritic stainless steels of the invention.
- the dissolution temperature was calculated using thermodynamic simulation software Thermo-Calc version 2018b for the alloys of table 1. The results are presented in table 4.
- the values for the dissolution temperature are favourable and above the target service temperature of 900°C for the alloys A - H.
- the dissolution temperatures are unfavourably below the target temperature of 900°C for the reference materials.
- Alloy Tsol (°C) Invention A 929 B 986 C 1003 D 1013 E 1009 F 1039 G 1009 H 1009 Reference EN 1.4509 849 EN 1.4622 839
- the mechanical strength Rm is considered insufficient when Rm ⁇ 30MPa at 950°C or Rm ⁇ 20 MPa at 1000°C.
- the results in the table 5 show that the steels in accordance with the invention satisfy these requirements whereas the reference materials EN 1.4509 and EN 1.4622 do not satisfy these requirements.
- the pitting corrosion potential of all the alloys listed in the table 1 was determined potentiodynamically.
- the alloys were wet ground with 320 mesh and allowed to repassivate in air at ambient temperature for at least 24 hours.
- the pitting potential measurements were done in naturally aerated aqueous 1.2 wt-% NaCI-solution (0.7 wt-% CI-, 0.2 M NaCI) at room temperature of about 22°C.
- the polarization curves were recorded at 20 mV/min using crevice-free flushed-port cells (Avesta cells as described in ASTM G150) with an electrochemically active area of about 1 cm 2 .
- Platinum foils served as counter electrodes.
- KCl saturated calomel electrodes (SCE) were used as reference electrodes. The average value of six breakthrough pitting potential measurements for each alloy was calculated and is listed in table 2.
- the equiaxial, fine grained structure of welds is ensured if a sufficient amount of titanium is used for stabilization.
- the compounds formed by titanium in the liquid weld metal, such as TiN act as nucleation sites for heterogenous solidification resulting in equiaxed, fine grained structure in welds.
- the other elements used for stabilization, vanadium and niobium do not form compounds that will act as nucleation sites in the liquid metal. Therefore, a coarse-grained weld with columnar grain structure results if the amount of titanium is not sufficiently high enough.
- the coarse-grained, columnar structure can cause hot cracking as impurities may segregate to the weld centreline. Large columnar grains also decrease the toughness of the weld.
- Figure 3 shows an illustrative example of coarse-grained, columnar weld structure obtained in autogenous welding when insufficient amount of titanium is alloyed in the steel.
- Figure 4 shows an example of fine-grained, equiaxial weld structure obtained in autogenous welding when sufficient amount of titanium was alloyed in the steel.
- the alloys A-H according to the invention and the reference materials EN 1.4509 and 1.4622 have favourable amount of titanium in order to produce fine-grained equiaxial weld structure in autogenous welding.
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SI201830780T SI3670692T1 (sl) | 2018-12-21 | 2018-12-21 | Feritno nerjavno jeklo |
ES18215480T ES2927078T3 (es) | 2018-12-21 | 2018-12-21 | Acero inoxidable ferrítico |
EP18215480.7A EP3670692B1 (de) | 2018-12-21 | 2018-12-21 | Ferritischer edelstahl |
PCT/EP2019/085663 WO2020127275A1 (en) | 2018-12-21 | 2019-12-17 | Ferritic stainless steel |
KR1020217018178A KR20210107657A (ko) | 2018-12-21 | 2019-12-17 | 페라이트계 스테인리스 강 |
BR112021011181-6A BR112021011181A2 (pt) | 2018-12-21 | 2019-12-17 | Aço inoxidável ferrítico |
JP2021535108A JP7464606B2 (ja) | 2018-12-21 | 2019-12-17 | フェライト系ステンレス鋼の製造方法 |
CN201980083092.5A CN113195762A (zh) | 2018-12-21 | 2019-12-17 | 铁素体不锈钢 |
AU2019406425A AU2019406425A1 (en) | 2018-12-21 | 2019-12-17 | Ferritic stainless steel |
US17/309,717 US20220056565A1 (en) | 2018-12-21 | 2019-12-17 | Ferritic stainless steel |
CA3122043A CA3122043A1 (en) | 2018-12-21 | 2019-12-17 | Ferritic stainless steel |
MX2021006953A MX2021006953A (es) | 2018-12-21 | 2019-12-17 | Acero inoxidable ferritico. |
TW108146912A TW202035732A (zh) | 2018-12-21 | 2019-12-20 | 肥粒鐵不鏽鋼 |
ZA2021/03639A ZA202103639B (en) | 2018-12-21 | 2021-05-27 | Ferritic stainless steel |
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CN (1) | CN113195762A (de) |
AU (1) | AU2019406425A1 (de) |
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CA (1) | CA3122043A1 (de) |
ES (1) | ES2927078T3 (de) |
MX (1) | MX2021006953A (de) |
SI (1) | SI3670692T1 (de) |
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CN113699428A (zh) * | 2021-07-19 | 2021-11-26 | 北京科技大学 | 减少TP321不锈钢无缝管分层缺陷的Ti合金化工艺 |
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- 2019-12-17 MX MX2021006953A patent/MX2021006953A/es unknown
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- 2019-12-17 CN CN201980083092.5A patent/CN113195762A/zh active Pending
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CN113699428A (zh) * | 2021-07-19 | 2021-11-26 | 北京科技大学 | 减少TP321不锈钢无缝管分层缺陷的Ti合金化工艺 |
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CA3122043A1 (en) | 2020-06-25 |
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WO2020127275A1 (en) | 2020-06-25 |
ES2927078T3 (es) | 2022-11-02 |
EP3670692B1 (de) | 2022-08-10 |
CN113195762A (zh) | 2021-07-30 |
TW202035732A (zh) | 2020-10-01 |
US20220056565A1 (en) | 2022-02-24 |
ZA202103639B (en) | 2023-11-29 |
BR112021011181A2 (pt) | 2021-08-24 |
JP7464606B2 (ja) | 2024-04-09 |
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