WO2022243397A1 - Flat steel product having an al-coating, process for production thereof, steel component and process for production thereof - Google Patents
Flat steel product having an al-coating, process for production thereof, steel component and process for production thereof Download PDFInfo
- Publication number
- WO2022243397A1 WO2022243397A1 PCT/EP2022/063495 EP2022063495W WO2022243397A1 WO 2022243397 A1 WO2022243397 A1 WO 2022243397A1 EP 2022063495 W EP2022063495 W EP 2022063495W WO 2022243397 A1 WO2022243397 A1 WO 2022243397A1
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- WO
- WIPO (PCT)
- Prior art keywords
- weight
- steel
- protective coating
- mass fraction
- flat
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 201
- 239000010959 steel Substances 0.000 title claims abstract description 201
- 238000000034 method Methods 0.000 title claims description 31
- 238000000576 coating method Methods 0.000 title claims description 26
- 239000011248 coating agent Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 230000008569 process Effects 0.000 title description 19
- 239000011253 protective coating Substances 0.000 claims abstract description 104
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 238000005275 alloying Methods 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- 229910052748 manganese Inorganic materials 0.000 claims description 55
- 238000000137 annealing Methods 0.000 claims description 54
- 229910045601 alloy Inorganic materials 0.000 claims description 47
- 239000000956 alloy Substances 0.000 claims description 47
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 46
- 229910052749 magnesium Inorganic materials 0.000 claims description 43
- 229910052782 aluminium Inorganic materials 0.000 claims description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 15
- 238000003618 dip coating Methods 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 claims 4
- 238000010276 construction Methods 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract 3
- 239000011572 manganese Substances 0.000 description 66
- 239000000047 product Substances 0.000 description 59
- 239000011777 magnesium Substances 0.000 description 46
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 44
- 239000010703 silicon Substances 0.000 description 44
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 17
- 239000000155 melt Substances 0.000 description 17
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 11
- 239000011651 chromium Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 239000010955 niobium Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910000734 martensite Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000005269 aluminizing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011733 molybdenum Substances 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
- 239000011574 phosphorus Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
-
- 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
-
- 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
- C21D1/28—Normalising
-
- 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
- C21D1/62—Quenching devices
- C21D1/673—Quenching devices for die 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- 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
- C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
-
- 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
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment
- C21D8/0484—Application of a separating or insulating coating
-
- 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
- C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
- C22C21/04—Modified aluminium-silicon alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
Definitions
- the invention relates to a steel flat product for hot forming consisting of a steel substrate composed of a steel containing 0.1-3 wt.% Mn and optionally up to 0.01 wt.% B and a protective coating applied to the steel substrate based on Al, which optionally contains a total of up to 20% by weight of other alloying elements.
- the invention also relates to a method for producing a flat steel product according to the invention.
- flat steel product includes all rolled products whose length is much greater than their thickness. This includes steel strips and sheets as well as blanks and blanks made from them.
- the invention relates to a steel component produced by hot forming.
- hot press hardening also known as hot forming
- steel blanks which are separated from cold or hot-rolled steel strip, are heated to a deformation temperature that is generally above the austenitization temperature of the respective steel and placed in the heated state in the tool of a forming press.
- the sheet metal blank or the component formed from it experiences rapid cooling through contact with the cool tool.
- the cooling rates are set in such a way that a hardened structure results in the component.
- the structure is transformed into a martensitic structure.
- the invention also relates to a method for producing such a steel component.
- Typical steels suitable for hot press hardening are steels A-E, the chemical composition of which is listed in Table 2.
- EP 0 971 044 B1 specifies an alloy specification according to which, in addition to iron and unavoidable impurities (in wt %) a carbon content of more than 0.20% but less than 0.5% a manganese content of more than 0.5% but less than 3% a silicon content of More than 0.1% but less than 0.5% Chromium more than 0.01% but less than 1% Titanium less than 0.2% Aluminum less than 0.1% %, a phosphorus content of less than 0.1%, a sulfur content of less than 0.05% and a boron content of more than 0.0005% but less than 0.08%.
- the Al coating is a so-called AISi coating, which consists of 9-10% by weight Si, 2-3.5% by weight iron and the remainder aluminum.
- the flat steel products produced and coated in this way are annealed at a heating temperature of more than 700 °C.
- the protective coating melts and the protective coating is alloyed through.
- iron diffuses from the steel substrate into the protective coating, so that phases are formed that have a higher temperature stability.
- the melted protective coating is rigid.
- a solidified, temperature-stable protective coating is a prerequisite for the subsequent forming step.
- the flat steel product is placed in a press-forming tool, hot-formed into the steel component and cooled so quickly that a hardened structure is created in the steel substrate of the flat steel product.
- the AISi coating described has the disadvantage that, in comparison to uncoated material, long annealing times are required for thorough alloying.
- the object of the present invention is therefore to provide a flat steel product for hot forming that can be further processed in a shorter time.
- a steel flat product for hot forming which consists of a steel substrate consisting of a steel containing 0.1-3% by weight Mn and optionally up to 0.01% by weight B, and a Steel substrate applied protective coating based on Al.
- the non-ferrous mass fraction of additional alloy components of the protective coating is optionally up to 10% in total.
- the remaining non-ferrous mass fraction is made up of aluminum.
- the protective coating consists of iron, aluminum and, optionally, additional alloy components other than iron.
- the non-ferrous mass fraction of the protective coating of Mg as an additional alloy component is less than 2.50% Mg, preferably less than 1.50%, in particular the proportion is 0.10-0.50% Mg of the protective coating of Mn as an additional alloy component in total more than 0.30% Mn, preferably more than 0.60% Mn, particularly preferably more than 0.80% Mn, particularly preferably 1.35 Mn, particularly preferably 1.40 Mn.
- the ironless Mass fraction of the protective coating of Si as an additional alloy component in total less than 1.80% Si, preferably less than 1.20% Si, preferably less than 0.80% Si, particularly preferably less than 0.60% Si.
- an iron-free mass fraction of an alloy component in the protective coating is understood to be the fraction of the total mass of this alloy component in the total mass of all elements in the protective coating except iron.
- the protective coating thus comprises a proportion of up to 2.5% by weight magnesium, more than 0.30% by weight manganese and less than 1.80% by weight silicon based on the total mass of all elements except iron in the protection coating.
- Using the non-ferrous mass fraction to characterize the protective coating has the advantage that the numerical values do not change as a result of iron diffusing in from the steel substrate.
- Magnesium has proven to be an advantageous, additional alloying component, which can be easily alloyed into Al protective coatings of the type in question here.
- the amount of Mg added is adjusted in such a way that the total iron-free mass fraction of magnesium is less than 2.50%, in particular less than 1.50%.
- the non-ferrous mass fraction of magnesium in the protective coating is preferably at least 0.10% and at most 0.50% Mg, with Mg contents of less than 0.50%, in particular less than 0.45% or up to 0.40% or up to 0.35%, have proven to be particularly favorable in practice.
- the small amounts of magnesium added to the Al coating are characterized by a higher affinity for oxygen than the main component, aluminum, of the protective coating. Even with the presence of such small amounts of magnesium, a thin oxide layer forms on the surface of the protective coating, which covers the aluminum lying between it and the steel substrate. During the heating required for the hot forming of the flat steel product, this thin layer prevents the aluminum from reacting with the moisture present in the atmosphere of the furnace used for heating the flat steel product.
- alloying magnesium reduces the amount of hydrogen entering the steel substrate. If a very high local hydrogen concentration is reached, this weakens the bond at the grain boundaries of the steel substrate structure to such an extent that a crack occurs along the grain boundary during use as a result of the resulting stress.
- the layer thickness of the protective coating is typically in the range of 5-35 ⁇ m, in particular 10-25 ⁇ m.
- the faster alloying of the protective coating has several advantages.
- the duration of the hot forming process can be shortened, which makes the production process more efficient.
- energy savings can be achieved through the shortened annealing time.
- other furnaces can also be used for heating and keeping at the heating temperature.
- Roller hearth furnaces for example, are used for this process step.
- shorter roller hearth furnaces can be used due to the shortened annealing time.
- furnaces that were originally designed for process safety of uncoated material can be used.
- the non-ferrous mass fraction of the protective coating of Mn as an additional alloy component is more than 1.00% Mn, in particular more than 1.30% Mn. It has been shown that from a non-ferrous mass fraction of 1.00% manganese, the annealing time is significantly reduced.
- a special design variant of the steel flat product is characterized by the fact that the non-ferrous mass fraction of the protective coating consists of Mn as an additional alloy component in Total is less than 1.80% manganese, preferably less than 1.60% manganese.
- Mn content increases, the melting point increases, making the protective coating more difficult to apply by hot dip coating.
- high manganese contents promote slag formation in the melt and are therefore also disadvantageous.
- the illustrated embodiment examples with 1.60% manganese have the advantages of the invention, however, showed major slag problems, which makes production difficult.
- the non-ferrous mass fraction of the protective coating of Si as an additional alloy component is less than 1.50% Si, in particular less than 1.00% Si, preferably less than 0.80% Si.
- melts with a silicon content well below 0.50% are technically difficult to implement, since contamination with silicon is difficult to avoid.
- the silicon content is therefore in particular more than 0.03%, preferably 0.05%, in particular 0.10%.
- the effect according to the invention still occurs significantly, but the coating process can be implemented much more cost-effectively, since it is not necessary to pay so much attention to silicon impurities.
- the Al-based protective coating can be applied particularly economically to the flat steel product by hot-dip coating, also known as "hot-dip aluminizing" in technical jargon.
- the object according to the invention is also achieved by a steel component produced by hot press-forming a flat steel product as described above.
- the steel component comprises in particular a steel substrate made from a steel containing 0.1-3% by weight Mn and optionally up to 0.01% by weight B, and a protective coating based on Al applied to the steel substrate .
- the non-ferrous mass fraction of additional alloy components of the protective coating is optionally up to 10% in total.
- the non-ferrous mass fraction of the protective coating of Mg as an additional alloy component is less than 2.5% Mg in total.
- the non-ferrous mass fraction of the protective coating of Mn as an additional alloy component is more than 0.30% Mn in total.
- the non-ferrous mass fraction of the protective coating of Si as an additional alloying component is less in total than 1.80% Si.
- the steel component has the same advantages that are explained above in relation to the steel flat product.
- Hot dip coating also known as "fire aluminizing" in technical jargon, is a particularly economical process for applying a protective coating.
- a melt consisting of aluminum with an optional admixture of up to 10% non-ferrous mass fraction of additional alloy components.
- the non-ferrous mass fraction of magnesium as an additional alloy component in the melt is less than 2.50% magnesium in total.
- the non-ferrous mass fraction of manganese as an additional alloy component in the melt totals more than 0.30% manganese and the non-ferrous mass fraction of silicon as an additional alloy component in the melt totals less than 1.80% silicon.
- Hot dip coating results in the protective coating being made up of an alloy layer which adjoins the steel substrate and a top layer which adjoins the alloy layer.
- the composition of the top layer essentially corresponds to the composition ment of the melt, whereas the alloy layer already contains an iron content of typically more than 30% by weight, since there is mixing between the steel substrate and the adjacent melt during the hot dipping process. Since the steel substrate essentially comprises iron, this mixing in the alloy layer does not change the non-iron mass fractions.
- the melt and protective coating therefore have the same non-ferrous mass fractions of the alloying elements.
- the layer thickness of the protective coating is typically in the range of 5-35 ⁇ m, in particular 10-25 ⁇ m.
- preferred non-ferrous mass fractions of the various elements e.g. manganese, silicon and magnesium
- These preferred non-ferrous mass fractions and their advantages also apply to the process for producing the flat steel product and in particular to the composition of the melt if production is carried out by means of hot-dip coating.
- the flat steel product is pre-alloyed immediately after coating by holding it at a pre-alloying temperature of 500°C-600°C for a pre-alloying time of 15-30 seconds.
- pre-alloying temperature 500°C-600°C for a pre-alloying time of 15-30 seconds.
- intermediately is to be understood as meaning that the flat steel product does not cool after coating until the protective coating has completely solidified. In practice, depending on the design of the coating system, there can be up to 10 seconds between coating and pre-alloying.
- the pre-alloying step leads to increased diffusion, so that iron is already diffusing from the substrate into the protective coating and increased iron-containing phases are beginning to form there.
- the subsequent annealing process for the through-alloying can be further shortened.
- the manganese content alone shortens the annealing time in the annealing process (see below).
- the master alloy enables this annealing time to be shortened even further.
- the object of the invention is achieved by a method for producing a steel component as described above, comprising the following work steps:
- the annealing of the steel flat product in a furnace preheated to a temperature T for an annealing time t defined by a polygon ABCD is to be understood within the meaning of this application that the value pair of temperature T and annealing time t is within the polygon formed by the points ABCD becomes.
- the object according to the invention is thus also achieved by a method for producing a steel component as described above, comprising the following work steps: producing a flat steel product by using the method explained above;
- Annealing of the flat steel product with a thickness d in a furnace preheated to a temperature T for an annealing time t according to a variant from the table above, for example annealing of the flat steel product with a thickness of 0.7 - 0.9 mm in a temperature oven preheated to 910-930°C for an annealing time of 1.5 - 5 minutes.
- Hot forming of the steel flat product into the steel component for example annealing of the flat steel product with a thickness of 0.7 - 0.9 mm in a temperature oven preheated to 910-930°C for an annealing time of 1.5 - 5 minutes.
- the diffusion process of the iron from the steel substrate into the protective coating is accelerated by alloying manganese with simultaneous limitation of the silicon content, i. H. shortened the alloying time.
- the annealing time can therefore be significantly reduced compared to a standard process, such as that described in EP2086755.
- the so-called Fe seam forms in the protective coating.
- This is a high ferrous phase in the protective coating at the interface with the steel substrate.
- the thickness of the Fe seam is a measure of the degree of alloying penetration of the protective coating.
- the term fully alloyed is used when the thickness of the Fe seam is greater than 2.5 ⁇ m, in particular greater than 8 ⁇ m, preferably greater than 10 ⁇ m.
- the thickness of the Seams after a certain annealing time is therefore a measure of the alloying penetration rate of the coating.
- the method is further developed in such a way that when the steel flat product is annealed in a furnace preheated to a temperature T for an annealing time t defined by the polygon ABCD according to FIG furnace preheated to a temperature T for an annealing time t defined by the polygon EFGH according to FIG pm, preferably greater than lOpm.
- the thickness of the Fe seam is adjusted according to the other requirements. A sufficiently thick Fe seam ensures that no liquid phases (e.g. liquid aluminium) occur in the protective coating during hot forming. This has several advantages. On the one hand, liquid phases would lead to contamination of furnace rollers or the forming tool. On the other hand, the more rapid alloying causes the surface of the steel flat product to discolour.
- the surface of the steel flat product is dark and dull after the protective coating has been thoroughly alloyed.
- the faster the protective coating is alloyed the faster the surface discolours.
- the dark, matt surface means that the heat coupling is significantly improved.
- the necessary core temperature for hot forming is therefore also reached more quickly. This results in a self-reinforcing effect of the manganese content according to the invention.
- the alloying time of the protective coating is reduced.
- the faster alloying leads to an increased heating rate in the steel substrate and thus to a faster annealing process.
- the flat steel product is removed from the furnace at a heating temperature.
- the heating temperature corresponds to the temperature T of the preheated oven.
- the heating temperature is so high that the flat steel product has a hot forming temperature at the start of forming at which the structure of the steel substrate is completely or partially converted into an austenitic structure, and that the flat steel product after forming or in the course of forming is quenched so that hardened structure is formed in the structure of the steel substrate of the steel flat product.
- the heating temperature is at least 700°C, in particular 880°C to 950°C.
- the steel substrate is of a steel containing 0.1-3 wt% Mn and optionally up to 0.01 wt% B.
- the microstructure of the steel can be converted into a martensitic or partially martensitic microstructure by hot forming.
- the microstructure of the steel substrate of the steel component is therefore preferably a martensitic or at least partially martensitic microstructure, since this has a particularly high degree of hardness.
- the steel substrate is particularly preferably a steel which, in addition to iron and unavoidable impurities (in % by weight), consists of
- Ca ⁇ 0.005% by weight and optionally one or more of the elements "Cr, B, Mo, Ni, Cu, Nb, Ti, V" in the following contents
- the elements P, S, N, Sn, As, Ca are impurities that cannot be completely avoided in the steelmaking process. In addition to these elements, other elements can also be present as impurities in the steel. These other elements are summarized under the "unavoidable impurities".
- the total content of unavoidable impurities is preferably not more than 0.2% by weight, preferably not more than 0.1% by weight.
- the optional alloying elements Cr, B, Nb, Ti, for which a lower limit is given, can also occur in contents below the respective lower limit as unavoidable impurities in the steel substrate.
- the unavoidable impurities are also counted among the unavoidable impurities, the total content of which is limited to a maximum of 0.2% by weight, preferably a maximum of 0.1% by weight.
- the individual upper limits for the respective contamination of these elements are preferably as follows:
- the carbon content of the steel is at most 0.37% by weight and/or at least 0.06% by weight. In particularly preferred variants, the C content is in the range from 0.06 to 0.09% by weight or in the range from 0.12 to 0.25% by weight or in the range from 0.33 to 0.37% by weight %.
- the Si content of the steel is at most 1.00% by weight and/or at least 0.06% by weight.
- the Mn content of the steel is at most 2.4% by weight and/or at least 0.75% by weight. In particularly preferred variants, the Mn content is in the range of 0.75-0.85% by weight or in the range of 1.0-1.6% by weight.
- the Al content of the steel is at most 0.75% by weight, in particular at most 0.5% by weight, preferably at most 0.25% by weight. Alternatively or additionally, the Al content is preferably at least 0.02%.
- the sum of the contents of Si and Al (usually referred to as Si+Al) is therefore at most 1.5% by weight, preferably at most 1.2% by weight. Additionally or alternatively, the sum of the contents of Si and Al is at least 0.06% by weight, preferably at least 0.08% by weight.
- the elements P, S, N are typical impurities that cannot be completely avoided in steel production.
- the maximum P content is 0.03% by weight.
- the S content is preferably at most 0.012%.
- the N content is preferably at most 0.009% by weight.
- the steel also contains chromium with a content of 0.08 - 1.0% by weight.
- the Cr content is preferably at most 0.75% by weight, in particular at most 0.5% by weight.
- the sum of the chromium and manganese contents is preferably limited.
- the total is at most 3.3% by weight, in particular at most 3.15% by weight.
- the sum is at least 0.5% by weight, preferably at least 0.75% by weight.
- the steel preferably also optionally contains boron with a content of 0.001-0.005% by weight.
- the B content is at most 0.004% by weight.
- the steel can optionally contain molybdenum with a maximum content of 0.5% by weight, in particular a maximum of 0.1% by weight.
- the steel can optionally contain nickel with a content of at most 0.5% by weight, preferably at most 0.15% by weight.
- the steel can also contain copper with a content of at most 0.2% by weight, preferably at most 0.15% by weight.
- the steel can optionally contain one or more of the micro-alloying elements Nb, Ti and V.
- the optional Nb content is at least 0.02% by weight and at most 0.08% by weight, preferably at most 0.04% by weight.
- the optional Ti content is at least 0.01% by weight and at most 0.08% by weight, preferably at most 0.04% by weight.
- the optional V content is at most 0.1% by weight, preferably at most 0.05% by weight.
- the sum of the contents of Nb, Ti and V is preferably limited.
- the total is at most 0.1% by weight, in particular at most 0.068% by weight. Furthermore, the sum is preferably at least 0.015% by weight.
- the steel substrate is a steel from the group of steels A-E, the chemical analysis of which is given in Table 2.
- Table 2 is to be understood in such a way that for each steel from the group of steels A-E the element proportions are given in percent by weight. A minimum and a maximum weight percentage is given here.
- steel A therefore has a carbon content C: 0.05% by weight-0.10% by weight.
- FIG. 2 shows a cross section of a steel component according to the invention with a protective cover
- FIG. 7 shows the thickness of the Fe seam with an annealing time of 3 minutes as a function of the nonferrous mass fraction of manganese
- FIG. 8 shows the thickness of the Fe seam with an annealing time of 3 minutes as a function of the iron-free mass fraction of silicon.
- FIG. 9 shows the thickness of the Fe seam as a function of the annealing time for three different variants without magnesium
- FIG. 10 shows the thickness of the Fe seam as a function of the annealing time for three different variants without magnesium after a master alloy
- FIG. 11 suitable annealing parameters for the method for producing a steel component.
- FIG. 12 shows a schematic representation of a flat steel product
- FIGS. 1-4 show cross-sections of steel components that were produced using the same steel substrate and the same forming process. Only the composition of the protective coating was varied.
- Shaped blanks were cut from a 1.5 mm thick strip of steel grade D according to Table 2 with a 25 ⁇ m thick aluminum-based protective coating on both sides. Both a punching tool and a laser were used as cutting methods.
- the detailed chemical composition of the substrate was C: 0.223 wt%, Si: 0.294 wt%, Mn: 1.275 wt%, P: 0.008 wt%, S: 0.002 wt%, Al: 0.046 wt%, Cr: 0.181 wt%, Cu: 0.054 wt%, Mo: 0.001 wt%, N: 0.001 wt%, Ni: 0.035 wt%, Nb: 0.002 wt%. -%, Ti: 0.033 wt%, V: 0.007 wt%, B: 0.0033 wt%, Sn: 0.002 wt%.
- FIGS. 1-4 show examples of cross-sections of the steel component produced in this way with different compositions.
- Figures 5-8 show diagrams which are used to explain the various effects.
- FIG. 1 shows a steel component 21 with a protective coating 15 based on aluminum on a steel substrate 13.
- the protective coating 15 was applied by hot dip coating.
- the melt consisted of aluminum with an additional alloy of 0.4% by weight Mg, 0.8% by weight Mn and 2.0% by weight Si.
- the flat steel product 11 accordingly had a protective coating 15 with a thickness of 25 ⁇ m, the protective coating 15 having an iron-free mass fraction of 0.4% Mg, 0.8% Mn and 2.0% Si.
- the steel component 21 shown in the cross section with the protective coating 15 based on aluminum resulted, the protective coating 15 having an iron-free mass fraction of 0.4% Mg, 0.8% Mn and 2.0% Si.
- FIG. 2 shows a steel component 21 with a protective coating 15 based on aluminum on a steel substrate 13.
- the protective coating 15 was applied by hot dip coating. Since the melt consisted of aluminum with an additional alloy of 0.4% by weight Mg, 1.6% by weight Mn and 2.0% by weight Si. After coating, the flat steel product 11 (see FIG. 12) accordingly had a protective coating 15 with a thickness of 25 ⁇ m, the protective coating 15 having an iron-free mass fraction of 0.4% Mg, 0.8% Mn and 2.0% Si. After the explained hot forming, the steel component 21 shown in the cross-section resulted with the protective coating 15 based on aluminum, the protective coating 15 having an iron-free mass fraction of 0.4% Mg, 1.6% Mn and 2.0% Si.
- the two steel components 21 in FIG. 1 and FIG. 2 only show indications of an Fe seam.
- the thickness of the Fe seam is less than lpm.
- the protective coating 15 is therefore not sufficiently alloyed in the 3 minutes at 920°C.
- FIG. 3 shows a steel component 21 with a protective coating 15 based on aluminum on a steel substrate 13.
- the protective coating 15 was applied by hot dip coating. Since the melt consisted of aluminum with an additional alloy of 0.4% by weight Mg, 0.8% by weight % mn Apart from impurities in the range of 0.2% by weight, the melt contained no silicon.
- the flat steel product 11 (see FIG.
- the steel component 21 shown in the cross section image resulted with the protective coating 15 based on aluminum, the protective coating 15 having an iron-free mass fraction of 0.4% Mg, 0.8% Mn and less than 0.50% Si.
- FIG. 3 It can be clearly seen in FIG. 3 that an Fe seam 17 has formed in the protective coating. This has a thickness of 3pm. The alloying of the protective coating 15 is therefore complete after 3 minutes at 920°C. Although the steel components 21 shown in FIG. 1 and FIG. 3 have gone through an identical manufacturing process, apart from the silicon content of the melt, a pronounced Fe seam results in FIG. The reduction in the silicon content means that the process time can be significantly reduced.
- FIG. 4 shows a steel component 21 with a protective coating 15 based on aluminum on a steel substrate 13.
- the protective coating 15 was applied by hot dip coating. Since the melt consisted of aluminum with an additional alloy of 0.4% by weight Mg and 1.6% by weight Mn. Apart from impurities in the range of 0.2% by weight, the melt contained no silicon. Accordingly, after coating, the flat steel product had a protective coating 15 with a thickness of 25 ⁇ m, the protective coating 15 having an iron-free mass fraction of 0.4% Mg, 1.6% Mn and less than 0.50% Si. After the hot forming explained, the result was the steel component 21 shown in the cross section with the protective coating based on aluminum, where the protective coating 15 has an iron-free mass fraction of 0.4% Mg, 1.6% Mn and less than 0.50% Si.
- FIG. 4 shows that this effect of the manganese only occurs with a low proportion of silicon.
- the manganese content is increased in the variant according to FIG. 2 compared to the variant according to FIG. 1, due to the higher silicon content, there is no stronger Fe fringe in FIG. 2 compared to FIG.
- Figure 5 shows the thickness of the Fe seam as a function of the annealing time for three different variants for the non-ferrous mass fractions:
- FIG. 6 shows the same representation as FIG. 5.
- the silicon content was also increased to an iron-free mass fraction of 2%.
- the following variants are therefore shown (the last two curves are identical and therefore cannot be distinguished in the diagram):
- FIG. 7 shows the thickness of the Fe seam with an annealing time of 3 minutes as a function of the iron-free mass fraction of manganese.
- the ironless mass fraction of silicon is about 0.2%. From an iron-free mass fraction of manganese of about 0.3%, a thicker Fe seam results, where the thickness of the Fe seam increases with the manganese content.
- FIG. 8 shows the effects of the silicon.
- the thickness of the Fe seam with an annealing time of 3 minutes is plotted as a function of the non-ferrous mass fraction of silicon.
- the non-ferrous mass fraction of manganese was 1.6%.
- the manganese effect is still significant, with the effect being greater the smaller the massless fraction of silicon is.
- FIG. 9 shows the described effects again for variants without magnesium.
- the thickness of the Fe seam is shown as a function of the annealing time for three different variants for the ironless mass fractions:
- Figure 10 shows the thickness of the Fe seam as a function of the annealing time for the same layer compositions as in Figure 9.
- pre-alloying was carried out before annealing, in which the blanks were pre-alloyed for a pre-alloying time of 13 seconds at a pre-alloying temperature of 680 °C were maintained.
- the Fe seam forms much earlier in all cases and is thicker than without a master alloy for the same annealing time.
- the manganese effect can be seen, that a significant Fe fringe forms faster with manganese alloying. This is the case with both 0% Si and 0.5% silicon.
- FIG. 12 shows a schematic representation of a flat steel product 11 for hot forming, which is made from a steel substrate 13 made from a steel containing 0.1-3% by weight Mn and optionally up to 0.01% by weight B. and an Al-based protective coating 15 applied to the steel substrate 13 .
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP22729619.1A EP4341454A1 (en) | 2021-05-21 | 2022-05-18 | Flat steel product having an al-coating, process for production thereof, steel component and process for production thereof |
CN202280036669.9A CN117355620A (en) | 2021-05-21 | 2022-05-18 | Flat steel product with aluminum coating, method for producing same, steel component and method for producing same |
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EP21175294.4A EP4092141A1 (en) | 2021-05-21 | 2021-05-21 | Flat steel product with an al coating, method for producing the same, steel component and method for producing the same |
EP21175294.4 | 2021-05-21 |
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WO2022243397A1 true WO2022243397A1 (en) | 2022-11-24 |
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PCT/EP2022/063495 WO2022243397A1 (en) | 2021-05-21 | 2022-05-18 | Flat steel product having an al-coating, process for production thereof, steel component and process for production thereof |
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EP (2) | EP4092141A1 (en) |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5623265A (en) * | 1979-08-01 | 1981-03-05 | Nisshin Steel Co Ltd | Hot dip aluminized steel excellent in corrosion |
JPH05171393A (en) * | 1991-12-26 | 1993-07-09 | Sumitomo Metal Ind Ltd | Hot-dip al plated steel excellent in wet corrosion resistance |
EP0971044B1 (en) | 1998-07-09 | 2003-05-14 | Sollac | Clad hot-rolled and cold-rolled steel sheet, presenting a very high resistance after thermal treatment |
EP2086755A1 (en) | 2006-10-30 | 2009-08-12 | ArcelorMittal France | Coated steel strips, methods of making the same, methods of using the same, stamping blanks prepared from the same, stamped products prepared from the same, and articles of manufacture which contain such a stamped product |
EP2993248A1 (en) * | 2014-09-05 | 2016-03-09 | ThyssenKrupp Steel Europe AG | Flat steel product with an Al coating, method for producing the same, steel component and method for producing the same |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1219719B1 (en) * | 2000-12-25 | 2004-09-29 | Nisshin Steel Co., Ltd. | A ferritic stainless steel sheet good of workability and a manufacturing method thereof |
CN111575622B (en) * | 2020-05-11 | 2022-07-15 | 马鞍山钢铁股份有限公司 | Aluminum-plated steel sheet for hot-formed parts having excellent coating properties, method for producing same, and hot-formed parts |
-
2021
- 2021-05-21 EP EP21175294.4A patent/EP4092141A1/en not_active Withdrawn
-
2022
- 2022-05-18 EP EP22729619.1A patent/EP4341454A1/en active Pending
- 2022-05-18 CN CN202280036669.9A patent/CN117355620A/en active Pending
- 2022-05-18 WO PCT/EP2022/063495 patent/WO2022243397A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5623265A (en) * | 1979-08-01 | 1981-03-05 | Nisshin Steel Co Ltd | Hot dip aluminized steel excellent in corrosion |
JPH05171393A (en) * | 1991-12-26 | 1993-07-09 | Sumitomo Metal Ind Ltd | Hot-dip al plated steel excellent in wet corrosion resistance |
EP0971044B1 (en) | 1998-07-09 | 2003-05-14 | Sollac | Clad hot-rolled and cold-rolled steel sheet, presenting a very high resistance after thermal treatment |
EP2086755A1 (en) | 2006-10-30 | 2009-08-12 | ArcelorMittal France | Coated steel strips, methods of making the same, methods of using the same, stamping blanks prepared from the same, stamped products prepared from the same, and articles of manufacture which contain such a stamped product |
EP2993248A1 (en) * | 2014-09-05 | 2016-03-09 | ThyssenKrupp Steel Europe AG | Flat steel product with an Al coating, method for producing the same, steel component and method for producing the same |
Also Published As
Publication number | Publication date |
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CN117355620A (en) | 2024-01-05 |
EP4092141A1 (en) | 2022-11-23 |
EP4341454A1 (en) | 2024-03-27 |
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