WO2022253912A1 - Pièce en acier mise en forme à chaud et procédé de fabrication - Google Patents
Pièce en acier mise en forme à chaud et procédé de fabrication Download PDFInfo
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- WO2022253912A1 WO2022253912A1 PCT/EP2022/064945 EP2022064945W WO2022253912A1 WO 2022253912 A1 WO2022253912 A1 WO 2022253912A1 EP 2022064945 W EP2022064945 W EP 2022064945W WO 2022253912 A1 WO2022253912 A1 WO 2022253912A1
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- WIPO (PCT)
- Prior art keywords
- traces
- hot
- steel
- steel part
- ferrite
- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 53
- 239000010959 steel Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 39
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 27
- 229910001562 pearlite Inorganic materials 0.000 claims abstract description 21
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 9
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims description 43
- 229910001563 bainite Inorganic materials 0.000 claims description 30
- 229910052750 molybdenum Inorganic materials 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 18
- 239000011265 semifinished product Substances 0.000 claims description 18
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000003754 machining Methods 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000005496 tempering Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 2
- 238000005482 strain hardening Methods 0.000 claims description 2
- 239000011572 manganese Substances 0.000 description 28
- 238000007792 addition Methods 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- 229910052720 vanadium Inorganic materials 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 13
- 230000009466 transformation Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 229910001021 Ferroalloy Inorganic materials 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 238000005242 forging Methods 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—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
- 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
- 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
- C21D1/06—Surface hardening
- C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
- C21D1/10—Surface hardening by direct application of electrical or wave energy; by particle radiation by electric induction
-
- 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
- C21D1/20—Isothermal quenching, e.g. bainitic hardening
-
- 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
- C21D1/26—Methods of annealing
- C21D1/30—Stress-relieving
-
- 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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
- C21D7/08—Modifying the physical properties of iron or steel by deformation by cold working of the surface by burnishing or the like
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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
-
- 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
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C22C38/06—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
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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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
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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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
- C22C38/42—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
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/009—Pearlite
Definitions
- TITLE Hot formed steel part and manufacturing process
- the present invention relates to the use of a steel of determined composition for the manufacture of a mechanical part whose mechanical characteristics are obtained by natural cooling after a hot forming step (rolling, forging, etc.)
- Some mechanical parts such as the crankshaft, wishbones, etc. require mechanical strengths of the order of 850-1000 MPa. These requirements explain the use of micro-alloyed ferritic-pearlitic grades such as 38MnVS6. These grades, which are described by the DIN EN 10267 standard, use the phenomenon of interphase precipitation of vanadium to obtain mechanical characteristics superior to those of conventional ferrito-pearlitic steels. They make it possible to obtain, without heat treatment after hot forming, the mechanical resistances mentioned above. Being moreover relatively simple to implement (the mechanical properties are obtained without subsequent heat treatment), these grades have been widely imposed since the 1990s.
- EP 1 780 293 A2 presents a bainito-martensitic steel shaped hot, and making it possible to obtain high mechanical characteristics without heat treatment (examples of mechanical resistance at 1180 MPa are given).
- WO 2005/100618 presents a steel with an acicular ferrite structure (that is to say, in theory, bainite formed intragranularly) making it possible to obtain, without heat treatment, a mechanical strength of approximately 1150 MPa according to the examples.
- WO 2009/138586 A2 relates to a steel with a bainitic structure making it possible to obtain a mechanical strength of at least 1100 MPa without heat treatment.
- WO 2016/151345 A1 is similar to the previous example in that it describes a grade having a predominantly bainitic microstructure (70 to 100%) and having a mechanical strength greater than 1100 MPa in all the examples. The same is true for WO 2019/180563 A1.
- Document EP 3061838A1 relates to a grade with a predominantly bainitic structure (minimum 60% bainite) having a mechanical strength greater than 1150 MPa.
- SEW 605-Ed1 suggests that, from the point of view of mechanical characteristics, some of the proposed solutions could nevertheless be suitable. This is the case for grades called 27MnCr6-3, and to a lesser extent 37Mn7 and 37MnCr4-3. Indeed, all these grades are likely to present mechanical resistances of the level of that of 38MnVS6 (taken here because being the most used of the grades of NF EN 10267). However, the detail of the chemical compositions shows that for all of these shades, additions of V are necessary. These solutions are therefore also not likely to respond to the problem posed, of a grade having a mechanical resistance between 850 and 1000 MPa without heat treatment and without significant use of vanadium (or other critical ferro-alloys).
- vanadium just like molybdenum (which has the same disadvantages in terms of cost) have the particularity of greatly slowing down the formation of ferrite-pearlite without however influencing the kinetics of the formation of bainite. It is therefore understood that they are used for bainitic grades, especially when it is desired to limit the additions of Mn and Cr as the present problem imposes.
- bainite or bainitic ferrite sometimes called acicular ferrite or intragranular bainite are not considered to be distinct from the microstructure claimed for the steels of the invention, and that bainite should be understood in a general way, in the thus excluding ferrite-pearlite, Widmanstaetten ferrite, or martensite.
- the subject of the invention is a hot-formed steel part, characterized in that the composition of the steel, in weight percentages, consists of:
- C%, Mn%, Cr%, Mo%, Ni%, Ti% and N% designate the C, Mn, Cr, Mo, Ni, Ti and N contents of the steel, in percentages by weight, and in that its microstructure consists of, in surface fractions: at least 70% of a mixture of bainitic ferrite and carbides or residual austenite, the fraction of residual austenite being less than or equal to 10%, at most 30% martensite and/or pro-eutectoid ferrite and/or pearlite, the fraction of pro-eutectoid ferrite and/or pearlite being less than or equal to 10%.
- the mixture of bainite ferrite and carbides or residual austenite constitutes bainite, bainite including the morphologies of bainite or bainite ferrite called acicular ferrite or intragranular bainite.
- the residual austenite fraction is less than or equal to 5%.
- the steel part according to the invention preferably has one or more of the following characteristics, taken individually or in combination:
- composition is such that 0.25% ⁇ C ⁇ 0.35%, preferably 0.25% ⁇ C ⁇ 0.30%;
- composition is such that 1.10% £ Mn £ 1.70%;
- the composition is such that traces £ Mo £ 0.10%; the composition is such that traces £Si ⁇ 0.35%, preferably traces £Si ⁇ 0.25%, preferably traces £Si ⁇ 0.15%;
- composition is such that traces £Ni£ 0.35%
- composition is such that traces £ Cu £ 0.30%;
- composition is such that traces £ V £ 0.05%
- composition is such that traces £ Al £ 0.05%
- composition is such that 0.001% £ B £ 0.006%;
- composition is such that traces £ Nb £ 0.02%;
- composition is such that traces £ N £ 0.010%
- the invention also relates to a process for manufacturing a steel part, characterized in that:
- the hot-shaped semi-finished product is cooled in calm air, forced air, under a hood or in a box.
- the method according to the invention preferably has one or more of the following characteristics, taken individually or in combination:
- the cooling rate between 750°C and 550°C is greater than or equal to 0.15°C/s
- the cooling rate between 550°C and 250°C is between 0.1 and 0 .5°C/s
- the cooling rate below 250°C is between 0.1 and 100°C/s
- the semi-finished product is shaped by machining or cold deformation
- the semi-finished product shaped hot is shaped by cold machining or cold deformation
- the hot-shaped semi-finished product is subjected to tempering at a temperature of between 150° C. and 350° C.; the purpose of such tempering is to adjust the hardness of the part of the semi-finished product treated by surface treatment by high-frequency induction;
- - mechanical reinforcement of the hot-shaped semi-finished product is carried out in order to obtain hardening of at least part of the hot-shaped semi-finished product, by processes such as burnishing or autofrettage.
- a deposit is made, for example by electrogalvanizing, painting and any heat treatment of such a deposit would make it necessary (degassing, baking);
- composition is such that 0.25% ⁇ C ⁇ 0.35%, preferably 0.25% ⁇ C ⁇ 0.30%;
- composition is such that 1.10% £ Mn £ 1.70%;
- composition is such that traces £ Mo £ 0.10%;
- composition is such that traces £Si ⁇ 0.35%; preferably traces £Si ⁇ 0.25%, preferably traces £Si ⁇ 0.15%;
- composition is such that traces £Ni£ 0.35%; - the composition is such that traces £ Cu £ 0.30%;
- composition is such that traces £ V £ 0.05%
- composition is such that traces £ Al £ 0.05%
- composition is such that 0.001% £ B £ 0.006%;
- composition is such that traces £ Nb £ 0.02%;
- composition is such that traces £ N £ 0.010%
- the part concerned may be, but is not limited to, a crankshaft or an injection rail.
- the carbon content is between 0.22 and 0.35%.
- Low carbon contents can be favorable to the rapid formation of bainite, and this point has moreover been the subject of a specific patent (WO2011124851 -A2); however, the low carbon contents also facilitate the formation of pro-eutectoid ferrite. In the absence of vanadium in particular, this ferrite has a particularly low hardness and can constitute a privileged initiation site for fatigue fractures.
- the low carbon contents also lead to the need for ferroalloys in large quantities to maintain the mechanical properties.
- a lower limit of 0.22% has therefore been adopted, which is significantly more than many so-called bainitic grades, which favor contents of the order of 0.16-0.20%.
- the carbon content is strictly greater than 0.25%, or even greater than 0.26%.
- too high carbon contents lead to a significant slowing down of the bainitic transformation while promoting the formation of pearlite (which is not desired).
- the carbon content is less than or equal to 0.30%.
- the Mn content is between 0.50 and 1.7%, preferably greater than or equal to 1.10% and/or less than or equal to 1.70%.
- Mn is used, together with Cr, to control the Bs parameter, an indicator of the temperature at which bainite begins to form during continuous cooling. In particular, the addition of Mn lowers this Bs parameter. If the effect on the Bs can be obtained for relatively low contents (0.50%), it will also be preferable to avoid excessively high contents (>1.70% ) which lead to problems of excessive segregation and an excessive lowering of the parameter Bs.
- the Cr content is between 0.50 and 1.70%.
- Cr is used in the same way as Mn for the purpose of controlling the Bs parameter, it can be used as such to substitute a more or less significant part of the manganese.
- a minimum content of 0.50% is required to guarantee obtaining the microstructure of the invention, and a maximum content of 1.70% is imposed to limit the phenomena of segregation and the cost of the grade.
- the Mo content is between traces and 0.15% and preferably between traces and 0.10%.
- Mo in slowing down the ferritic-pearlitic transformation, a particularly favorable role for obtaining a bainitic microstructure.
- the additions of Mo are, in the present invention, limited to 0.15%, or even 0.10%. This latter content can be approximated by the mere presence of residuals in any scrap used, so that it does not necessarily constitute a deliberate addition.
- the Mo content is strictly less than 0.10%.
- the Si content is between traces and 0.40%, preferably between traces and 0.35%.
- the Si content is less than or equal to 0.25%, preferably less than or equal to 0.15%.
- TRIP' effect Transformation Induced Plasticity
- This effect is generally observed for additions of the order of 1.2 to 1.5% for isothermal transformations.
- document EP 0787 812 B1 specifically mentions that silicon has no stabilizing effect on the residual austenite below 0.8%.
- the TRIP effect mentioned above is not desirable, because it involves an excess mechanical resistance of the lens (850-1000 MPa); it is therefore a matter of guaranteeing its absence or strongly limiting it.
- the inventors were able to show that the views on the role of Si were erroneous, and that, in the range of claimed compositions and on components of dimensions typical of automotive parts, Si could contribute to the presence of residual austenite from 0.40% and even in some cases from 0.35%. We therefore voluntarily limited the Si content to these values, the preferred content guaranteeing the result with greater certainty.
- Ni content is between traces and 0.50%, preferably between traces and 0.35%.
- Nickel may only be present by its introduction into the raw materials as a residual element, in which case its content will naturally be limited to 0.35%.
- the latter may be increased to 0.50% but additions in excess of this limit are prohibited for the same reasons as those of Mo and V (cost and fluctuation in the cost of ferro-alloys, environmental impact).
- the Cu content is between traces and 0.50%, preferably between traces and 0.30%. Like Ni and a small amount of Mo, Cu can only be present by its introduction into the raw materials as a residual element. Additions are therefore not required, but its content is limited to 0.50%, better still to 0.30% to avoid possible hot forming difficulties.
- the V content is between traces and 0.08%, preferably between traces and 0.05%.
- vanadium can be oxidized during production from scrap, so that a content of less than 0.015% is always possible.
- modest additions may be made to improve the hardenability and resistance to tempering, without however exceeding 0.08%, and preferably 0.05% to minimize the consequences on the cost and the variability of the cost of the grade.
- the AI is between traces and 0.10% and preferably between traces and 0.05%.
- Al is optionally added to ensure the deoxidation of the steel. Additions are capped at 0.10% to limit the risk of formation of re-oxidation inclusions by contact of the liquid metal with air. This limitation will be all the more effective if the preference interval is respected.
- the B is between 0.001 and 0.010%, preferably between 0.001 and 0.006%.
- Boron is a powerful retarder of the formation of pro-eutectoid ferrite which is essential to the invention. It is well known to those skilled in the art that its addition in very small quantities makes it possible to obtain a pronounced effect, but a reproducible effect requires a minimum content of 0.001% (10 ppm). Furthermore, to avoid the formation of boron precipitates and its harmful effects, the additions are limited to 0.010%. We will guarantee with greater certainty the absence of these precipitates by limiting our to additions of less than 0.006%.
- the Ti is between 0.01 and 0.06%. Titanium is essential to fix the nitrogen inevitably present during production and thus allow the boron to remain in solid solution.
- the inventors have established that, under the conditions of implementation of the invention, a content of the order of 0.01% could be sufficient. Conversely, a content greater than 0.06% is not necessary from the point of view of the desired effect, and can moreover lead to the formation of precipitates which are harmful for the fatigue life. Additions beyond this limit are also undesirable for cost reasons.
- a minimum of Ti is imposed in relation to the N content (Ti% 3 2.5 N%), in order to guarantee the effectiveness of the protection of B.
- the Nb is between traces and 0.05%.
- additions of niobium may be made to improve the hardenability and/or to refine the austenitic grain at high temperature. These additions are however limited to 0.05% for reasons similar to those mentioned for Ti. Preferably, for cost reasons, the content will be limited to 0.02%.
- the S is between traces and 0.15%.
- sulfur can be added to improve the machinability of the grade, it is then given contents between 0.05 and 0.15%.
- the composition may comprise additions of Ca up to 0.010%, and/or Te up to 0.030%, and/or Se up to 0.050% and/or Bi up to 0.050% and/or Pb up to 0.100%.
- the P is between traces and 0.100%.
- the presence of P will be limited to 0.030% if it is desired to limit the consequences of its embrittling effect.
- contents greater than or equal to 0.030% either because ductility is not a desired property, or even because fragility is desired (case of breakable connecting rods).
- the grade will nevertheless remain limited to 0.100%, a grade beyond which production and rolling difficulties are significant.
- the N is between traces and 0.013%, preferably between traces and 0.010%. Although inevitably present, nitrogen must be limited to maintain the effectiveness of boron additions. To this end, a maximum content of 0.013% is imposed, noting that a limitation to 0.010% will improve the guarantee of obtaining the result.
- the other elements present in the steel of the invention are iron, and impurities resulting from the production, present at usual levels taking into account the raw materials used and the method of production of the liquid steel (use of a converter or an electric arc furnace to obtain the liquid metal, treatment under vacuum or not of the liquid metal, etc.).
- Bs 830 - 270 * C% - 90 * Mn% - 70 * Cr% - 83 * Mo% - 37 * Ni%, in which C%, Mn%, Cr%, Mo% and Ni% designate the C contents , Mn, Cr, Mo and Ni respectively in the composition of the steel, expressed in weight percentages.
- the inventors place themselves against the current approach which requires this parameter to be mainly limited by the upper value, and the lowest possible.
- the Bs parameter according to the invention makes it possible to form bainite at high temperature during cooling, such that a coarse bainitic structure is obtained.
- bainite has a lower mechanical strength than in the steels according to the state of the art mentioned above.
- the Bs parameter is greater than 560°C, better still greater than 570°C.
- the microstructure of the steel consists of, in surface fractions: at least 70% of a mixture of bainitic ferrite and carbides or residual austenite, the fraction of residual austenite being less than or equal to 10%, at most 30 % martensite and/or pro-eutectoid ferrite and/or pearlite, the fraction of pro-eutectoid ferrite and/or pearlite being less than or equal to 10%.
- bainite is in the form of a matrix of bainitic ferrite slats or plates, between which carbides and/or austenite are present.
- the bainite in particular the bainitic ferrite, is formed during the cooling, as soon as the temperature becomes lower than the temperature at which the bainitic transformation begins Bs.
- bainite is formed at relatively high temperature.
- the residual austenite fraction must be less than or equal to 10%, preferably less than or equal to 5%.
- a fraction of residual austenite greater than 10% would lead to an excess mechanical strength of the lens (850-1000 MPa).
- a high residual austenite fraction is therefore detrimental to achieving the objective of the present invention.
- a residual austenite fraction of less than or equal to 5% is therefore preferred.
- the structure may comprise martensite, pro-eutectoid ferrite and/or pearlite, but the sum of the fractions of these constituents must remain no more than 30% and the sum of the fractions of pro-eutectoid ferrite and pearlite of at most 10% to achieve the desired mechanical characteristics.
- the part is produced by hot forming, in the austenitic phase, of a steel semi-finished product with the composition described above.
- the semi-finished product is for example a billet or a bar.
- the semi-finished product before the hot shaping, is subjected to an initial shaping by machining or cold deformation.
- Hot forming is, for example, hot forging or hot rolling.
- Hot forming is carried out in the austenitic phase (typically between 1100 and 1250°C).
- Cooling is, for example, carried out in still air, forced air, under a hood or in the box, depending on the desired cooling speed.
- the desired mechanical characteristics are obtained without implementation of heat treatments after hot forming, nor very constraining particular control of the cooling rate which can be carried out naturally, in calm air.
- the cooling rate between 750° C. and 550° C. is preferably greater than or equal to 0.15° C./s, in order to avoid or limit the formation of ferrite and pearlite, liable to form in this temperature range.
- the cooling rate between 550°C and 250°C is between 0.1 and 0.5°C/s.
- bainitic ferrite is formed in this temperature range.
- the cooling rate should not be too high in order to maximize the formation of bainite in this temperature range.
- Below 250°C the phase transformation is generally complete, so that the cooling rate is between 0.1°C/s and 100°C/s.
- still air cooling may be sufficient to achieve the cooling rate ranges specified above.
- an adaptation of the cooling can in certain cases be used, in particular because of the diameter of the parts.
- cooling at calm air could lead to too slow cooling, especially in the heart of the parts, and lead to the appearance of ferrite and/or pearlite in excessive quantities.
- forced air cooling can be implemented to obtain a sufficient cooling rate.
- cooling can be implemented under a hood or in a crate to reduce the cooling rate.
- shaping is carried out by cold machining or cold deformation, to obtain the part, in particular to obtain the precise dimensions and surface characteristics of the final part.
- a surface treatment is carried out on the surface of the part by high-frequency induction to give it the benefits of this technique (increase in hardness, residual stresses compression, etc).
- This surface treatment is generally carried out on a specific part of the part.
- tempering can be performed to adjust the hardness of the treated areas of the part.
- a part of the part is mechanically reinforced by a process such as burnishing, autofrettage, or other processes aimed at obtaining local work hardening as well as residual compressive stresses in the part. strengthen.
- the part is subjected to a deposition of a coating, for example by electrogalvanizing or a deposition of paint, as well as to any heat treatments required by such a deposition.
- compositions according to the invention Inv1 to Inv4
- compositions close to but not in accordance with the invention Step to Steel7
- 38MnVS6 All of the compositions selected are presented in [Table 1]. It should be understood that the complement to 100% of the cited compositions is Fe, the elements not mentioned in this table being present only in the form of traces including those which may only be optionally present in the invention, such as the machinability elements Ca, Te, Se, Bi, Pb which have not been added in the examples considered.
- the underlined values are not in accordance with the invention.
- the underlined values are the values not in accordance with the invention.
- the reference grade 38MnVS6
- this grade uses the interphase precipitation of vanadium to obtain its mechanical properties, an element whose addition we precisely want to avoid.
- the Alt1 steel has a microstructure and a tensile strength in accordance with the expected, but with carbon and molybdenum contents not in accordance with the invention.
- Alt2 illustrates well the reason for the limitations on the carbon content. Indeed, Alt2, for which the Mo content has been reduced compared to Alt1, has a microstructure that does not comply with the requirements of the invention, with in particular -25% pearlite. This result clearly illustrates the difficulty of avoiding the formation of this constituent without using molybdenum in excess of 0.2%.
- Alt3 steel has a non-conforming Bs parameter with a compliant microstructure and Si content.
- Bs lower than the minimum required, the mechanical strength is greater than the requirements of the invention, which may lead to machining difficulties in production.
- the Alt4 and Alt5 steels have compositions very close to those of the invention, with the exception of the Si content which is in excess of the maximum imposed by the invention. This results in a mechanical strength significantly higher than that targeted (850-1000 MPa).
- these steels exhibited residual austenite contents of 11 and 15% respectively as they are. It was also explained that this residual austenite was responsible for the high mechanical strengths through the TRI P effect. This result is central to the invention, because it is in opposition to the whole of the scientific corpus, generally estimating the limit for the stabilization of residual austenite at 0.6-1 Si%.
- the Alt6 steel is compliant in many points with the exception of the addition of Ti and B. This results in a microstructure not in accordance with the invention (the experience of the inventors being that the mixed pearlite-bainite microstructures exhibit a very high sensitivity to cooling conditions and being undesirable for use in industrial conditions).
- Alt7 steel is also close to those of the invention, but has a Bs parameter significantly lower than that required, resulting in a mechanical strength well above the target.
- Steels Inv1 to Inv 4 all have a structure consisting of, in surface fractions, at least 70% of a mixture of bainitic ferrite and carbides or residual austenite, the fraction of residual austenite being less than or equal to 5% , and at most 30% martensite and/or pro-eutectoid ferrite and/or pearlite, the fraction of pro-eutectoid ferrite and/or pearlite being less than or equal to 10%.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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BR112023025290A BR112023025290A2 (pt) | 2021-06-02 | 2022-06-01 | Peça de aço conformada a quente e método de fabricação de uma peça de aço |
US18/565,931 US20240254610A1 (en) | 2021-06-02 | 2022-06-01 | Hot-Formed Steel Part and Manufacturing Method |
KR1020247000114A KR20240018573A (ko) | 2021-06-02 | 2022-06-01 | 열간 성형 강철 부품 및 제조 방법 |
EP22731603.1A EP4347903A1 (fr) | 2021-06-02 | 2022-06-01 | Pièce en acier mise en forme à chaud et procédé de fabrication |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR2105812A FR3123659A1 (fr) | 2021-06-02 | 2021-06-02 | Pièce en acier mise en forme à chaud et procédé de fabrication |
FRFR2105812 | 2021-06-02 |
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WO2022253912A1 true WO2022253912A1 (fr) | 2022-12-08 |
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PCT/EP2022/064945 WO2022253912A1 (fr) | 2021-06-02 | 2022-06-01 | Pièce en acier mise en forme à chaud et procédé de fabrication |
Country Status (6)
Country | Link |
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US (1) | US20240254610A1 (fr) |
EP (1) | EP4347903A1 (fr) |
KR (1) | KR20240018573A (fr) |
BR (1) | BR112023025290A2 (fr) |
FR (1) | FR3123659A1 (fr) |
WO (1) | WO2022253912A1 (fr) |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5820706A (en) * | 1996-02-08 | 1998-10-13 | Ascometal | Process for manufacturing a forging |
JPH11350074A (ja) * | 1998-04-07 | 1999-12-21 | Nippon Steel Corp | ガス圧接性に優れたベイナイト系レール |
WO2005100618A2 (fr) | 2004-03-18 | 2005-10-27 | Mittal Steel Gandrange | Piece mecanique de taille moyenne ou petite issue de la forge ou de la frappe |
EP1780293A2 (fr) | 2005-10-28 | 2007-05-02 | Saarstahl AG | Procédure de fabrication de la matière brute de l'acier par déformer ä chaud |
WO2009138586A2 (fr) | 2008-05-15 | 2009-11-19 | Arcelormittal Gandrange | Acier micro-allié pour forge à chaud de pièces mécaniques à hautes caractéristiques |
WO2011124851A2 (fr) | 2010-04-07 | 2011-10-13 | Ascometal | Pièce mécanique en acier à hautes caractéristiques et son procédé de fabrication |
EP3061838A1 (fr) | 2015-02-27 | 2016-08-31 | Swiss Steel AG | Produit longitudinal bainitique nu et son procédé de fabrication |
WO2016151345A1 (fr) | 2015-03-23 | 2016-09-29 | Arcelormittal | Pieces a structure bainitique a hautes proprietes de resistance et procede de fabrication |
EP3378957A1 (fr) * | 2017-03-23 | 2018-09-26 | Ascometal France Holding SAS | Acier, procédé pour la fabrication de pièces mécaniques en cet acier, et pièces ainsi fabriquées |
WO2019180563A1 (fr) | 2018-03-23 | 2019-09-26 | Arcelormittal | Pièce forgée en acier bainitique et son procédé de fabrication |
-
2021
- 2021-06-02 FR FR2105812A patent/FR3123659A1/fr active Pending
-
2022
- 2022-06-01 WO PCT/EP2022/064945 patent/WO2022253912A1/fr active Application Filing
- 2022-06-01 EP EP22731603.1A patent/EP4347903A1/fr active Pending
- 2022-06-01 US US18/565,931 patent/US20240254610A1/en active Pending
- 2022-06-01 KR KR1020247000114A patent/KR20240018573A/ko unknown
- 2022-06-01 BR BR112023025290A patent/BR112023025290A2/pt unknown
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5820706A (en) * | 1996-02-08 | 1998-10-13 | Ascometal | Process for manufacturing a forging |
EP0787812B1 (fr) | 1996-02-08 | 2004-03-17 | ASCOMETAL (Société anonyme) | Procédé de fabrication d'une pièce forgée en acier |
JPH11350074A (ja) * | 1998-04-07 | 1999-12-21 | Nippon Steel Corp | ガス圧接性に優れたベイナイト系レール |
WO2005100618A2 (fr) | 2004-03-18 | 2005-10-27 | Mittal Steel Gandrange | Piece mecanique de taille moyenne ou petite issue de la forge ou de la frappe |
EP1780293A2 (fr) | 2005-10-28 | 2007-05-02 | Saarstahl AG | Procédure de fabrication de la matière brute de l'acier par déformer ä chaud |
WO2009138586A2 (fr) | 2008-05-15 | 2009-11-19 | Arcelormittal Gandrange | Acier micro-allié pour forge à chaud de pièces mécaniques à hautes caractéristiques |
WO2011124851A2 (fr) | 2010-04-07 | 2011-10-13 | Ascometal | Pièce mécanique en acier à hautes caractéristiques et son procédé de fabrication |
EP3061838A1 (fr) | 2015-02-27 | 2016-08-31 | Swiss Steel AG | Produit longitudinal bainitique nu et son procédé de fabrication |
WO2016151345A1 (fr) | 2015-03-23 | 2016-09-29 | Arcelormittal | Pieces a structure bainitique a hautes proprietes de resistance et procede de fabrication |
EP3378957A1 (fr) * | 2017-03-23 | 2018-09-26 | Ascometal France Holding SAS | Acier, procédé pour la fabrication de pièces mécaniques en cet acier, et pièces ainsi fabriquées |
WO2019180563A1 (fr) | 2018-03-23 | 2019-09-26 | Arcelormittal | Pièce forgée en acier bainitique et son procédé de fabrication |
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Publication number | Publication date |
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US20240254610A1 (en) | 2024-08-01 |
KR20240018573A (ko) | 2024-02-13 |
FR3123659A1 (fr) | 2022-12-09 |
BR112023025290A2 (pt) | 2024-02-27 |
EP4347903A1 (fr) | 2024-04-10 |
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