EP2732062A2 - Method for producing a flat steel product which is provided with a metallic protective layer by means of hot dip coating - Google Patents
Method for producing a flat steel product which is provided with a metallic protective layer by means of hot dip coatingInfo
- Publication number
- EP2732062A2 EP2732062A2 EP12735114.6A EP12735114A EP2732062A2 EP 2732062 A2 EP2732062 A2 EP 2732062A2 EP 12735114 A EP12735114 A EP 12735114A EP 2732062 A2 EP2732062 A2 EP 2732062A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- atmosphere
- flat steel
- steel product
- product
- flat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 154
- 239000010959 steel Substances 0.000 title claims abstract description 154
- 238000003618 dip coating Methods 0.000 title claims abstract description 21
- 239000011241 protective layer Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000137 annealing Methods 0.000 claims abstract description 93
- 239000007789 gas Substances 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 239000000155 melt Substances 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 45
- 230000003647 oxidation Effects 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 230000001603 reducing effect Effects 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000013022 venting Methods 0.000 claims 1
- 238000009736 wetting Methods 0.000 abstract description 20
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 109
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 14
- 239000011572 manganese Substances 0.000 description 13
- 239000011651 chromium Substances 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- 238000005275 alloying Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002737 fuel gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 241001474791 Proboscis Species 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005244 galvannealing Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
-
- 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
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
-
- 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
Definitions
- the invention relates to a method for producing a by hot dip coating with a
- metallic protective layer provided flat steel product, in particular a high-strength steel flat product with a tensile strength of at least 500 MPa or a high-strength steel flat product with a tensile strength of at least 1000 MPa.
- the flat steel products in question usually have appreciable contents of certain alloying elements, which typically include manganese (Mn), aluminum (Al), silicon (Si) or chromium (Cr).
- Mn manganese
- Al aluminum
- Si silicon
- Cr chromium
- a layer of debris not only increases the resistance of the steel flat products to corrosion and thus
- Hot dip coating In addition to an electrolytically produced finish, the hot dip finishing has proven to be particularly economical and ecologically favorable
- Hot-dip coating cool, optional
- thermal, mechanical or chemical post-treatment and coiling is subjected to a coli.
- the annealing treatment carried out in this way can be used to activate the steel surface.
- an N 2 -H 2 -Glühgasatmospotrore typically with unavoidable traces of H 2 0 and 0 2 in the continuously running in the continuous furnace
- Alloying elements (Mn, Al, Si, Cr, 7) selectively form passive, non-wettable oxides on the steel surface, thereby improving the coating quality or adhesion on the steel surface
- a first method of this kind is from the
- Oxidation of Sauerstoffäffinen alloying elements are promoted without thereby FeO is formed on the surface of the flat steel product.
- the prerequisite for this, however, is a precisely coordinated interaction of the various influencing factors on the annealing gas-metal reaction, such as the composition of the annealing gas, the moisture content or
- Annealing temperature As a rule, these are distributed in an inhomogeneous manner over the entire furnace space due to the plant. This inhomogeneity makes it difficult to effectively use these processes on a large scale.
- Oxidation potential of the atmosphere surrounding the steel flat product adjusted so that forms a covering FeO layer targeted on the surfaces of the flat steel product. This FeO layer inhibits the selective
- DFI-Booster DFI
- DFI Direct Flame Impingement
- FeO layer is produced on the surface of each processed flat steel product by feeding 0.01 to 1% by volume of O 2 over a period of 1 to 10 s into a closed reaction chamber.
- a reaction chamber is only possible in an indirectly heated RTF oven, in which the
- RTF Radiant Tube Furnace
- Annealing furnace can be adjusted by a targeted humidification so that the desired internal oxidation of the alloying elements of each processed
- the pre-oxidation of the flat steel product is carried out in an indirectly heated RTF-type furnace.
- the object of the invention was to develop a method with which high and
- High-strength steels with significant alloy contents of oxygen-containing alloying elements can be hot-dip-coated cost-effectively and resource-effectively on a continuously operating plant.
- a process according to the invention for producing a flat steel product provided by hot-dip coating with a metallic protective layer accordingly comprises at least the following working steps: a) provision of a cold-rolled or hot-rolled product
- Flat steel product which in addition to Fe and unavoidable impurities (in% by weight) up to 35.0% Mn, up to 10.0% Al, up to 10.0% Si, up to 5.0% Cr, up to 2 0% Ni, each containing up to 0.5% of Ti, V, Nb, Mo, up to 0.1% each of S, P, N, up to 1.0% C; b) optional cleaning of the flat steel product; c) heating the flat steel product to a
- the heating c.l) within a heating time of 5 - 60 s c.2) takes place in a preheating furnace of the DFF type, c.3) in which a Voroxidationsabêt is formed, in which the flat steel product
- Voroxidationsatmosphotre is introduced to the surface of the flat steel product to form a covering FeO layer, c.4) while outside the pre-oxidation section in the preheating furnace, one opposite to the
- Atmosphere consisting of N 2 and additionally 5 to 15% by volume C0 2 , 0.1 to 2.0% by volume CO and in total at most 10% by volume H 2 , 0 2 and HO; Steel flat product recrystallizing annealing by keeping the steel flat product for one
- Flat steel product existing metallic protective layer i) optionally heat treating the steel flat product provided with the metallic protective layer.
- Hot-dip coating system with DFF preheater and a holding zone heat-treated, immediately cooled and surface-finished in-line.
- Annealing atmosphere in the holding zone is prepared so that the surface of the flat steel product when entering the respective Schmelztauchbad largely free of
- cold-rolled steel flat product typically has a thickness of 0.2-4.0 mm and in addition to Fe and unavoidable impurities (in% by weight)
- Mn up to 35% Mn, in particular up to 2.5% Mn, with Mn contents of at least 0.5% being typical,
- Al contents of at least 0.005% are typical
- Si up to 10.0% Si, in particular up to 2.0% Si, Si, if Si is present in effective levels, Si contents of at least 0.2% being typical, up to 5.0% Cr, in particular up to 2.0% Cr, where, if Cr is present in effective levels,
- Ni levels of at least 0.01% are typical
- the flat steel product thus provided is, if necessary, a conventionally performed
- the steel flat product is heated to a temperature of 600-1100 ° C. within a heating time of 5 to 60 s, in particular 5 to 30 s, in a DFF-type preheating furnace.
- a heating time of at least 5 s is
- Heating-up times carry the risk, the necessary mechanical properties of the final product can not be achieved.
- a shortening of the heating time to a maximum of 30 s contributes to the improvement of the plant output and the economic efficiency of the process.
- the flat steel product is exposed to a preoxidation atmosphere during the heating phase for 1-15 s, which amounts to 0.01-3.0% by volume. Contains O 2 .
- the pre - oxidation should be carried out at temperatures of at least 550 ° C, because only from this temperature onwards, the selective oxidation of the
- the pre-oxidation is carried out at temperatures up to 850 ° C, because at higher temperatures, the oxide layer is too thick.
- Voroxidationsatmospotrore forms on the processed steel flat product 20 - 300 nm, optimally 20 to 200 nm thick FeO layer, which covers the steel surface covering.
- the holding temperature is preferably 750-850 ° C, because this is the optimal production range in terms of plant utilization or
- the relevant process window within the heating phase can be realized in that at least one of the pre-oxidation zone associated burner with 0 2 - excess ( ⁇ > 1) is operated.
- the aim is to produce a very homogeneous FeO layer of uniform thickness on the flat steel product.
- Jet pipe For this purpose, a significant 0 2 - or air flow can be injected separately by means of a so-called "jet pipe" in the combustion flame.
- An example of such a jet pipe is described in DE 10 2004 047 985 A1. Jet tubes allow a highly concentrated gas flow with high flow velocity and correspondingly high kinetic energy. The inventively directed in the burner flame, from the jet pipe
- the temperature of the injected gas can be up to 100 ° C above the pre-oxidation temperature.
- At least two burners are used in the preheating furnace, one of which is one of the top and the other of the bottom of each processed
- Aligned surface of the flat steel product direct that the flat steel product from the burner flames
- the DFF preheat oven can be any suitable material. If necessary, the DFF preheat oven.
- DFI booster which heats evenly and quickly without pre-oxidizing the steel strip and improves belt cleaning. This can additionally increase plant output.
- the inventively preoxidized flat steel product After heating to the holding temperature, the inventively preoxidized flat steel product passes through 30 - 120 s, in particular 30 - 60 s, one to the
- Preheating furnace connected annealing furnace in which there is a recrystallizing annealing at the respective
- Holding temperature is subjected.
- the annealing furnace in which holding at the holding temperature is carried out, is typically designed in RTF-type.
- the ruling in the annealing furnace Glühgasatmosphotre consists of 0.01 to 85.0 vol .-% H 2 , up to 5 vol .-% H 2 0, less than 0.01 vol .-% 0 2 and the balance N 2 .
- the preferred embodiment 0.01 to 85.0 vol .-% H 2 , up to 5 vol .-% H 2 0, less than 0.01 vol .-% 0 2 and the balance N 2 .
- Range for the hydrogen content is 3.0 - 10.0 vol .-%. From 3 vol .-% hydrogen in the atmosphere, it is possible to set a sufficient reduction potential compared to FeO even with short annealing times. It is preferable to set levels of less than or equal to 10.0% by volume of hydrogen for resource saving and to reduce H 2 consumption.
- the dew point "TP" of the annealing atmosphere is included
- the dew point is preferably at most 0 ° C in order to minimize the risk of surface decarburization.
- the annealing parameters of the recrystallizing annealing are to be adjusted overall so that during the annealing a reduction of the FeO is produced, which has been formed in the course of the preceding pre-oxidation (step c)) on the surfaces of the flat steel product.
- step c the preceding pre-oxidation
- Adhesion of the metallic coating could form interfering oxides.
- Preoxidized steel flat product existing FeO layer is the incipient reduction by the contained in the annealing atmosphere H 2 to form
- At least one moistening device is provided according to the invention with which the annealing atmosphere can be selectively supplied with moisture in order to compensate for moisture losses or irregularities in the direction of the exit of the annealing furnace.
- annealing furnaces used for the recrystallizing annealing of a flat steel product are from one of its output towards its entrance against the conveying direction of each to be treated
- the inventively provided moistening device may consist of a slotted or perforated tube, wherein optimally each such tube is arranged transversely to the conveying direction of the flat steel product above and below the conveying path.
- the individual plant design may require additional humidifiers over the
- the speed of the gas flow flowing through the annealing furnace can thereby
- Preheating furnace is positioned. This change can be made by regulating the suction power or the
- the pressure gradient is usually set to values of 2 - 10 mmWs.
- the preheating furnace should be separated from the annealing furnace so that possibly from the annealing furnace
- a 0 2 -containing for example, as pure 0 2 gas flow or air flow present gas flow are introduced to vent from the annealing furnace in this area penetrating H 2 to H 2 0 .
- the 0 2 quantity fed in each case is regulated in such a way that it usually tunnel-like formed transition region between preheating and annealing furnace metrologically largely H 2 is not detectable.
- the targeted Abresure of reaching into the preheating furnace hydrogen can also be done by at least one arranged in the vicinity of the output of the preheating furnace last burner of the preheating furnace with such a high 0 2 excess
- penetrating hydrogen binds to water vapor.
- Annealing atmosphere is the flat steel product, which now has an essentially consisting of metallic iron, active surface, to the required
- Bath inlet temperature cooled. Depending on the type of hot-dip bath, the bath inlet temperature is varied between 430 and 800 ° C. That's how it is
- Steel flat product should be dip-coated with a zinc-based metallic protective layer, typically at 430-650 ° C and the temperature of the molten bath in the range of 420-600 ° C.
- a zinc-based metallic protective layer typically at 430-650 ° C and the temperature of the molten bath in the range of 420-600 ° C.
- Aluminum-based protective layers are dip-dip coated, so bath entry temperatures typically become of the flat steel product of 650 - 800 ° C at
- Inert gas atmosphere in the trunk is not required in principle. However, it proves to be advantageous depending on tape speed and
- the dew point should be between -80 - -25 ° C, especially -50 ° C to -25 ° C.
- the dew point of the inert gas atmosphere in the trunk should not be below -80 ° C, because the atmosphere is too dry underneath. This could lead to the formation of dust, which in turn would negatively affect the coating result.
- the dew point of the inert gas atmosphere in the trunk should not be above -25 ° C, because otherwise the atmosphere would be too wet, which in turn would bring an increased slag formation with it.
- a minimized risk of dust formation and simultaneously high process stability arise when the dew point in the trunk is between -50 ° C to -25 ° C.
- the steel flat product thus conducted into the melt bath passes through the melt bath within a residence time of 1 to 10 s, in particular 2 to 5 s.
- a residence time is at least 1 s, it is ensured that in the molten bath, a reactive wetting between the steel surface and the coating bath takes place.
- the cycle time should not take longer than 10 s to prevent unwanted coating sagging
- Adhesion guarantee optimized surface finish The composition of the melt bath depends on the respective specifications of the end user and may, for example, be as follows (all
- Impurities including traces of Si, Mn, Pb and rare earths; (ii) so-called 'ZM coatings':
- AS coatings less than 15% Si, less than 5.0% Fe, balance AI and unavoidable impurities, including traces of Zn and rare earths;
- the thickness of the metallic protective layer present on the steel flat product exiting the melt bath is adjusted in a conventional manner. This can be known per se
- Facilities such as wiping or similar can be used.
- ZF coating Fe-Zn alloy coating
- Melting bath proven which contains in addition to zinc and unavoidable impurities, including traces of Si, Mn and Pb, 0.1 to 0.15 wt .-% Al and up to 0.5 wt .-% Fe.
- the invention is based on
- Fig. 2 is a in the hot dip coating according to
- Fig. 1 used combination of burner and jet pipe to produce a particularly homogeneous 0 2 distribution within the combustion flame for the purpose of pre-oxidation;
- Fig. 3 is an illustration of an inventive
- dew point stabilization shows a representation of the dew point stabilization according to the invention above the critical dew point limit over the entire length of the annealing furnace by combined use of targeted pre-oxidation (dew point as a result of FeO reduction) and moistening (dew point in succession moistening).
- the hot-dip coating installation A has a horizontally oriented conveying direction F of the steel strip
- DFI booster 1 a connected to its input 2 to the DFI booster preheating furnace 3, in which a pre-oxidation section 4 is formed, an annealing furnace 6, which is connected to a transition region 7 to the output 8 of the preheating furnace 3, one to the Exit 9 of the annealing furnace 6 connected cooling zone 10, connected to the cooling zone 10 proboscis 11, which is connected to the output 12 of the cooling zone 10 and immersed with its free end in a molten bath 13, a arranged in the molten bath 13 first deflecting device 14, a Device 15 for adjusting the thickness of the applied on the flat steel product S in the molten bath 13 metallic coating and a second deflection 16 on.
- the preheating furnace 3 is of the DFF type. In it, distributed over the conveyor line of the preheating furnace 3 in Fig. 1 for clarity, not shown burner arranged. One group of these burners is assigned to the underside and another group of the upper side of the flat steel product S to be coated. Outside the pre-oxidation section 4, the burners are in
- the burners each form a jet / jet-tube combination 17 of the type shown in FIG. 2 with a jet tube.
- the burners 18 of the burner / jet-tube combinations 17 are each via a fuel gas line 19 connected to a fuel gas supply, not shown here, and via an oxygen supply line 20 to an oxygen supply, also not shown here.
- a control valve 21 Before entering the burner 18 is via a control valve 21 each have an oxygen branch line 22 to the
- Oxygen supply line 20 connected.
- Oxygen branch line 22 leads in each case to a jet pipe 23 designed in the manner of the prior art described in DE 10 2004 047 985 A1, which directs the oxygen gas jet emerging from it with high flow energy and concentration into the burner flame. In this way, a strong swirl of the
- transition area 7 is here also in the
- Transition area 7 is provided.
- the purpose of this feed is the setting of hydrogen, possibly due to the flowing in the annealing furnace 6 from the outlet 9 in the direction of its inlet gas flow G in the
- Transition area 7 arrives.
- a suction device 24 is arranged in the region of the entrance of the annealing furnace 6, which sucks the reaching to the entrance of the annealing gas flow G.
- Adjacent to the exit 9 of the annealing furnace 6 are two
- Humidifying 25,26 arranged, one of which is assigned to the top and the other of the underside of the flat steel product S to be coated.
- the moistening 25,26 are as slotted or perforated, transverse to the conveying direction F of
- the cooling zone 10 may be designed so that the cooled to the respective bath inlet temperature
- the hot-dip coated samples each consisted of one of the high / highest strength steels
- Table 1 shows the experimental parameters for the hot dip refinement of the tested samples set in the experiments. The following terms apply here:
- Tl pre-oxidation temperature in ° C
- Atml composition of the pre-oxidation atmosphere
- T2 holding temperature in ° C
- Atm2 composition of the annealing atmosphere during the
- TP1 dew point at the beginning of the annealing furnace in ° C
- TP2 dew point in the center of the annealing furnace in ° C
- TP3 dew point at the end of the annealing furnace in ° C
- T4 belt inlet temperature in ° C
- Atm3 Atmospheric composition of the trunk zone (the
- TP4 dew point of the cooling atmosphere in the trunk zone
- Hot-dip coated flat steel product is excellently suited for further processing by means of one-stage, two-stage or multi-stage cold or hot forming into a high-strength / high-strength sheet-metal component due to its mechanical properties and its surface properties. This applies primarily to applications of
- the hot-dip coated flat steel product thus not only raises the potential for lightweight construction, but also extends the product's service life.
- optimal wetting and adhesion of the hot-dip coating can be achieved by a pre-oxidation in a DFF preheating furnace and a humidification of the annealing atmosphere in a holding zone.
- a pre-oxidation in a DFF preheating furnace and a humidification of the annealing atmosphere in a holding zone.
- Voroxidationsabitess in DFF furnace prevails over the steel surface reducing or neutral atmosphere. Then, the flat steel product is reduced to a holding temperature of 600 - 1100 ° C heated flat steel product under a FeO
- Atmosphere recrystallizing annealed the dew point is maintained by addition of moisture at -40 ° C to +25 ° C, under a ⁇ 100% N2 and a dew point of -80 ° C to -25 ° C having atmosphere to one
- Bath inlet temperature of 420 - 780 ° C cooled and passed through a melt bath.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating With Molten Metal (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102011051731A DE102011051731B4 (en) | 2011-07-11 | 2011-07-11 | Process for the preparation of a flat steel product provided by hot dip coating with a metallic protective layer |
PCT/EP2012/063069 WO2013007578A2 (en) | 2011-07-11 | 2012-07-05 | Method for producing a flat steel product which is provided with a metallic protective layer by means of hot dip coating |
Publications (2)
Publication Number | Publication Date |
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EP2732062A2 true EP2732062A2 (en) | 2014-05-21 |
EP2732062B1 EP2732062B1 (en) | 2016-06-29 |
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EP12735114.6A Not-in-force EP2732062B1 (en) | 2011-07-11 | 2012-07-05 | Method for producing a flat steel product which is provided with a metallic protective layer by means of hot dip coating |
Country Status (9)
Country | Link |
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US (1) | US9096919B2 (en) |
EP (1) | EP2732062B1 (en) |
JP (1) | JP5753319B2 (en) |
KR (1) | KR101940250B1 (en) |
CA (1) | CA2839183C (en) |
DE (1) | DE102011051731B4 (en) |
ES (1) | ES2593490T3 (en) |
RU (1) | RU2573843C2 (en) |
WO (1) | WO2013007578A2 (en) |
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- 2012-07-05 EP EP12735114.6A patent/EP2732062B1/en not_active Not-in-force
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DE102019200338A1 (en) | 2018-01-12 | 2019-07-18 | Sms Group Gmbh | Process for continuous heat treatment of a steel strip, and plant for hot dip coating a steel strip |
Also Published As
Publication number | Publication date |
---|---|
DE102011051731B4 (en) | 2013-01-24 |
KR101940250B1 (en) | 2019-01-18 |
US9096919B2 (en) | 2015-08-04 |
RU2014104593A (en) | 2015-08-20 |
WO2013007578A3 (en) | 2013-05-02 |
ES2593490T3 (en) | 2016-12-09 |
CA2839183C (en) | 2018-12-11 |
JP5753319B2 (en) | 2015-07-22 |
EP2732062B1 (en) | 2016-06-29 |
KR20140059777A (en) | 2014-05-16 |
CA2839183A1 (en) | 2013-01-17 |
RU2573843C2 (en) | 2016-01-27 |
DE102011051731A1 (en) | 2013-01-17 |
WO2013007578A2 (en) | 2013-01-17 |
JP2014525986A (en) | 2014-10-02 |
US20140251505A1 (en) | 2014-09-11 |
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