WO2024013542A1 - Acier laminé à chaud et son procédé de fabrication - Google Patents
Acier laminé à chaud et son procédé de fabrication Download PDFInfo
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- WO2024013542A1 WO2024013542A1 PCT/IB2022/056421 IB2022056421W WO2024013542A1 WO 2024013542 A1 WO2024013542 A1 WO 2024013542A1 IB 2022056421 W IB2022056421 W IB 2022056421W WO 2024013542 A1 WO2024013542 A1 WO 2024013542A1
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- Prior art keywords
- hot rolled
- rolled steel
- steel
- temperature
- anyone
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 120
- 239000010959 steel Substances 0.000 title claims abstract description 120
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 239000010955 niobium Substances 0.000 claims abstract description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 20
- 238000005496 tempering Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 12
- 238000005098 hot rolling Methods 0.000 claims description 7
- 229910001005 Ni3Al Inorganic materials 0.000 claims description 3
- 238000003303 reheating Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000011265 semifinished product Substances 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 22
- 229910001240 Maraging steel Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 238000009749 continuous casting Methods 0.000 description 4
- 230000001627 detrimental effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- -1 Aluminum Nitrides Chemical class 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
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 229910001563 bainite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007571 dilatometry Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
- C21D1/22—Martempering
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- C—CHEMISTRY; METALLURGY
- 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
- C21D6/02—Hardening by precipitation
-
- 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
- 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
-
- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
- C22C38/18—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
- 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
Definitions
- the present invention relates to hot rolled steel suitable for use under corrosive environment particularly under the environments containing chlorides.
- US20100037994 claims for a method of processing a workpiece of maraging steel comprising receiving a workpiece of maraging steel having a composition comprising 17wt%-19wt% of nickel, 8wt%-12wt% of cobalt, 3wt%-5wt% of molybdenum, 0.2wt%- 1.7wt% of titanium, 0.15wt%-0.15wt% of aluminum, and a balance of iron and that has been subjected to thermomechanical processing at an austenite solutionizing temperature; and directly aging the workpiece of maraging steel at an aging temperature to form precipitates within
- EP2840160 p provide a maraging steel excellent in fatigue characteristics, including, in terms of % by mass: C: ⁇ 0.015%, Ni: from 12.0 to 20.0%, Mo: from 3.0 to 6.0%, Co: from 5.0 to 13.0%, Al: from 0.01 to 0.3%, Ti: from 0.2 to 2.0%, O: ⁇ 0.0020%, N: ⁇ 0.0020%, and Zr: from 0.001 to 0.02%, with the balance being Fe and unavoidable impurities.
- EP2840160 provide adequate strength required but does not provides for a steel that has corrosion resistance in Chloride environment.
- the purpose of the present invention is to solve these problems by making available a hot rolled steel that simultaneously have: - a tensile strength greater than or equal to 1100 MPa and preferably above 1200 MPa, - a hardness of less than or equal to 545 Hv and preferably less than or equal to 535Hv. - a corrosion resistance steel wherein a steel is considered corrosion resistance when the loss of thickness due to corrosion is less than 0.07mm/year and preferably less than 0.06mm/year
- the steel according to the invention may also present a yield strength 850 MPa or more
- such steel can also have a good suitability for forming, in particular for rolling with good weldability and coatability.
- the hot rolled steel sheet of the present invention may optionally be coated to further improve its corrosion resistance.
- the above object and other advantages of the present invention will become more apparent by describing in detail the preferred embodiment of the present invention.
- the chemical composition of the hot rolled martensitic steel comprises of the following elements wherein the each element is denoted by its presence in weight percentage: Nickel is present in the steel from 5% to 16%. Nickel is an essential element for the steel of present invention to impart strength to the steel by forming inter-metallics with Aluminum and Titanium during the heating before tempering.
- Nickel is also effective in suppressing the ferrite phase formation to increase the martensite phase ratio and improving the corrosion resistance. Nickel also plays a pivotal role in formation of reverted austenite during the tempering which restricts the hardness of steel till 550Hv. But Nickel less than will 5% will not be able to be able to impart strength due to the decrease in formation of inter-metallics whereas when Nickel is present more than 16% it will form more than 10% reverted austenite which is also detrimental for the tensile strength of the steel. A preferable content for Nickel for the present invention may be kept from 6% to 15% and more preferably from 6.5% to 14%. Aluminum is an essential element that that constitutes 0.5% to 3% of the Steel of present invention.
- Aluminum increases the strength of the steel of present invention by forming inter-metallics with Nickel and titanium during the tempering.
- Aluminum is an essential element for imparting the corrosion resistance properties to the steel of present invention.
- Further Aluminum is also added to the molten state of the steel to clean steel of present invention by removing oxygen existing in molten steel to prevent oxygen from forming a gas phase.
- Preferable limit for Aluminum is from 0.8% to 2.5% and more preferably from 0.9% to 2%.
- Titanium content of the steel of present invention is from 0.1% to 1%. Titanium forms inter-metallic to impart strength to the steel. If titanium is less than 0.1% the requisite effect is not achieved.
- a preferable content for the present invention may be kept from 0.1% to 0.9% and more preferably from 0.2% to 0.8%.
- Chromium is an essential element that constitutes 4% to 15% of the Steel of present invention. Chromium is an important element for ensuring the corrosion resistance under severe corrosive environments, the stress corrosion cracking resistance. Further, when Chromium assists in effectively transforming the steel microstructure to martensite during the cooling after annealing. To obtain these effects, Cr must be contained at least 4%. However, when the content exceeds 15%, ferrite is easily formed in the metal structure of steel, and it becomes difficult to obtain a martensite structure by quenching. Therefore, the preferred Chromium content is from 5% to 14% and a more preferred range is 6% to 12%. Carbon is present in the steel from 0.0001% to 0.03%. Carbon is a residual element and comes from processing.
- Impurity Carbon below 0.0001% is not possible due to process limitation and presence of Carbon above 0.03 must be avoided as it decreases the corrosion resistance of the steel.
- Phosphorus constituent of the steel of present invention is from 0.002% to 0.02%. Phosphorus reduces the spot weldability and the hot ductility, particularly due to its tendency to segregate at the grain boundaries or co-segregation. For these reasons, its content is limited to 0.02% and preferably lower than 0.015%.
- Sulfur is not an essential element but may be contained as an impurity in steel and from point of view of the present invention the Sulfur content is preferably as low as possible but is 0.005% or less from the viewpoint of manufacturing cost.
- Nitrogen is limited to 0.01% to avoid ageing of material, nitrogen forms the nitrides which impart strength to the steel of present invention by precipitation strengthening with Vanadium and Niobium but whenever the presence of nitrogen is more than 0.01% it can form high amount of Aluminum Nitrides which are detrimental for the present invention hence the preferable upper limit for nitrogen is 0.005%.
- Cobalt is an optional element for the steel of present invention and is present from 0% to 7%. The purpose of adding cobalt is to assist in imparting ductility to the steel.
- cobalt also helps in forming the inter-metallics of Nickel by decreasing the rate Nickel to form solid solution. But when Cobalt is present more than 7% it forms reverted austenite in excess which is detrimental for the strength of the steel.
- a preferable content for Cobalt for the present invention may be kept from 0% to 6% and more preferably from 0% to 5%.
- Molybdenum is an optional element that constitutes 0% to 6% of the Steel of present invention; Molybdenum increases the strength of the steel of present invention by forming inter-metallics with Nickel and titanium during the heating for tempering. Molybdenum assists for achieving the corrosion resistance properties to the steel of present invention.
- Molybdenum excessively increases the cost of the addition of alloy elements, so that for economic reasons its content is limited to 6%.
- Preferable limit for molybdenum is from 0% to 5% and more preferably from 0% to 4%.
- Niobium is an optional element for the present invention. Niobium content may be present in the steel of present invention from 0% to 0.1% and is added in the steel of present invention for forming carbides or carbo-nitrides to impart strength to the steel of present invention by precipitation strengthening.
- Vanadium is an optional element that constitutes from 0% to 0.3% of the steel of present invention.
- Vanadium is effective in enhancing the strength of steel by forming carbides, nitrides or carbo-nitrides and the upper limit is 0.3% due to the economic reasons. These carbides, nitrides or carbo-nitrides are formed during the second and third step of cooling.
- Preferable limit for Vanadium is from 0 % to 0.2%.
- Copper may be added as an optional element in an amount of 0% to 0.5% to increase the strength of the steel and to improve its corrosion resistance. A minimum of 0.01% of Copper is required to get such effect. However, when its content is above 0.5%, it can degrade the surface aspects.
- Manganese content of the steel of present invention is from 0 % to 2%. This element is gammagenous.
- Manganese provides solid solution strengthening and suppresses the ferritic transformation temperature and reduces ferritic transformation rate hence assist in the formation of martensite. But when Manganese content is more than 2% it produces adverse effects such as it retards transformation of Austenite to Martensite during cooling after annealing. Manganese content of above 2% can get excessively segregated in the steel during solidification and homogeneity inside the material is impaired which can cause surface cracks during a hot working process.
- the preferred limit for the presence of Manganese is from 0 % to 1%.
- Silicon content of the steel of present invention is from 0% to 1%. Silicon is an element that contributes to increasing the strength by solid solution strengthening.
- Silicon is a constituent that can retard the precipitation of carbides during cooling after annealing, therefore, Silicon promotes formation of Martensite. But Silicon is also a ferrite former and also increases the Ac3 transformation point which will push the annealing temperature to higher temperature ranges that is why the content of Silicon is kept at a maximum of 1%. Silicon content above 1% can also temper embrittlement.
- the preferred limit for the presence of Silicon is from 0% to 0.5% and more preferably from 0% to 0.4%.
- Other elements such as Boron, Oxygen or Magnesium can be added individually or in combination in the following proportions by weight: Boron 0.001%, Oxygen ⁇ 0.004%, Magnesium ⁇ 0.0010%.
- the remainder of the composition of the Steel consists of iron and inevitable impurities resulting from processing.
- the microstructure of the Steel comprises: Martensite constitutes at least 95% of the microstructure by area fraction and is the matrix microstructure of the steel of present invention.
- the martensite of the present invention can comprise both fresh and tempered martensite.
- fresh martensite is an optional microconstituent which is preferably limited in the steel at an amount of from 0% to 4%, preferably from 0 to 2% and even better equal to 0%.
- Fresh martensite may form during cooling after tempering.
- Tempered martensite is formed from the martensite which forms during the second step of cooling after annealing and particularly after below Ms temperature and more particularly from Ms-10°C to 20°C.Such martensite is then tempered during the holding at a tempering temperature Temper from 450°C to 680°C.
- the martensite of the present invention imparts ductility and strength to such steel.
- the content of martensite is from 96% to 99% and more preferably from 96% to 98%.
- Reverted Austenite is present in the steel of present invention from 1% to 5% by area fraction.
- the reverted austenite is formed from the transformation of martensite into austenite during the tempering of the steel and also get enriched and stabilized with Nickel simultaneously.
- the reverted austenite of the steel of present invention imparts both hardness as well as corrosion resistance.
- the content of reverted austenite is from 1% to 4% and more preferably from 1% to 3%.
- Inter-metallic compounds of Nickel, Titanium and Aluminum are present in the steel of present invention.
- the inter-metallic are formed during the heating to tempering temperature as well as during the tempering process.
- Inter-metallic compounds formed are both inter -granular as well as intra-granular inter-metallic.
- Inter granular Inter- metallic compounds of the present invention are present in both Martensite and Reverted Austenite. These inter-metallic compounds of present invention can be cylindrical or globular in shape.
- Inter-metallic compounds of the steel of present invention are formed as Ni3Ti, Ni3Al or Ni3(Ti,Al) inter-metallic compounds.
- Inter- metallic compound of the steel of present invention imparts the steel of present invention strength and corrosion resistance especially against the chlorides environment.
- G-phase intermetallic such as Ti 6 Si 7 Ni 16 or Mn 6 Si 7 Ni 16 are present in the steel they increase the hardness of the steel beyond 550Hv and are also detrimental for the corrosion resistance properties of the steel of present invention.
- G-phase also makes the steel brittle. Therefore, the steel of present invention is kept free from G-phase inter-metallics.
- the microstructure of the hot rolled steel sheet is free from microstructural components, such as Ferrite, Bainite, Pearlite and Cementite but may be found in traces. Some traces of inter-metallic compound of Iron such as Iron-Aluminum and Iron-Nickel may be present but their presence has no significant influence over the in-use properties of the steel.
- the steel of present invention can be formed in to seamless tubular product or steel sheet or even a structural or operational part to be used industry having a harsh environment containing chlorides or any other industry that has corrosive environment.
- a steel sheet according to the invention can be produced by the following method.
- a preferred method consists in providing a semi-finished casting of steel with a chemical composition according to the invention.
- the casting can be done either into ingots, billets, bars or continuously in form of thin slabs or thin strips, i.e. with a thickness ranging from approximately 220mm for slabs up to several tens of millimeters for thin strip.
- a slab having the above-described chemical composition is manufactured by continuous casting wherein the slab optionally underwent the direct soft reduction during the continuous casting process to avoid central segregation.
- the slab provided by continuous casting process can be used directly at a high temperature after the continuous casting or may be first cooled to room temperature and then reheated for hot rolling.
- the temperature of the slab, which is subjected to hot rolling is preferably at least 1150° C and must be below 1300°C. In case the temperature of the slab is lower than 1150° C, excessive load is imposed on a rolling mill. Therefore, the temperature of the slab is preferably sufficiently high so that hot rolling can be completed in the in 100% austenitic range. Reheating at temperatures above 1275°C causes productivity loss and is also industrially expensive. Therefore, the preferred reheating temperature is from 1150°C to 1275°C. Thereafter the reheated slab is subjected to hot rolling.
- the hot rolling finishing temperature for the present invention is from 800°C to 975°C and preferably from 800°C to 950°C.
- the preferred CS1 temperature range is 15°C to Ms-20°C.
- the cooling rate CR1 from hot roll finishing temperature to CS1 is preferably from 1°C/s to 100°C/s.
- the CR1 for cooling after hot roll finishing temperature is from 1°C/s to 80°C/s and more preferably from 1°C/s to 50°C/s.
- the TA is from Ae3 +20°C to Ae3 +350°C and more preferably from Ae3 +40°C to Ae3 +300°C.
- the heating starts from CS1 to the TA temperature at a heating rate HR1 of at least 1°C/s, In a preferred embodiment, the heating rate HR1 for such heating is at least 5°C/s and more preferably at least 10°C/s or more. Then cooling the hot rolled steel strip after holding at annealing temperature, preferably at a cooling rate CR2 of 1°C/s to 100°C/s.
- the cooling rate CR2 for cooling after holding at annealing temperature is from 1°C/s to 80°C/s and more preferably from 1°C/s to 50°C/s.
- the hot rolled steel strip is cooled to temperature range CS2 which is from 10°C to Ms after annealing and preferably the CS2 temperature is from 15°C to Ms-20°C.
- the fresh Martensite is formed and the cooling rate CS2 must be above 1°C/s to ensures that the hot rolled strip is completely martensitic in nature.
- the annealed hot rolled steel strip is heated to the tempering temperature Ttemper at a heating rate HR2 which is from 0.1°C/s to 100°C/s, preferably from 0.1°C/s to 50°C/s, an even more preferably from 0.1°C/s to 30°C/s.
- HR2 heating rate
- inter-metallic of Nickel, Titanium and Aluminum are formed.
- Inter-metallic compounds formed during this heating and tempering are both intra-granular as well as intergranular which forms as Ni3Ti, Ni3Al or Ni3(Ti,Al) inter- metallic compounds.
- the tempering temperature Ttemper is from 450°C to 700°C where the steel is tempered for a duration from 30 minutes to 72 hours.
- the Ttemper is from 490°C to 690°C and more preferably from 500°C to 680°C.
- the reverted austenite formed during tempering is enriched with nickel due to the reason that in tempering temperature range of present invention some of the inter-metallic formed during heating dissolves and enriches the austenite with nickel and this nickel enriched reverted austenite is stable at room temperature.
- the hot rolled steel strip is cooled to room temperature to obtain the hot rolled steel.
- the surface fractions of phases in the microstructure are determined through the following method: a specimen is cut from the steel sheet, polished and etched with a reagent known per se, to reveal the microstructure.
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Abstract
Acier laminé à chaud présentant une composition comprenant les éléments suivants : 5 % ≤ Nickel ≤ 16 %, 0,5 % ≤ aluminium ≤ 3 %, 0,1 % ≤ titane ≤ 1 %, 4 % ≤ chrome ≤ 15 %, 0,0001 % ≤ carbone ≤ 0,03 %, 0,002 % ≤ phosphore ≤ 0,02 %, 0 % ≤ soufre ≤ 0,005 %, 0 % ≤ azote ≤ 0,01 %, 0 % ≤ cobalt ≤ 7 %, 0 % ≤ molybdène ≤ 6 %, 0 % ≤ niobium ≤ 0,1 %, 0 % ≤ vanadium ≤ 0,3 %, 0 % ≤ cuivre ≤ 0,5 %, 0 % ≤ manganèse ≤ 2 %, 0 % ≤ silicium ≤ 1 %, 0 % ≤ bore ≤ 0,001 %, 0 % ≤ oxygène ≤ 0,004 %, 0 % ≤ magnésium ≤ 0,0010 %, le reste étant composé de fer et d'impuretés inévitables résultant du traitement, la microstructure de ladite tôle d'acier comprenant, en fraction surfacique, au moins 95 % de martensite, de 1 % à 5 % d'austénite de réversion et des composés intermétalliques d'aluminium, de titane et de nickel.
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JPH02310339A (ja) * | 1989-05-24 | 1990-12-26 | Kawasaki Steel Corp | 強度、バネ特性及び成形性に優れたマルテンサイト系ステンレス鋼 |
US20100037994A1 (en) | 2008-08-14 | 2010-02-18 | Gopal Das | Method of processing maraging steel |
US20120114496A1 (en) * | 2010-11-09 | 2012-05-10 | Shinji Oikawa | Precipitation Hardening Martensitic Stainless Steel and Steam Turbine Component Made Thereof |
US20130224033A1 (en) * | 2012-02-27 | 2013-08-29 | Hitachi, Ltd. | Steam Turbine Rotor |
EP2840160A2 (fr) | 2013-08-23 | 2015-02-25 | Daido Steel Co.,Ltd. | Acier maraging présentant d'excellentes caractéristiques de fatigue |
EP3178948A1 (fr) * | 2015-12-10 | 2017-06-14 | General Electric Company | Turbine à vapeur, godet et procédé de fabrication de godet |
CN108251759A (zh) * | 2018-02-01 | 2018-07-06 | 南京理工大学 | 逆变奥氏体韧化的马氏体不锈钢及其制造方法 |
WO2020054540A1 (fr) * | 2018-09-13 | 2020-03-19 | 大同特殊鋼株式会社 | Acier inoxydable à base de martensite de type à durcissement par précipitation et élément de forage d'excavation souterrain |
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2022
- 2022-07-12 WO PCT/IB2022/056421 patent/WO2024013542A1/fr unknown
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JPH02310339A (ja) * | 1989-05-24 | 1990-12-26 | Kawasaki Steel Corp | 強度、バネ特性及び成形性に優れたマルテンサイト系ステンレス鋼 |
US20100037994A1 (en) | 2008-08-14 | 2010-02-18 | Gopal Das | Method of processing maraging steel |
US20120114496A1 (en) * | 2010-11-09 | 2012-05-10 | Shinji Oikawa | Precipitation Hardening Martensitic Stainless Steel and Steam Turbine Component Made Thereof |
US20130224033A1 (en) * | 2012-02-27 | 2013-08-29 | Hitachi, Ltd. | Steam Turbine Rotor |
EP2840160A2 (fr) | 2013-08-23 | 2015-02-25 | Daido Steel Co.,Ltd. | Acier maraging présentant d'excellentes caractéristiques de fatigue |
EP3178948A1 (fr) * | 2015-12-10 | 2017-06-14 | General Electric Company | Turbine à vapeur, godet et procédé de fabrication de godet |
CN108251759A (zh) * | 2018-02-01 | 2018-07-06 | 南京理工大学 | 逆变奥氏体韧化的马氏体不锈钢及其制造方法 |
WO2020054540A1 (fr) * | 2018-09-13 | 2020-03-19 | 大同特殊鋼株式会社 | Acier inoxydable à base de martensite de type à durcissement par précipitation et élément de forage d'excavation souterrain |
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S.M.C. VAN BOHEMENJ. SIETSMA, METALLURGICAL AND MATERIALS TRANSACTIONS, vol. 40, May 2009 (2009-05-01), pages 1059 |
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