EP1857567B1 - Verfahren zum Herstellen eines mit einem Korrosionsschutzsystem überzogenen Stahlflachprodukts - Google Patents
Verfahren zum Herstellen eines mit einem Korrosionsschutzsystem überzogenen Stahlflachprodukts Download PDFInfo
- Publication number
- EP1857567B1 EP1857567B1 EP06113963.0A EP06113963A EP1857567B1 EP 1857567 B1 EP1857567 B1 EP 1857567B1 EP 06113963 A EP06113963 A EP 06113963A EP 1857567 B1 EP1857567 B1 EP 1857567B1
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- EP
- European Patent Office
- Prior art keywords
- coating
- steel substrate
- layer
- steel
- zinc
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- 229910000831 Steel Inorganic materials 0.000 title claims description 102
- 239000010959 steel Substances 0.000 title claims description 102
- 238000005260 corrosion Methods 0.000 title claims description 55
- 230000007797 corrosion Effects 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000576 coating method Methods 0.000 claims description 136
- 239000011248 coating agent Substances 0.000 claims description 128
- 239000010410 layer Substances 0.000 claims description 90
- 239000000758 substrate Substances 0.000 claims description 69
- 239000011701 zinc Substances 0.000 claims description 40
- 229910052725 zinc Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 229910052749 magnesium Inorganic materials 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000003618 dip coating Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 229910052745 lead Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011253 protective coating Substances 0.000 claims description 6
- 229910018084 Al-Fe Inorganic materials 0.000 claims description 5
- 229910018192 Al—Fe Inorganic materials 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 description 37
- 239000004922 lacquer Substances 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000005246 galvanizing Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001474791 Proboscis Species 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B1/00—Cleaning by methods involving the use of tools
- B08B1/10—Cleaning by methods involving the use of tools characterised by the type of cleaning tool
- B08B1/16—Rigid blades, e.g. scrapers; Flexible blades, e.g. wipers
- B08B1/165—Scrapers
-
- 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
-
- 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
- C23C2/26—After-treatment
-
- 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
- C23C2/29—Cooling or quenching
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
Definitions
- the invention relates to a method for producing a steel flat product coated with a corrosion protection system, in which a zinc-based coating is applied to a steel substrate, such as steel strip or sheet, by means of hot-dip coating and an organic coating is applied to the zinc-based coating.
- metallic coatings are applied, in particular on steel sheets or strips, which are based on zinc or zinc alloys in the majority of applications.
- Such zinc or zinc alloy coatings protect due to their barrier and cathodic protection effect the corresponding coated steel sheet in practical use against corrosion.
- the corrosion resistance of zinc-coated sheets can be further improved by application of organic coatings, which in practice are generally multi-layer coating systems.
- a method of coating for example, steel sheets provided with a zinc coating with one Paint system is in the WO 98/24857 described.
- the substrate surface is first cleaned.
- an inorganic and / or organic pretreatment agent is applied to the coating.
- a so-called "primer” serving as an adhesion promoter is then applied to the coating layer prepared in this way, onto which in turn one of an amine-modified epoxy resin and a crosslinking agent-containing coating material is applied by spraying, dipping, knife coating, rolling or brushing.
- the coated substrates should therefore have a good and uniform surface quality and are characterized by good formability, durability, resistance to chemical substances, corrosion and weathering resistance.
- the object of the invention was to provide a method which allows an economical production of highly corrosion-resistant and at the same time readily processable flat steel products.
- a steel substrate present in the form of a steel sheet or strip is subjected to a coating process, the steps of which are preferably completed in continuous operation with regard to the economic efficiency of its large-scale implementation.
- the throughput speeds set in practice can be in the range from 60 to 150 m / min, depending on the respective performance and the time required for the respective processing step.
- the steel substrate is first preheated.
- DFF Direct Fired Furnace
- RTF Radiant Tube Furnace
- the maximum band temperature achieved is set to 720 ° C. to 850 ° C., depending on the steel grade.
- the steel substrate runs under exclusion of air in a zinc bath. This can be done in a conventional manner, for example by a with the Inside the annealing furnace connected and with its opening into the melt bath dipping proboscis into which the melt bath are led.
- the melt bath consists of a melt which, in addition to zinc and the usual manufacturing-related impurities, has magnesium and aluminum contents.
- the composition of the melt is chosen so that forms a Zn-Mg-Al-Fe-containing metallic corrosion protection coating on the steel substrate. This has due to the distribution of the alloying elements contained in it on the one hand optimal adhesion to the steel substrate and on the other hand, a surface finish, which is suitable for a direct application of an organic coating without complex pretreatment. At the same time, the coating has excellent weldability, which makes flat steel products according to the invention particularly suitable for spot welding.
- the layer structure of the coating can be formed so that in its immediately adjacent to the surface surface boundary layer whose thickness is limited to max. 10% of the total thickness of the coating is limited, the elements Mg and Al are initially present enriched as an oxide. In addition, Zn oxide is present on the surface. The amount of Al enrichment on the immediate surface is at most about 1 wt%.
- the oxide layer forming on the zinc alloy coating passivates the surface and allows a direct paint connection.
- the operating parameters of the zinc dip coating according to the invention are preferably adjusted so that the thickness of the surface boundary layer is less than 5%, in particular less than 1%, of the total thickness of the metallic coating.
- the surface boundary layer is followed, to a thickness of at least 25% of the total overlay of the coating, by an intermediate layer having Al contents of not more than 0.25% by weight.
- the Al content rises to 4.5% at the boundary to the steel substrate.
- the Mg enrichment on the immediate surface of the coating is significantly greater than the Al enrichment. Mg contents of up to 10% are achieved here.
- the amount of Mg decreases over the intermediate layer and is 0.5 to 2% at a depth of about 25% of the total overlay thickness of the overlay.
- An increase of the Mg content in the direction of the steel substrate then takes place via the boundary layer. At the border to the steel substrate, the Mg content is up to 3.5%.
- the low Al content in the intermediate layer ensures a particularly good weldability and a uniform surface formation, while the alloy alloyed into the boundary layer ensures the particularly good adhesion of the coating to the steel substrate.
- the especially good even with low coating thicknesses Anti-corrosive effect of the coating is guaranteed by the high levels of Mg and Al in the boundary layer.
- the information on the structure of the corrosion-coating layer and its individual layers contained herein and in the claims relates to a layer profile determined by a GDOS measurement (glow discharge optical emission spectrometry).
- a GDOS measurement low discharge optical emission spectrometry
- Hubert Gräfen, VDI-Verlag GmbH, Dusseldorf, 1993 is a standard method for rapidly detecting a concentration profile of coatings.
- the above enumerated properties of a metallic anticorrosive coating produced according to the invention are particularly certain in that, according to the invention, the Al content of the melt bath is 0.15-0.4% by weight. It has been found that with such a relatively low Al contents of a melt bath used for carrying out the method according to the invention, the expression of the desired layer structure according to the invention can be directly influenced by a suitable adjustment of the tape immersion and / or bath temperature.
- the process according to the invention during hot dip coating ensures that high Al and Mg contents accumulate in the boundary layer of the metallic corrosion protection coating adjacent to the steel substrate, while in particular low Al contents are present in the intermediate layer.
- the difference between the temperature of the strip during immersion and the temperature of the melt bath comes one special importance.
- the inventively minimized presence of Al in the intermediate layer can be set safely and selectively.
- the Mg content of the melt bath can be limited to 0.2-2.0% by weight, in particular 0.5-1.5% by weight.
- Elements from the group Pb, Bi, Cd, Ti, B, Si, Cu, Ni, Co, Cr, Mn, Sn and rare earths can be obtained in a corrosion protection coating produced according to the invention up to a total of their contents of 0.8% by weight. be present in the coating according to the invention.
- Pb, Bi and Cd can be used to form a larger crystal structure (zinc flower), Ti, B, Si to improve the formability, Cu, Ni, Co, Cr, Mn to influence the boundary layer reactions, Sn for influencing the surface oxidation and rare earths, in particular Lanthanum and cerium, can be added to improve the flow behavior of the melt.
- the impurities which may be present in a corrosion protection coating according to the invention also include the constituents which, as a result of the hot-dip coating, enter the coating from the steel substrate in quantities which do not affect the properties of the coating.
- the coating thickness of the coating is set to 3 - 20 .mu.m , which a pad weight of the metallic corrosion protection coating of 20 - 140 g / m 2 each Page corresponds.
- the excellent corrosion protection effect of coatings formed according to the invention makes it possible to limit the thickness of the coating to values of 4 to 12 ⁇ m , which corresponds to a coating weight of 30 to 85 g / m 2 per side. With such thin coatings coated steel substrates can be particularly well processed.
- the stripping of superfluous coating material carried out to adjust the coating thickness can be carried out, for example, in a manner known per se by means of gas jets ejected from a nozzle scraper system.
- nitrogen is preferably used as the gas for the gas jets in order to largely suppress oxidation of the surface of the coating.
- the steel strip now provided with the zinc-based, Mg- and Al-containing metallic corrosion protection coating has been led out of the zinc bath, it is purposefully cooled.
- the final temperature reached corresponds typically to the room temperature.
- the steel substrate provided with the metallic anticorrosion coating can be subjected to a skin pass rolling in order to obtain a texturizing of its surface which is optimally suitable for the subsequent coating.
- Both the controlled cooling and optionally carried out temper rolling are carried out in view of the economy and the output preferably in a line and in continuous flow with the galvanizing process.
- the steel substrate coated in accordance with the invention is organically coated. This can be done in a separate coil coating plant or also be carried out inline directly after cooling or, if necessary, additionally performed skin-pass. A procedure that is continuous with the preceding step is also favorable here, because then the coating can be applied with particularly good results of work directly on the freshly produced metallic surface. In particular, in the case of an organic coating following in line with the respective previous working step, it is avoided that the metallic coating is altered by aging, lubrication or degreasing.
- the organic coating may discontinuously in a manner known per se via a separate coil coating system.
- the steel substrate provided with the coating may first be oiled after the galvanizing, the cooling or the rolling, in order to ensure a temporary corrosion protection.
- Another variant is a "sealing" of the steel substrate and galvanizing.
- a layer of polyacrylate or polyester up to about 2 .mu.m thick is applied as a simple corrosion protection and further processing aid, which may, inter alia, be made thermally or UV-curing.
- a “mild cleaning” is understood to mean a cleaning in which the surface of the metallic anticorrosive coating is mixed with a mildly alkaline cleaning agent (pH 9-10, free alkalinity up to 14) or a strongly alkaline one (pH 12-12 5, free alkalinity 5), but with a low concentration of detergent.
- a mildly alkaline cleaning agent pH 9-10, free alkalinity up to 14
- a strongly alkaline one pH 12-12 5, free alkalinity 5
- Detergents suitable for this purpose are, for example, liquids based on phosphate-containing potassium or sodium hydroxide solutions whose temperature is typically in the range from 40 to 70.degree.
- a pre-treatment can be applied to the strip surface by means of spraying, dipping or with the aid of a roll coater, which passivates the metallic surface and ensures adhesion between the metal coating and the lacquer.
- This pretreatment is preferably a Cr VI -free system, preferably a completely Cr-free system which is produced, for example, based on Ti, Zr, P and / or Si. Because the native oxide layers deposited on the coated steel substrate set, already ensure a very good passivation of the surface, however, can be completely dispensed with in many practical applications such a pretreatment and applied the paint directly on the possibly only degreased metallic substrate.
- the curing of the coating by means of heat or radiation.
- hardening by radiation in particular UV radiation
- thermal post-combustion of released solvents can be dispensed with.
- a plant for UV curing can be realized on a length that is significantly shorter than the length that must be provided for a required for thermal drying convection oven.
- the procedure of the invention using Cr VI- free pretreatment agents achieves corrosion protection properties at least as good as those of products pretreated with Cr VI- containing agents according to the prior art.
- Diag. 1 and 2 Two possible in the context of the invention sequences of the individual steps of the method according to the invention are in Diag. 1 and 2 are shown by way of example.
- the respective steel substrate (steel sheet or strip) is first preheated, then hot-dip galvanized and after an adjustment of the thickness of the metallic coating produced on the substrate nach rolled up to form an optimized surface structure with low degrees of deformation.
- an organic coating system formed from a primer and a lacquer is either applied directly to the metallic anti-corrosion coating without intermediate cleaning and pretreatment, or applied to the metallic anti-corrosion coating only after a subsequent post-rolling cleaning and optionally pretreatment.
- the thickness of the superficial oxidation surface boundary layer is max. 0.2 ⁇ m and is based on the determined in a GDOS measurement layer profile in each case in the range of up to 2.7% of the total overlay thicknesses.
- the amount of Al enrichment on the immediate surface is at most about 1 wt .-%. This is followed up to a thickness of at least 25% of the total overlay of the coating, the intermediate layer with a low Al content of maximum 0.25 wt .-% of. In the boundary layer, the Al content rises to 4.5% at the boundary to the steel substrate.
- the Mg enrichment on the immediate surface of the coating is significantly greater than the Al enrichment. Mg contents of up to 20% are achieved here.
- the amount of Mg decreases over the intermediate layer and is 0.5 to 2% at a depth of about 25% of the total overlay thickness of the overlay.
- An increase of the Mg content in the direction of the steel substrate then takes place via the boundary layer. At the border to the steel substrate, the Mg content is up to 3.5%.
- the about 2.5 ⁇ m thick intermediate layer to the surface boundary layer includes, whose Al content is below 0.2%, respectively.
- the thickness of the intermediate layer is therefore approximately 36% of the total overlay thickness of the respective anti-corrosion coating of 7 ⁇ m .
- the intermediate layer merges into a boundary layer adjacent to the steel substrate, in which the contents of Al, Mg and Fe have increased significantly compared with the corresponding contents of the intermediate layer.
- Fig. 1 does not show to scale a section of a produced and obtained in accordance with the invention and flat steel flat product in cross section. Accordingly, S initially an about 7.5 ⁇ m thick metallic corrosion protection coating K applied to the exterior in use, the corrosive attack particularly exposed to side A of a present as a steel sheet steel substrate, which consists essentially of Zn, Al, Mg and Fe.
- a primer layer P On the surface of the corrosion protection coating K is directly, ie without further pretreatment, a primer layer P applied.
- the layer thickness of the primer layer P is 5 ⁇ m in conventional primer products. Be so-called "thick-layer primer” used the thickness of the primer layer P may be up to 20 ⁇ m.
- a lacquer layer L has been applied, whose thickness is about 20 ⁇ m.
- the primer layer P can be previously pretreated by means of UV rays.
- a topcoat D is applied, which is up to 17 .mu.m thick.
- the primer layer P, the lacquer layer L and the topcoat D together form an organic coating which, in spite of the omission of a pretreatment of the surface of the anticorrosive coating K, together with the metallic anticorrosive coating K, protects the steel substrate S particularly well against corrosion.
- an approximately 7.5 ⁇ m thick metallic corrosion protection coating Ki is also initially applied, substantially consisting of Zn, Al, Mg and Fe.
- a paint layer Li is applied, whose thickness is 5 - 10 microns .
- Fig. 2 does not show to scale a section of a second in accordance with the invention produced and procured, also for use in the field of vehicle construction particularly suitable steel flat product in cross section. Accordingly, on the outside in use, the corrosive attack is particularly strong exposed side of the present as a steel sheet steel substrate S is first applied an approximately 5 ⁇ m thick metallic corrosion protection coating K, which consists essentially of Zn, Al, Mg and Fe.
- the surface of the anticorrosive coating K has first of all been subjected to a pretreatment in which a thin pretreatment layer V has remained on the anticorrosive coating K.
- a V about 8 ⁇ m thick primer layer P1 is applied.
- the primer layer P1 carries an approximately 5 ⁇ m thick adhesive layer E, via the one laid on the adhesive layer E, about 52 ⁇ m thick laminated film F is adhered to the primer layer P1.
- a further primer layer P2 is applied, in turn, an approximately 20 ⁇ m thick topcoat carries D.
- the top coat layer D forms the outer finish of the organic coating system formed from the primer layer P1, the adhesive layer E, the composite film F, the primer layer P2 and the topcoat layer D.
- an approximately 5 ⁇ m thick metallic corrosion protection coating Ki is also initially applied, which consists essentially of Zn, Al, Mg and Fe.
- the surface of the anti-corrosion coating Ki has been pretreated in this case to form a thin pretreatment layer Vi first.
- a lacquer layer has been applied, which is typically 5 ⁇ m thick.
- Fig. 3 does not show to scale a section of a third in accordance with the invention produced and created, for general building exterior applications particularly suitable flat steel product in cross section. Accordingly, S is first applied an approximately 10 ⁇ m thick metallic corrosion protection coating K to the external in use, the corrosive attack particularly exposed side of the present as a steel sheet steel substrate, consisting essentially of Zn, Al, Mg and Fe. The surface of the anticorrosive coating K has also been subjected to a pretreatment in this case, in which a thin pretreatment layer V has remained on the anticorrosive coating K.
- an approximately 5 ⁇ m thick primer layer P is applied, which in turn carries an approximately 20 ⁇ m thick topcoat layer D.
- the topcoat D itself carries on its outer side a peelable protective film U, which protects the flat steel product during its transport and storage.
- the protective film U can also be listed as a permanently adhering film to improve the surface properties.
- an approximately 10 ⁇ m thick metallic corrosion protection coating Ki is also initially applied, the substantially Zn, Al, Mg and Fe.
- the surface of the anticorrosion coating Ki has also been pretreated in this case to form a thin pretreatment layer V first.
- a resist layer Li has been applied, which is typically 7-15 ⁇ m thick.
- Fig. 4 does not show to scale a section of a fourth produced in accordance with the invention and procured, in particular suitable for home appliance steel flat product in cross section. Accordingly, first an about 4 on the exterior in use, the corrosive attack particularly exposed side of a present as a steel sheet steel substrate S - applied 5 ⁇ m thick metallic corrosion protection coating K, consisting essentially of Zn, Al, Mg and Fe.
- an approximately 8 ⁇ m thick primer layer P On the surface of the anticorrosive coating K is immediate, that is applied, without further pretreatment, an approximately 8 ⁇ m thick primer layer P.
- a so-called “structure primer” has been used here, which forms a structured, elevations and depressions having surface.
- a lacquer layer L has been applied, whose thickness is about 20 ⁇ m.
- a permanently adhering protective layer can be applied to the lacquer layer, which is used inter alia to improve the surface properties.
- less corrosive attacked side of the steel substrate S is also initially an approximately 4 - 5 ⁇ m thick metallic corrosion protective coating applied Ki, which consists essentially of Zn, Al, Mg and Fe.
- Ki metallic corrosion protective coating
- a lacquer layer is applied directly Li, the thickness of 7 - is 10 ⁇ m.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Coating With Molten Metal (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06113963.0A EP1857567B1 (de) | 2006-05-15 | 2006-05-15 | Verfahren zum Herstellen eines mit einem Korrosionsschutzsystem überzogenen Stahlflachprodukts |
PL06113963T PL1857567T3 (pl) | 2006-05-15 | 2006-05-15 | Sposób wytwarzania płaskiego produktu stalowego powleczonego ochronnym systemem przeciwkorozyjnym |
US12/300,966 US20100055344A1 (en) | 2006-05-15 | 2006-05-15 | Process for Producing a Sheet Steel Product Coated with an Anticorrosion System |
ES06113963.0T ES2629109T3 (es) | 2006-05-15 | 2006-05-15 | Procedimiento para la fabricación de un producto plano de acero revestido con un sistema de protección frente a la corrosión |
KR1020087027956A KR101154534B1 (ko) | 2006-05-15 | 2007-05-15 | 부식 방지 시스템으로 코팅된 평판형 강재 제품의 제조 방법 |
CA2650719A CA2650719C (en) | 2006-05-15 | 2007-05-15 | Method for production of a flat steel product coated with a corrosion protection system |
CN2007800176384A CN101454474B (zh) | 2006-05-15 | 2007-05-15 | 制备覆有防腐蚀体系的扁钢产品的方法 |
BRPI0711621-7A BRPI0711621B1 (pt) | 2006-05-15 | 2007-05-15 | Método para produção de um produto do aço plano revestido com um sistema de proteção à corrosão |
AU2007251551A AU2007251551B2 (en) | 2006-05-15 | 2007-05-15 | Process for producing a sheet steel product coated with an anticorrosion system |
JP2009510445A JP5112422B2 (ja) | 2006-05-15 | 2007-05-15 | 防食システムによりコーティングされるフラット鋼生成物の製造方法 |
PCT/EP2007/054712 WO2007132008A1 (de) | 2006-05-15 | 2007-05-15 | Verfahren zum herstellen eines mit einem korrosionsschutzsystem überzogenen stahlflachprodukts |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06113963.0A EP1857567B1 (de) | 2006-05-15 | 2006-05-15 | Verfahren zum Herstellen eines mit einem Korrosionsschutzsystem überzogenen Stahlflachprodukts |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1857567A1 EP1857567A1 (de) | 2007-11-21 |
EP1857567B1 true EP1857567B1 (de) | 2017-04-05 |
Family
ID=37075626
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06113963.0A Not-in-force EP1857567B1 (de) | 2006-05-15 | 2006-05-15 | Verfahren zum Herstellen eines mit einem Korrosionsschutzsystem überzogenen Stahlflachprodukts |
Country Status (11)
Country | Link |
---|---|
US (1) | US20100055344A1 (ja) |
EP (1) | EP1857567B1 (ja) |
JP (1) | JP5112422B2 (ja) |
KR (1) | KR101154534B1 (ja) |
CN (1) | CN101454474B (ja) |
AU (1) | AU2007251551B2 (ja) |
BR (1) | BRPI0711621B1 (ja) |
CA (1) | CA2650719C (ja) |
ES (1) | ES2629109T3 (ja) |
PL (1) | PL1857567T3 (ja) |
WO (1) | WO2007132008A1 (ja) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL1857566T3 (pl) * | 2006-05-15 | 2017-10-31 | Thyssenkrupp Steel Europe Ag | Płaski wyrób stalowy z powłoką chroniącą przed korozją i sposób jego wytwarzania |
WO2010012235A1 (zh) * | 2008-07-30 | 2010-02-04 | 攀枝花新钢钒股份有限公司 | 热镀锌钢板及其生产方法 |
JP4778083B2 (ja) * | 2008-08-21 | 2011-09-21 | 川田工業株式会社 | 溶射被覆性に優れた溶融亜鉛めっき部材 |
JP5436009B2 (ja) * | 2009-04-07 | 2014-03-05 | 株式会社神戸製鋼所 | めっき密着性に優れた高強度合金化溶融亜鉛めっき鋼板及びその製造方法 |
CN101984130A (zh) * | 2010-10-12 | 2011-03-09 | 中国电力科学研究院 | 一种紧固件高耐腐蚀性热浸镀合金镀层及其制备工艺 |
CN102345034B (zh) * | 2011-10-12 | 2013-04-24 | 东北大学 | 一种多元素耐蚀热浸合金镀层及原料的制取方法 |
KR101353241B1 (ko) | 2011-12-28 | 2014-01-20 | 주식회사 포스코 | 고속의 금속 스트립의 생산공정과 직결한 연속 수지코팅 방법 및 이를 이용한 연속 수지코팅 시스템 |
WO2013160566A1 (fr) * | 2012-04-25 | 2013-10-31 | Arcelormittal Investigacion Y Desarrollo, S.L. | Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante. |
DE102012109855B4 (de) | 2012-10-16 | 2015-07-23 | Thyssenkrupp Steel Europe Ag | Verfahren zum Herstellen eines mit einer metallischen Korrosionsschutzschicht beschichteten Stahlprodukts |
WO2014125173A1 (fr) * | 2013-02-18 | 2014-08-21 | Arcelormittal Investigacion Y Desarrollo, S.L. | Procédé de préparation d'une tôle à revêtement znmg ou znaimg comprenant l'application d'une solution basique d'un agent complexant les ions magnésium et tôle obtenue |
CN103173707B (zh) * | 2013-02-20 | 2016-08-31 | 国网智能电网研究院 | 一种钢构件高耐腐蚀性热浸镀锌合金镀层及其制备工艺 |
WO2015052546A1 (fr) * | 2013-10-09 | 2015-04-16 | ArcelorMittal Investigación y Desarrollo, S.L. | Tôle à revêtement znaimg à flexibilité améliorée et procédé de réalisation correspondant |
CN103924123A (zh) * | 2014-02-17 | 2014-07-16 | 陕西理工学院 | 一种低铝热浸镀Zn-Al-Mg-Si合金及其制备方法 |
CN103981474B (zh) * | 2014-05-13 | 2017-07-21 | 国家电网公司 | 一种用于钢铁溶剂法热浸镀的高耐蚀锌基合金镀层 |
CN104480419A (zh) * | 2014-08-19 | 2015-04-01 | 陕西理工学院 | 一种低铝热浸镀Zn-Al-Mg-Si合金镀层的施镀方法 |
CN104895479B (zh) * | 2015-05-25 | 2016-08-24 | 安徽先锋门业科技有限公司 | 一种采用热镀锌静电喷塑管材加工生产电动伸缩门的方法 |
KR101767788B1 (ko) * | 2015-12-24 | 2017-08-14 | 주식회사 포스코 | 내마찰성 및 내백청성이 우수한 도금 강재 및 그 제조방법 |
US20210115527A1 (en) | 2016-11-29 | 2021-04-22 | Tata Steel Ijmuiden B.V. | Method for manufacturing a hot-formed article, and obtained article |
DE102017211076B4 (de) * | 2017-06-29 | 2019-03-14 | Thyssenkrupp Ag | Verfahren zum Herstellen eines mit einem Überzug versehenen Stahlbauteils und Stahlbauteil |
DE102018132171A1 (de) * | 2018-12-13 | 2020-06-18 | Thyssenkrupp Steel Europe Ag | Batteriegehäuse und Verwendung |
CN111152393A (zh) * | 2020-01-03 | 2020-05-15 | 河北工业大学 | 一种提高钢带与接枝聚乙烯界面结合力的方法 |
DE102020200326A1 (de) * | 2020-01-13 | 2021-07-15 | Thyssenkrupp Steel Europe Ag | Verfahren zur Herstellung eines oberflächenveredelten und oberflächenkonditionierten Stahlblechs |
KR102360526B1 (ko) * | 2020-05-27 | 2022-02-09 | 포스코강판 주식회사 | 내공식성이 우수한 도금강판 및 그 제조방법 |
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EP1621645A1 (en) * | 2004-07-28 | 2006-02-01 | Corus Staal BV | Steel sheet with hot dip galvanized zinc alloy coating |
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IT1036986B (it) * | 1975-06-13 | 1979-10-30 | Centro Speriment Metallurg | Lega di acciaio e prodotti contale lega rivestiti |
AU525668B2 (en) * | 1980-04-25 | 1982-11-18 | Nippon Steel Corporation | Hot dip galvanizing steel strip with zinc based alloys |
JPS5891162A (ja) * | 1981-11-18 | 1983-05-31 | Nisshin Steel Co Ltd | 溶融亜鉛めつき鋼板の製造方法 |
US4401727A (en) * | 1982-06-23 | 1983-08-30 | Bethlehem Steel Corporation | Ferrous product having an alloy coating thereon of Al-Zn-Mg-Si Alloy, and method |
US4812371A (en) * | 1986-11-17 | 1989-03-14 | Nippon Steel Corporation | Zn-Al hot-dip galvanized steel sheet having improved resistance against secular peeling of coating |
JP2755387B2 (ja) * | 1988-04-12 | 1998-05-20 | 大洋製鋼株式会社 | プレコート鋼板用溶融亜鉛アルミニウム合金めっき鋼板の製造方法およびプレコート鋼板 |
JPH02145777A (ja) * | 1988-11-28 | 1990-06-05 | Nkk Corp | 加工性、塗装性に優れた合金化溶融亜鉛めっき鋼板の製造方法 |
JPH02285057A (ja) * | 1989-04-27 | 1990-11-22 | Sumitomo Metal Ind Ltd | 溶融亜鉛めっき用鋼板の連続焼鈍方法 |
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-
2006
- 2006-05-15 EP EP06113963.0A patent/EP1857567B1/de not_active Not-in-force
- 2006-05-15 PL PL06113963T patent/PL1857567T3/pl unknown
- 2006-05-15 US US12/300,966 patent/US20100055344A1/en not_active Abandoned
- 2006-05-15 ES ES06113963.0T patent/ES2629109T3/es active Active
-
2007
- 2007-05-15 KR KR1020087027956A patent/KR101154534B1/ko active IP Right Grant
- 2007-05-15 BR BRPI0711621-7A patent/BRPI0711621B1/pt not_active IP Right Cessation
- 2007-05-15 AU AU2007251551A patent/AU2007251551B2/en not_active Ceased
- 2007-05-15 CN CN2007800176384A patent/CN101454474B/zh active Active
- 2007-05-15 CA CA2650719A patent/CA2650719C/en not_active Expired - Fee Related
- 2007-05-15 WO PCT/EP2007/054712 patent/WO2007132008A1/de active Application Filing
- 2007-05-15 JP JP2009510445A patent/JP5112422B2/ja not_active Expired - Fee Related
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SCHUHMACHER B ET AL: "Element distribution of aluminium and lead in hot-dip galvanized coatings and their influences on the coating properties", PROCEEDINGS OF THE 4TH INTERNATIONAL CONFERENCE ON ZINC AND ZINC ALLOY COATED STEEL SHEET (GALVATECH '98) MAKUHARI, CHIBA [JP], C11-6, 20 September 1998 (1998-09-20) - 23 September 1998 (1998-09-23), The Iron and Steel Institute of Japan, Tokyo [JP], pages 819 - 824 * |
Also Published As
Publication number | Publication date |
---|---|
EP1857567A1 (de) | 2007-11-21 |
CA2650719C (en) | 2011-11-15 |
ES2629109T3 (es) | 2017-08-07 |
JP5112422B2 (ja) | 2013-01-09 |
AU2007251551A1 (en) | 2007-11-22 |
CN101454474A (zh) | 2009-06-10 |
CN101454474B (zh) | 2012-06-20 |
KR20080109935A (ko) | 2008-12-17 |
KR101154534B1 (ko) | 2012-06-13 |
PL1857567T3 (pl) | 2017-09-29 |
BRPI0711621A2 (pt) | 2011-12-06 |
AU2007251551B2 (en) | 2011-08-11 |
US20100055344A1 (en) | 2010-03-04 |
BRPI0711621B1 (pt) | 2020-09-15 |
WO2007132008A1 (de) | 2007-11-22 |
JP2009537698A (ja) | 2009-10-29 |
CA2650719A1 (en) | 2007-11-22 |
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