EP2054536B1 - Process for coating a hot- or cold-rolled steel strip containing 6 - 30% by weight of mn with a metallic protective layer - Google Patents

Process for coating a hot- or cold-rolled steel strip containing 6 - 30% by weight of mn with a metallic protective layer Download PDF

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Publication number
EP2054536B1
EP2054536B1 EP07802701A EP07802701A EP2054536B1 EP 2054536 B1 EP2054536 B1 EP 2054536B1 EP 07802701 A EP07802701 A EP 07802701A EP 07802701 A EP07802701 A EP 07802701A EP 2054536 B1 EP2054536 B1 EP 2054536B1
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Prior art keywords
coating
steel strip
content
zinc
annealing
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German (de)
French (fr)
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EP2054536A2 (en
Inventor
Manfred Meurer
Ronny Leuschner
Harald Hofmann
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Steel Europe AG
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    • 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
    • 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
    • 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
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54—Furnaces for treating strips or wire
    • C21D9/56—Continuous furnaces for strip or wire
    • C21D9/561—Continuous furnaces for strip or wire with a controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • 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
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

Definitions

  • the invention relates to a process for coating a hot-rolled or cold-rolled steel strip containing 6 to 30% by weight of Mn with a metallic protective layer, in particular a zinc-based protective layer, in which the steel strip to be coated is heated below 800 to 1100 ° C annealed a nitrogen, water and hydrogen-containing annealing atmosphere and then subjected to a hot-dip coating.
  • steels with high manganese contents are, due to their favorable combination of properties consisting of high strengths of up to 1,400 MPa on the one hand and extremely high strains (uniform strains of up to 70% and elongations at break of up to 90%), in principle particularly suitable for use in the field of vehicle construction , especially in the automotive industry.
  • particularly suitable steels with high Mn contents of 6 wt .-% to 30 wt .-% are for example from DE 102 59 230 A1 , of the DE 197 27 759 C2 or the DE 199 00 199 A1 known. From the known steels produced flat products have at high strengths isotropic deformation behavior and are still ductile even at low temperatures.
  • JP 07-216524 A discloses a method of hot dipping a hot rolled steel plate having a high tensile strength.
  • the steel plate is first descaled, pickled and cleaned. Then, it is lightly oxidized to produce thereon an iron oxide film having a thickness of 500 - 10,000 ⁇ .
  • This iron oxide film is then reduced by reducing heating to active metallic iron. The reducing heating is carried out in such a way that a selective oxidation of Si and Mn in the steel and a concentration of these elements on the surface are avoided.
  • the reductive heating is carried out under an atmosphere whose hydrogen concentration is controlled in the range of 3 to 25% by volume so as to have a reducing ability sufficient for the reduction of the iron oxide but omitting the selective oxidation of Si and Mn ,
  • EP1612288 discloses a process for coating a 0.1 to 2.5 wt% Mn-containing steel strip with a zinc-based protective layer in which the steel strip to be coated is annealed at 650 to 900 ° C under a nitrogen, water and hydrogen containing Annealing annealed and then subjected to a hot dip coating.
  • BE1011131A6 discloses a method for coating a steel strip with a zinc-based protective layer, in which the steel strip to be coated is annealed under an annealing atmosphere and then subjected to hot-dip coating.
  • the ratio of the water content to the hydrogen content of the annealing atmosphere is between 0.07 and 0.35.
  • the object of the invention was to provide a method by which high cost manganese steel sheets can be hot dip coated in a cost effective manner.
  • the ratio% H 2 O /% H 2 of the water content% H 2 O to hydrogen Content% H 2 of the annealing atmosphere is set as a function of the respective annealing temperature T G as follows: % H 2 ⁇ O / % H 2 ⁇ 8th ⁇ 10 - 15 ⁇ T G 3 . 529
  • the invention is based on the recognition that, by a suitable setting of the annealing atmosphere, namely its hydrogen content in relation to its water content and its dew point, a surface finish of the steel strip to be coated sets during the annealing, the optimum adhesion of the subsequently applied by hot-dip coating ensured metallic protective coating.
  • the inventively set annealing atmosphere acts both with respect to the iron and against the manganese of the steel strip reducing.
  • the formation of a according to the inventors the adhesion of the melt coating on the high manganese steel substrate impairing oxide layer thus deliberately avoided.
  • the annealing and the hot dip coating can be carried out in a continuous pass.
  • This type of application of the method according to the invention is particularly suitable when the coating is carried out in a conventional coil coating plant, in which an annealing furnace and the hot dip are arranged inline in the usual way and are run continuously in succession in an uninterrupted sequence.
  • the inventive method is suitable for hot dip coating of high manganese steel strips with a substantially completely consisting of Zn and unavoidable impurities layer (so-called "Z-coating”), with a zinc-iron layer, which consists of up to 92 wt .-% Zn and up to 12% by weight of Fe (so-called “ZF coating”), with an aluminum-zinc layer whose Al content is up to 60% by weight and whose Zn content is up to 50% by weight.
  • the coating procedure according to the invention is particularly suitable for steel strips which are highly alloyed in order to ensure high strength and good elongation properties.
  • the steel strips which are provided with a metallic protective coating by hot-dip coating according to the invention typically contain (in% by weight) C: ⁇ 1.6%, Mn: 6 - 30%, Al: ⁇ 10%, Ni: ⁇ 10%, Cr: ⁇ 10%, Si: ⁇ 8%, Cu: ⁇ 3%, Nb: ⁇ 0.6%, Ti: ⁇ 0.3%, V: ⁇ 0.3%, P: ⁇ 0 , 1%, B: ⁇ 0.01%, N: ⁇ 1.0%, balance iron and unavoidable impurities.
  • a steel which (in wt .-%) C: ⁇ 1.00%, Mn: 7.00 - 30.00%, Al: 1.00 - 10.00%, Si :> 2.50 - 8.00% (assuming that the sum of Al content and Si content is> 3.50 - 12.00%), B: ⁇ 0.01%, Ni: ⁇ 8, 00%, Cu: ⁇ 3.00%, N: ⁇ 0.60%, Nb: ⁇ 0.30%, Ti: ⁇ 0.30%, V: ⁇ 0.30%, P: ⁇ 0.01% , Rest contains iron and unavoidable impurities.
  • both hot-rolled and cold-rolled steel strips can be coated in accordance with the invention.
  • the steel strips are first cleaned in a continuous operating sequence and then held in a continuous annealing process to the respective annealing temperature T G , on which they have been held over an annealing time Z G of 30 seconds under a set according to the invention hydrogen-containing annealing atmosphere, has been brought.
  • the annealed steel strips were each cooled to a bath inlet temperature of 470 ° C and passed in a continuous pass through a 460 ° C hot zinc molten bath consisting of 0.2% Al and balance of Zn and unavoidable impurities. After exiting the zinc molten bath, the thickness of the Zn protective coating on the steel strip has been adjusted in a manner known per se by means of a nozzle scraper system.
  • the steel strip provided with the coating can be oiled for transport to the end user and wound up into a coil.
  • test series V1 comprised five experiments V1.1 - V1.5 with a steel strip produced from steel S1. in the In the course of the test series V2, seven experiments V2.1 - V2.7 were carried out with a steel strip made of steel S2. In test series V3, eleven tests were finally carried out on a steel strip made of steel S3.
  • the ratio% H 2 O /% H 2 is plotted against the annealing temperature T G.
  • the area located below this curve is "E" in which according to the condition % H 2 ⁇ O / % H 2 ⁇ 8th ⁇ 10 - 15 ⁇ T G 3 . 529 the ratios% H 2 O /% H 2 maintained in the inventive setting of the annealing atmosphere are separated from the region "N" located above the curve K, in which the ratios% H 2 O /% H 2 of an atmosphere not adjusted according to the invention are arranged.
  • FIG. 4 shows the result of a ball impact test carried out on the steel sheet coated in experiment V1.2.
  • the poor adhesion of the coating to the steel substrate is evidenced by the cracks in the most deformed area of the cup formed in the steel sheet.
  • Table 1 stolen C Si Mn P Cr Ni V S1 0.60 0.28 22.5 0,021 0,003 0.077 0,006 S2 0.63 0.20 22.2 0,014 0.130 0.046 0,200 S3 0.62 0.30 22.5 0,018 0,600 0,170 0,300 Data in wt .-%, balance Fe and unavoidable impurities attempt T G [° C] % H 2 [%] TP [° C] % H 2 O [%] % H 2 O /% H 2 Evaluation of galvanizing According to the invention V1.1 850 50 -31 0.03375 0.0006750 Bad No V1.2 850 100 -30 0.03747 0.0003747 Bad No V1.3 900 50 -38 0.01584 0.0003168 Bad No V1.4 950 50

Abstract

A method for coating hot-rolled or cold-rolled steel strip containing 6-30 wt %. Mn with a metallic protective layer, includes annealing the steel strip at a temperature of 800-1100° C. under an annealing atmosphere containing nitrogen, water and hydrogen and then subjecting the steel strip to hot dip coating. The method provide an economical way of hot dip coating a high manganiferous sheet steel in that, in order to produce a metallic protective layer substantially free from oxidic sub-layers on the steel strip, the % H2O/% H2 ratio of the water content % H2O to the hydrogen content % H2 in the annealing atmosphere is adjusted as a function of the respective annealing temperature TG as follows: % H2O/% H2≰8·10−15·TG3.529.

Description

Die Erfindung betrifft ein Verfahren zum Beschichten eines 6 - 30 Gew.-% Mn enthaltenden warm- oder kaltgewalzten Stahlbands mit einer metallischen Schutzschicht, insbesondere einer auf Zink basierenden Schutzschicht, bei dem das zu beschichtende Stahlband bei einer 800 - 1100 C° betragenden Glühtemperatur unter einer Stickstoff, Wasser und Wasserstoff enthaltenden Glühatmosphäre geglüht und anschließend einer Schmelztauchbeschichtung unterzogen wird.The invention relates to a process for coating a hot-rolled or cold-rolled steel strip containing 6 to 30% by weight of Mn with a metallic protective layer, in particular a zinc-based protective layer, in which the steel strip to be coated is heated below 800 to 1100 ° C annealed a nitrogen, water and hydrogen-containing annealing atmosphere and then subjected to a hot-dip coating.

Stähle mit hohen Mangan-Gehalten eignen sich aufgrund ihrer günstigen Eigenschaftskombination aus hohen Festigkeiten von bis zu 1.400 MPa einerseits und extrem hohen Dehnungen (Gleichmaßdehnungen bis zu 70 % und Bruchdehnungen bis zu 90 %) andererseits grundsätzlich im besonderen Maße für die Verwendung im Bereich des Fahrzeugbaus, insbesondere im Automobilbau. Für diesen Einsatzzweck besonders geeignete Stähle mit hohen Mn-Gehalten von 6 Gew.-% bis 30 Gew.-% sind beispielsweise aus der DE 102 59 230 A1 , der DE 197 27 759 C2 oder der DE 199 00 199 A1 bekannt. Aus den bekannten Stählen erzeugte Flachprodukte weisen bei hohen Festigkeiten ein isotropes Verformungsverhalten auf und sind darüber hinaus auch bei tiefen Temperaturen noch duktil.On the other hand, steels with high manganese contents are, due to their favorable combination of properties consisting of high strengths of up to 1,400 MPa on the one hand and extremely high strains (uniform strains of up to 70% and elongations at break of up to 90%), in principle particularly suitable for use in the field of vehicle construction , especially in the automotive industry. For this purpose particularly suitable steels with high Mn contents of 6 wt .-% to 30 wt .-% are for example from DE 102 59 230 A1 , of the DE 197 27 759 C2 or the DE 199 00 199 A1 known. From the known steels produced flat products have at high strengths isotropic deformation behavior and are still ductile even at low temperatures.

Diesen Vorteilen steht jedoch gegenüber, dass hochmanganhaltige Stähle zu Lochfraß neigen und nur schwer zu passivieren sind. Diese im Vergleich zu niedriger legierten Stählen bei Einwirken erhöhter Chloridionen-Konzentrationen große Neigung zu lokal zwar begrenzter, jedoch intensiver Korrosion macht die Verwendung von zur Werkstoffgruppe der hochlegierten Stahlbleche gehörenden Stählen gerade im Karosseriebau schwierig. Zudem neigen hochmanganhaltige Stähle zu Flächenkorrosion, die das Spektrum ihrer Verwendung ebenfalls einschränkt.These advantages, however, contrast with the fact that high manganese steels tend to pitting and are difficult to passivate. This compared to lower alloyed steels when exposed to elevated chloride ion concentrations great tendency to locally limited, but intense corrosion makes the use of the material group of high-alloy steel sheets belonging steels straight in the body construction difficult. In addition, high manganese steels tend to surface corrosion, which also limits the spectrum of their use.

Daher ist vorgeschlagen worden, auch Stahlflachprodukte, die aus hochmanganhaltigen Stählen erzeugt sind, in an sich bekannter Weise mit einem metallischen Überzug zu versehen, die den Stahl vor korrosivem Angriff schützt. So ist versucht worden, durch elektrolytisches Beschichten auf das Stahlmaterial eine Zinkbeschichtung aufzutragen.It has therefore been proposed to also provide flat steel products, which are produced from high-manganese steels, in a manner known per se with a metallic coating which protects the steel from corrosive attack. Thus, it has been attempted to apply a zinc coating by electrolytic coating on the steel material.

Die auf diese Weise beschichteten, hochmanganlegierten Stahlbänder sind zwar durch die aufgetragene metallische Beschichtung gegen Korrosion geschützt. Allerdings ist das dazu erforderliche elektrolytische Beschichten ein verfahrenstechnisch relativ aufwändiges Verfahren. Dazu kommt die Gefahr einer für den Werkstoff schädlichen Wasserstoffaufnahme.Although the high-manganese steel strips coated in this way are protected against corrosion by the applied metallic coating. However, the electrolytic coating required for this is a procedurally relatively complicated process. In addition there is the danger of a hydrogen uptake which is detrimental to the material.

Praktische Versuche, Stahlbänder mit hohen Mangangehalten durch kostengünstiger durchführbares Schmelztauchbeschichten mit einer metallischen Schutzschicht zu versehen, brachten neben grundsätzlichen Problemen bei der Benetzung mit Schmelze insbesondere im Hinblick auf die bei einer Kaltverformung von dem Überzug geforderten Haftung auf dem Stahlsubstrat unbefriedigende Ergebnisse.Practical attempts to provide steel strips with high manganese contents by means of cost-effective hot-dip coating with a metallic protective layer brought about unsatisfactory results in addition to fundamental problems with wetting with melt, in particular with regard to the adhesion to the steel substrate required for cold deformation of the coating.

Als Grund für diese schlechten Haftungseigenschaften wurde die starke Oxidschicht ermittelt, die sich bei der für das Schmelztauchbeschichten unverzichtbaren Glühung einstellt. Die derart oxidierten Blechoberflächen lassen sich nicht mehr mit der erforderlichen Gleichmäßigkeit und Vollständigkeit mit dem Überzugsmetall benetzen, so dass das Ziel eines flächendeckenden Korrosionsschutzes nicht erreicht wird.The reason for these poor adhesion properties was found to be the thick oxide layer which sets in the annealing required for hot-dip coating. The thus oxidized sheet surfaces can no longer be wetted with the required uniformity and completeness with the coating metal, so that the goal of a nationwide corrosion protection is not achieved.

Die aus dem Bereich von hochlegierten, jedoch niedrigere Mn-Gehalte aufweisenden Stählen bekannten Möglichkeiten der Verbesserung der Benetzbarkeit durch Aufbringen einer Zwischenschicht aus Fe oder Ni führten bei Stahlblechen mit mindestens 6 Gew.-% Mangan nicht zu dem gewünschten Erfolg.The known from the field of high-alloyed, but lower Mn-containing steels known ways of improving the wettability by applying an intermediate layer of Fe or Ni resulted in steel sheets with at least 6 wt .-% manganese not to the desired success.

In der DE 10 2005 008 410 B3 ist vorgeschlagen worden, auf ein 6 - 30 Gew.-% Mn enthaltendes Stahlband vor der dem Schmelztauchbeschichten vorangehenden letzten Glühung eine Aluminiumschicht aufzutragen. Das auf dem Stahlband haftende Aluminium verhindert bei der der Schmelzbeschichtung vorgeschalteten Glühung des Stahlbands, dass dessen Oberfläche oxidiert. Anschließend bewirkt die Aluminium-Schicht nach Art eines Haftvermittlers, dass der durch die Schmelzbeschichtung erzeugte Überzug auch dann fest und vollflächig auf dem Stahlband haftet, wenn das Stahlband selbst aufgrund seiner Legierung dazu ungünstige Voraussetzungen bietet. Dazu wird bei dem bekannten Verfahren der Effekt genutzt, dass es bei der der Schmelzbeschichtung notwendig vorgeschalteten Glühbehandlung zu einer Diffusion des Eisens des Stahlbands in die Aluminiumschicht kommt. Im Zuge der Glühung entsteht auf dem Stahlband somit eine metallische, im Wesentlichen aus A1 und Fe bestehende Auflage, die stoffschlüssig mit dem durch das Stahlband gebildeten Untergrund verbunden ist.In the DE 10 2005 008 410 B3 For example, it has been proposed to apply an aluminum layer to a 6-30 wt.% Mn-containing steel strip prior to the final annealing preceding the hot-dip coating. The aluminum, which adheres to the steel strip, prevents the glowing of the hot melt coating from occurring Steel bands that oxidizes its surface. Subsequently, the aluminum layer in the manner of an adhesion promoter, that the coating produced by the melt coating adheres firmly and fully on the steel strip, even if the steel strip itself offers unfavorable conditions due to its alloy. For this purpose, in the known method, the effect is utilized that diffusion of the iron of the steel strip into the aluminum layer occurs during the annealing treatment necessary upstream of the melt coating. In the course of the annealing, a metallic, essentially consisting of A1 and Fe bearing on the steel strip thus formed, which is materially connected to the substrate formed by the steel strip.

Ein anderes Verfahren zum Beschichten eines hochmanganhaltigen, 0,35 - 1,05 Gew.-% C, 16 - 25 Gew.-% Mn, Rest Eisen sowie unvermeidbare Verunreinigungen enthaltendes Stahlband ist aus der WO 2006/042931 A1 bekannt. Gemäß diesem bekannten Verfahren wird das derart zusammengesetzte Stahlband zunächst kaltgewalzt und anschließend rekristallisierend in einer Atmosphäre geglüht, die sich in Bezug auf Eisen reduzierend verhält. Dabei sind die Glühparameter so gewählt, dass sich auf dem Stahlband beidseitig eine Zwischenschicht einstellt, die im Wesentlichen vollständig aus amorphem Oxid (FeMn)O besteht, und sich zusätzlich eine äußere Schicht einstellt, die aus kristallinem Mn-Oxid besteht, wobei die Dicke der beiden Schichten mindestens 0,5 µm beträgt. Praktische Untersuchungen haben gezeigt, dass auch derart aufwändig vorbeschichtete Stahlbänder in der Praxis nicht die für eine Kaltverformung geforderte Haftung auf dem Stahlsubstrat aufweisen.Another method of coating a high manganese content steel strip containing 0.35-1.05 wt% C, 16-25 wt% Mn, balance iron and unavoidable impurities is known from US Pat WO 2006/042931 A1 known. According to this known method, the steel strip thus composed is first cold-rolled and then annealed recrystallizing in an atmosphere which is reducing with respect to iron. In this case, the annealing parameters are selected such that on both sides of the steel strip an intermediate layer is formed, which consists essentially completely of amorphous oxide (FeMn) O, and additionally adjusts an outer layer consisting of crystalline Mn oxide, wherein the thickness of two layers is at least 0.5 microns. Practical investigations have shown that even such complex precoated steel strips in practice not have the required for a cold deformation adhesion to the steel substrate.

Neben dem voranstehend erläuterten Stand der Technik ist aus der JP 07-216524 A ein Verfahren zum Heißtauchbeschichten einer warmgewalzten Stahlplatte bekannt, die eine hohe Zugfestigkeit aufweist. Im Zuge dieses bekannten Verfahrens wird die Stahlplatte zunächst entzundert, gebeizt und gereinigt. Dann wird sie schwach oxidiert, um auf ihr einen Eisenoxidfilm zu erzeugen, der eine Dicke von 500 - 10.000 Å aufweist. Dieser Eisenoxidfilm wird anschließend durch reduzierendes Erhitzen zu aktivem metallischem Eisen reduziert. Die reduzierende Erhitzung wird dabei so durchgeführt, dass eine selektive Oxidation von Si und Mn in dem Stahl und eine Konzentrierung dieser Elemente an der Oberfläche vermieden werden. Zu diesem Zweck wird das reduzierende Erhitzen unter einer Atmosphäre durchgeführt, deren Wasserstoffkonzentration im Bereich von 3 - 25 Vol-% so reguliert wird, dass sie einerseits ein für die Reduzierung des Eisenoxids ausreichendes Reduktionsvermögen aufweist, andererseits jedoch die selektive Oxidation von Si und Mn unterbleibt.In addition to the above-described prior art is from the JP 07-216524 A discloses a method of hot dipping a hot rolled steel plate having a high tensile strength. In the course of this known method, the steel plate is first descaled, pickled and cleaned. Then, it is lightly oxidized to produce thereon an iron oxide film having a thickness of 500 - 10,000 Å. This iron oxide film is then reduced by reducing heating to active metallic iron. The reducing heating is carried out in such a way that a selective oxidation of Si and Mn in the steel and a concentration of these elements on the surface are avoided. For this purpose, the reductive heating is carried out under an atmosphere whose hydrogen concentration is controlled in the range of 3 to 25% by volume so as to have a reducing ability sufficient for the reduction of the iron oxide but omitting the selective oxidation of Si and Mn ,

EP1612288 offenbart ein Verfahren zum Beschichten eines 0,1 - 2,5 Gew.-% Mn enthaltenden Stahlbands mit einer auf Zink basierenden Schutzschicht, bei dem das zu beschichtende Stahlband bei einer 650 - 900 °C betragenden Glühtemperatur unter einer Stickstoff, Wasser und Wasserstoff enthaltenden Glühatmosphäre geglüht und anschließend einem Schmelztauchbeschichten unterzogen wird. EP1612288 discloses a process for coating a 0.1 to 2.5 wt% Mn-containing steel strip with a zinc-based protective layer in which the steel strip to be coated is annealed at 650 to 900 ° C under a nitrogen, water and hydrogen containing Annealing annealed and then subjected to a hot dip coating.

BE1011131A6 offenbart ein Verfahren zum Beschichten eines Stahlbands mit einer auf Zink basierenden Schutzschicht, bei dem das zu beschichtende Stahlband unter einer Glühatmosphäre geglüht und anschließend einem Schmelztauchbeschichten unterzogen wird. Das Verhältnis des Wasser-Gehaltes zum Wasserstoff-Gehalt der Glühatmosphäre ist zwischen 0,07 und 0,35. BE1011131A6 discloses a method for coating a steel strip with a zinc-based protective layer, in which the steel strip to be coated is annealed under an annealing atmosphere and then subjected to hot-dip coating. The ratio of the water content to the hydrogen content of the annealing atmosphere is between 0.07 and 0.35.

Ausgehend von dem voranstehend erläuterten Stand der Technik bestand die Aufgabe der Erfindung darin, ein Verfahren anzugeben, mit dem sich auf kostengünstige Weise hohe Mangangehalte aufweisende Stahlbleche Schmelztauchbeschichten lassen.Starting from the above-described prior art, the object of the invention was to provide a method by which high cost manganese steel sheets can be hot dip coated in a cost effective manner.

Diese Aufgabe ist bei einem Verfahren der eingangs angegebenen Art dadurch gelöst worden, dass erfindungsgemäß zur Herstellung einer im Wesentlichen von oxidischen Zwischenschichten freien metallischen Schutzschicht auf dem Stahlband das Verhältnis %H2O/%H2 des Wasser-Gehaltes %H2O zum Wasserstoff-Gehalt %H2 der Glühatmosphäre in Abhängigkeit von der jeweiligen Glühtemperatur TG wie folgt eingestellt wird: % H 2 ⁢ O / % H 2 ≤ 8 ⋅ 10 - 15 ⋅ T G 3 , 529

Figure imgb0001
This object has been achieved in a method of the type specified in that according to the invention for the production of a substantially free of oxidic interlayers metallic protective layer on the steel strip, the ratio% H 2 O /% H 2 of the water content% H 2 O to hydrogen Content% H 2 of the annealing atmosphere is set as a function of the respective annealing temperature T G as follows: % H 2 ⁢ O / % H 2 ≤ 8th ⋅ 10 - 15 ⋅ T G 3 . 529
Figure imgb0001

Bei Berücksichtigung dieses %H2O/%H2-Verhältnisses lässt sich über den gesamten Bereich der in Frage kommenden Glühtemperaturen TG ein optimales Arbeitsergebnis gewährleisten.Taking into account this% H 2 O /% H 2 ratio, it is possible to ensure an optimum work result over the entire range of possible annealing temperatures T G.

Die Erfindung geht von der Erkenntnis aus, dass durch eine geeignete Einstellung der Glühatmosphäre, nämlich ihres Wasserstoff-Gehaltes im Verhältnis zu ihrem WasserGehalt sowie ihres Taupunktes, sich beim Glühen eine Oberflächenbeschaffenheit des zu beschichtenden Stahlbands einstellt, die eine optimale Haftung des anschließend durch Schmelztauchbeschichten aufgetragenen metallischen Schutzüberzuges gewährleistet. Die erfindungsgemäß eingestellte Glühatmosphäre wirkt dabei sowohl gegenüber dem Eisen als auch gegenüber dem Mangan des Stahlbands reduzierend. Im Gegensatz zum beispielsweise in der WO 2006/042931 A1 beschriebenen Stand der Technik wird gemäß der Erfindung die Entstehung einer nach Feststellung der Erfinder die Haftung des Schmelzüberzugs auf dem hochmanganhaltigen Stahlsubstrat beeinträchtigenden Oxidschicht somit gezielt vermieden. Im Ergebnis wird auf diese Weise ein mit einem metallischen Überzug versehenes, hochfestes und gleichzeitig gut verformbares Stahlband erhalten, bei dem trotz seines hohen Mangangehalts eine überlegene Haftung des Überzugs gewährleistet ist. Diese ermöglicht es, erfindungsgemäß beschichtetes Stahlband problemlos zu Formteilen umzuformen, wie sie im Karosseriebau, insbesondere im Bereich des Automobilkarosseriebaus regelmäßig benötigt werden.The invention is based on the recognition that, by a suitable setting of the annealing atmosphere, namely its hydrogen content in relation to its water content and its dew point, a surface finish of the steel strip to be coated sets during the annealing, the optimum adhesion of the subsequently applied by hot-dip coating ensured metallic protective coating. The inventively set annealing atmosphere acts both with respect to the iron and against the manganese of the steel strip reducing. In contrast to, for example, in the WO 2006/042931 A1 According to the prior art described according to the invention, the formation of a according to the inventors, the adhesion of the melt coating on the high manganese steel substrate impairing oxide layer thus deliberately avoided. As a result, obtained in this way provided with a metallic coating, high-strength and at the same time well deformable steel strip, in which despite its high manganese content, a superior adhesion of the coating is ensured. This makes it possible to easily transform coated steel strip according to the invention to form parts, as are regularly required in body construction, in particular in the field of automobile body construction.

Typische, bei einem erfindungsgemäßen Verfahren angewendete Glühtemperaturen liegen im Bereich von 800 - 1100 °C. Über den gesamten Bereich dieser Glühtemperaturen sollte erfindungsgemäß das %H2O/%H2-Verhältnis jeweils unterhalb von 4,5·10-4 liegen.Typical annealing temperatures used in a process according to the invention are in the range from 800 to 1100 ° C. Over the entire range of these annealing temperatures, the% H 2 O /% H 2 ratio should in each case be below 4.5 × 10 -4 in accordance with the invention.

Indem entsprechend des erfindungsgemäß vorgegebenen Zusammenhangs mit abnehmender Glühtemperatur auch das %H2O/%H2- Verhältnis gesenkt wird, können optimierte Arbeitsergebnisse erreicht werden. Praktische Versuche haben dazu ergeben, dass sich der Erfolg der Erfindung bei einer Glühtemperatur von 850 °C besonders sicher einstellt, wenn das %H2O/%H2-Verhältnis auf bis 2·10-4 beschränkt wird. Bei einer Glühtemperatur von 950 °C ergibt sich eine besonders hohe Betriebssicherheit, wenn das %H2O/%H2-Verhältnis höchstens 2,5·10-4 beträgt. Vermindert werden kann das Verhältnis %H2O/%H2 dadurch, dass der H2-Gehalt angehoben oder der H2O-Gehalt des Atmosphärengases abgesenkt wird.By lowering the% H 2 O /% H 2 ratio in accordance with the context of the present invention with decreasing annealing temperature, optimized work results can be achieved. Practical experiments have shown that the success of the invention at an annealing temperature of 850 ° C sets particularly safe when the% H 2 O /% H 2 ratio is limited to 2 · 10 -4 . At an annealing temperature of 950 ° C results in a particularly high reliability when the% H 2 O /% H 2 ratio is at most 2.5 · 10 -4 . Can be reduced, the ratio% H 2 O /% H 2 characterized in that the H 2 content is raised or lowered, the H 2 O content of the atmosphere gas.

Wird das erfindungsgemäß verarbeitete Stahlband ein oder mehrstufig kaltgewalzt, so kann das Stahlband bei den zwischen den einzelnen Kaltwalzschritten vorgenommenen Zwischenglühungen oder beim im Anschluss an das Kaltwalzen durchgeführte Glühen zur Vorbereitung des Schmelztauchbeschichtens unter der erfindungsgemäß eingestellten Glühatmosphäre geglüht werden.If the steel strip processed according to the invention is cold-rolled one or more times, the steel strip can be annealed under the annealing atmosphere set according to the invention during the intermediate annealing carried out between the individual cold-rolling steps or during the annealing carried out after the cold-rolling to prepare the hot-dip coating.

Alternativ oder ergänzend dazu lassen sich das Glühen und das Schmelztauchbeschichten im kontinuierlichen Durchlauf durchführen. Diese Art der Anwendung des erfindungsgemäßen Verfahrens bietet sich insbesondere dann an, wenn das Beschichten in einer konventionellen Bandbeschichtungsanlage ausgeführt wird, bei der in üblicher Weise ein Glühofen und das Schmelztauchbad inline angeordnet sind und in einer unterbrechungsfreien Abfolge kontinuierlich aufeinander folgend durchlaufen werden.Alternatively or additionally, the annealing and the hot dip coating can be carried out in a continuous pass. This type of application of the method according to the invention is particularly suitable when the coating is carried out in a conventional coil coating plant, in which an annealing furnace and the hot dip are arranged inline in the usual way and are run continuously in succession in an uninterrupted sequence.

Das erfindungsgemäße Verfahren eignet sich zum Schmelztauchbeschichten von hochmanganhaltigen Stahlbändern mit einer im Wesentlichen vollständig aus Zn und unvermeidbaren Verunreinigungen bestehenden Schicht (so genannte "Z-Beschichtung"), mit einer Zink-Eisen-Schicht, die aus bis zu 92 Gew.-% Zn und bis zu 12 Gew.-% Fe besteht (so genannte "ZF-Beschichtung"), mit einer Aluminium-Zink-Schicht, deren Al-Gehalt bis zu 60 Gew.-% und deren Zn-Gehalt bis zu 50 Gew.-% (so genannte "AZ-Beschichtung") beträgt, mit einer Aluminium-Silizium-Schicht, die einen Al-Gehalt von bis zu 92 Gew.-% und einen Si-Gehalt von bis zu 12 Gew.-% aufweist (so genannte "AS-Beschichtung"), mit einer Zink-Aluminium-Schicht, die einen Gehalt von bis zu 10 Gew.-% A1, Rest Zink und unvermeidbare Verunreinigungen aufweist (so genannte "ZA-Beschichtung") oder mit einer Zink-Magnesium-Schicht, die einen Zn-Anteil von bis zu 99,5 Gew.-% und einen Mg-Anteil von bis zu 5 Gew.-% besitzt (so genannte "ZnMg-Beschichtung") sowie zusätzlich wahlweise bis zu 11 Gew.-% A1, bis zu 4 Gew.-% Fe und bis zu 2 Gew.-% Si enthalten kann.The inventive method is suitable for hot dip coating of high manganese steel strips with a substantially completely consisting of Zn and unavoidable impurities layer (so-called "Z-coating"), with a zinc-iron layer, which consists of up to 92 wt .-% Zn and up to 12% by weight of Fe (so-called "ZF coating"), with an aluminum-zinc layer whose Al content is up to 60% by weight and whose Zn content is up to 50% by weight. % (so-called "AZ coating") is, with an aluminum-silicon layer having an Al content of up to 92 wt .-% and an Si content of up to 12 wt .-% (see called "AS coating"), with a zinc-aluminum layer having a content of up to 10 wt .-% A1, balance zinc and unavoidable impurities (so-called "ZA coating") or with a zinc-magnesium Layer which has a Zn content of up to 99.5% by weight and an Mg content of up to 5% by weight (so-called "ZnMg coating") and additionally optionally up to 11% by weight. % A1, up to 4 wt% Fe, and up to 2 wt% Si.

Die erfindungsgemäße Vorgehensweise bei der Beschichtung ist insbesondere für solche Stahlbänder geeignet, die hoch legiert sind, um hohe Festigkeiten und gute Dehnungseigenschaften zu gewährleisten. Die Stahlbänder, die sich in erfindungsgemäßer Weise durch Schmelztauchbeschichten mit einem metallischen Schutzüberzug versehen lassen, enthalten dementsprechend typischerweise (in Gew.-%) C: ≤ 1,6 %, Mn: 6 - 30 %, Al: ≤ 10 %, Ni: ≤ 10 %, Cr: ≤ 10 %, Si: ≤ 8 %, Cu: ≤ 3 %, Nb: ≤ 0,6 %, Ti: ≤ 0,3 %, V: ≤ 0,3 %, P: ≤ 0,1 %, B: ≤ 0,01 %, N: ≤ 1,0 %, Rest Eisen und unvermeidbare Verunreinigungen.The coating procedure according to the invention is particularly suitable for steel strips which are highly alloyed in order to ensure high strength and good elongation properties. Accordingly, the steel strips which are provided with a metallic protective coating by hot-dip coating according to the invention typically contain (in% by weight) C: ≦ 1.6%, Mn: 6 - 30%, Al: ≦ 10%, Ni: ≦ 10%, Cr: ≦ 10%, Si: ≦ 8%, Cu: ≦ 3%, Nb: ≦ 0.6%, Ti: ≦ 0.3%, V: ≦ 0.3%, P: ≦ 0 , 1%, B: ≤ 0.01%, N: ≤ 1.0%, balance iron and unavoidable impurities.

Besonders vorteilhaft wirken sich die durch die Erfindung erzielten Effekte bei der Beschichtung von hochlegierten Stahlbändern aus, die Mangan-Gehalte von mindestens 6 Gew.-% enthalten. So zeigt sich, dass ein Stahlgrundmaterial, welches (in Gew.-%) C: ≤ 1,00 %, Mn: 20,0 - 30,0 %, Al: ≤ 0,5 %, Si: ≤ 0,5 %, B: ≤ 0,01 %, Ni: ≤ 3,0 %, Cr: ≤ 10,0 %, Cu: ≤ 3,0 %, N: < 0,6 %, Nb: < 0,3 %, Ti: < 0,3 %, V: < 0,3 %, P: < 0,1 %, Rest Eisen und unvermeidbare Verunreinigungen enthält, sich besonders gut mit einem vor Korrosion schützenden Überzug beschichten lässt.The effects achieved by the invention in the coating of high-alloy steel strips which contain manganese contents of at least 6% by weight are particularly advantageous. Thus, it can be seen that a steel base material containing (in wt%) C: ≤ 1.00%, Mn: 20.0-30.0%, Al: ≤ 0.5%, Si: ≤ 0.5% , B: ≦ 0.01%, Ni: ≦ 3.0%, Cr: ≦ 10.0%, Cu: ≦ 3.0%, N: <0.6%, Nb: < 0.3%, Ti: <0.3%, V: <0.3%, P: <0.1%, balance iron and unavoidable impurities, can be coated particularly well with a corrosion-protective coating.

Gleiches gilt, wenn ein Stahl als Grundmaterial eingesetzt wird, der (in Gew.-%) C: ≤ 1,00 %, Mn: 7,00 - 30,00 %, Al: 1,00 - 10,00 %, Si: >2,50 - 8,00 % (wobei gilt, dass die Summe aus Al-Gehalt und Si-Gehalt >3,50 - 12,00 % ist), B: < 0,01 %, Ni: < 8,00 %, Cu: < 3,00 %, N: < 0,60 %, Nb: < 0,30 %, Ti: < 0,30 %, V: < 0,30 %, P: < 0,01 %, Rest Eisen und unvermeidbare Verunreinigungen enthält.The same applies if a steel is used as the base material, which (in wt .-%) C: ≤ 1.00%, Mn: 7.00 - 30.00%, Al: 1.00 - 10.00%, Si :> 2.50 - 8.00% (assuming that the sum of Al content and Si content is> 3.50 - 12.00%), B: <0.01%, Ni: <8, 00%, Cu: <3.00%, N: <0.60%, Nb: <0.30%, Ti: <0.30%, V: <0.30%, P: <0.01% , Rest contains iron and unavoidable impurities.

Mit der Erfindung steht ein kostengünstiger Weg zur Verfügung, hochmanganhaltige Stahlbänder auf wirtschaftliche Weise so gegen Korrosion zu schützen, dass sie für die Produktion von Karosserien für den Fahrzeugbau, insbesondere den Automobilbau, eingesetzt werden können, bei deren praktischem Einsatz sie besonders korrosiven Medien ausgesetzt sind.With the invention, a cost-effective way is available to protect high manganese steel bands in an economical way so against corrosion that they can be used for the production of bodies for vehicle construction, especially automotive, in their practical use they are exposed to particularly corrosive media ,

Wie bei der üblichen Schmelztauchbeschichtung können sowohl warmgewalzte als auch kaltgewalzte Stahlbänder in erfindungsgemäßer Weise beschichtet werden.As with the conventional hot-dip coating, both hot-rolled and cold-rolled steel strips can be coated in accordance with the invention.

Nachfolgend wird die Erfindung anhand einer ein Ausführungsbeispiel darstellenden Zeichnung näher erläutert. Es zeigen jeweils schematisch:

Abb. 1
die Aufnahme eines in erfindungsgemäßer Weise mit einem Zinküberzug versehenen Stahlblechs nach einem Kugelschlagtest;
Abb. 2
die Aufnahme eines zum Vergleich in einer von der Erfindung abweichenden Weise mit einem Zinküberzug versehenen Stahlblechs nach einem Kugelschlagtest;
Abb. 3
die Aufnahme eines zweiten in erfindungsgemäßer Weise mit einem Zinküberzug versehenen Stahlblechs nach einem Kugelschlagtest;
Abb. 4
die Aufnahme eines zweiten zum Vergleich in einer von der Erfindung abweichenden Weise mit einem Zinküberzug versehenen Stahlblechs nach einem Kugelschlagtest;
Diag. 1
das Verhältnis %H2O/%H2 des Wasser-Gehaltes %H2O zum Wasserstoff-Gehalt %H2 der Glühatmosphäre in Abhängigkeit aufgetragen über die Glühtemperatur TG.
The invention will be explained in more detail with reference to a drawing illustrating an exemplary embodiment. Each show schematically:
Fig. 1
the inclusion of a provided according to the invention with a zinc coating steel sheet after a ball impact test;
Fig. 2
the inclusion of a comparison with in a deviating from the invention manner with a zinc-coated steel sheet after a ball impact test;
Fig. 3
the inclusion of a second provided in accordance with the invention with a zinc coating steel sheet after a ball impact test;
Fig. 4
the inclusion of a second steel sheet provided with a zinc coating for comparison in a manner deviating from the invention after a ball impact test;
Diag. 1
the ratio% H 2 O /% H 2 of the water content% H 2 O to the hydrogen content% H 2 of the annealing atmosphere in dependence plotted on the annealing temperature T G.

In drei Versuchsreihen V1, V2, V3 sind drei hochfeste, hochmanganhaltige Stähle S1, S2, S3, deren Zusammensetzung in Tabelle 1 angegeben ist, zu Brammen vergossen und zu Warmband ausgewalzt worden. Das jeweils erhaltene Warmband ist anschließend auf Enddicke kaltgewalzt und in eine konventionelle Schmelztauchbeschichtungsanlage geleitet worden.In three test series V1, V2, V3, three high-strength, high-manganese steels S1, S2, S3, the composition of which is given in Table 1, were cast into slabs and rolled into hot-rolled strip. The respective hot strip obtained was then cold rolled to final thickness and passed into a conventional hot dip coating plant.

In der Schmelztauchbeschichtungsanlage sind die Stahlbänder in einer kontinuierlich ablaufenden Arbeitsfolge zunächst gereinigt und danach in einem kontinuierlichen Glühprozess auf die jeweilige Glühtemperatur TG, auf der sie über eine Glühzeit ZG von jeweils 30 Sekunden unter einer in erfindungsgemäßer Weise eingestellten wasserstoffhaltigen Glühatmosphäre gehalten worden sind, gebracht worden.In the hot-dip coating plant, the steel strips are first cleaned in a continuous operating sequence and then held in a continuous annealing process to the respective annealing temperature T G , on which they have been held over an annealing time Z G of 30 seconds under a set according to the invention hydrogen-containing annealing atmosphere, has been brought.

Nach der Glühbehandlung sind die geglühten Stahlbänder jeweils auf eine Badeintrittstemperatur von 470 °C abgekühlt und im kontinuierlichen Durchlauf durch ein 460 °C warmes Zink-Schmelzbad geleitet worden, das aus 0,2 % Al und als Rest aus Zn und unvermeidbaren Verunreinigungen bestand. Nach Austritt aus dem Zink-Schmelzbad ist mittels eines Düsenabstreifsystems in an sich bekannter Weise die Dicke des Zn-Schutzüberzuges auf dem Stahlband eingestellt worden.After annealing, the annealed steel strips were each cooled to a bath inlet temperature of 470 ° C and passed in a continuous pass through a 460 ° C hot zinc molten bath consisting of 0.2% Al and balance of Zn and unavoidable impurities. After exiting the zinc molten bath, the thickness of the Zn protective coating on the steel strip has been adjusted in a manner known per se by means of a nozzle scraper system.

In der großtechnischen Anwendung kann auf das Schmelztauchbeschichten des Bandes und die Einstellung der Schichtdicke erforderlichenfalls ein Nachwalzen durchgeführt werden, um die Maßhaltigkeit des erhaltenen Bandes, sein Verformungsverhalten oder seine Oberflächenbeschaffenheit an die jeweiligen Anforderungen anzupassen. Im Anschluss kann das mit dem Überzug versehene Stahlband für den Transport zum Endverbraucher eingeölt und zu einem Coil aufgehaspelt werden.In the industrial application can be carried out on the hot dip coating of the strip and the adjustment of the layer thickness, if necessary, a Nachwalzen to adjust the dimensional accuracy of the obtained strip, its deformation behavior or its surface finish to the respective requirements. Subsequently, the steel strip provided with the coating can be oiled for transport to the end user and wound up into a coil.

Die Versuchsreihe V1 umfasste fünf Versuche V1.1 - V1.5 mit einem aus dem Stahl S1 produzierten Stahlband. Im Zuge der Versuchsreihe V2 sind sieben Versuche V2.1 - V2.7 mit einem aus dem Stahl S2 hergestellten Stahlband durchgeführt worden. Bei der Versuchsreihe V3 sind schließlich elf Versuche mit einem aus dem Stahl S3 erzeugten Stahlband gemacht worden.The test series V1 comprised five experiments V1.1 - V1.5 with a steel strip produced from steel S1. in the In the course of the test series V2, seven experiments V2.1 - V2.7 were carried out with a steel strip made of steel S2. In test series V3, eleven tests were finally carried out on a steel strip made of steel S3.

Die bei den voranstehend genannten Versuchsreihen jeweils angewendete Glühtemperatur TG, der jeweilige H2-Gehalt %H2 der Glühatmosphäre, ihr jeweiliger Taupunkt TP, der jeweilige H2O-Gehalt %H2O, das Verhältnis %H2O/%H2 sowie eine Bewertung des Beschichtungsergebnisses und eine Zuordnung der Versuchsergebnisse als "erfindungsgemäß" bzw. "nicht erfindungsgemäß" sind für die Versuchsreihe V1 in Tabelle 2, für die Versuchsreihe V2 in Tabelle 3 und für die Versuchsreihe V3 in Tabelle 4 angegeben.The annealing temperature T G applied in each case in the above-mentioned test series, the respective H 2 content% H 2 of the annealing atmosphere, their respective dew point TP, the respective H 2 O content% H 2 O, the ratio% H 2 O /% H 2 and an evaluation of the coating result and an assignment of the test results as "according to the invention" or "not according to the invention" are given for the test series V1 in Table 2, for the test series V2 in Table 3 and for the test series V3 in Table 4.

In Diag. 1 ist das Verhältnis %H2O/%H2 über die Glühtemperatur TG aufgetragen. Dabei ist durch eine Kurve K der unterhalb dieser Kurve sich befindende Bereich "E", in dem gemäß der Bedingung % H 2 ⁢ O / % H 2 ≤ 8 ⋅ 10 - 15 ⋅ T G 3 , 529

Figure imgb0002

die bei der erfindungsgemäßen Einstellung der Glühatmosphäre eingehaltenen Verhältnisse %H2O/%H2 liegen, von dem oberhalb der Kurve K sich befindenden Bereich "N" abgetrennt, in dem die Verhältnisse %H2O/%H2 einer nicht erfindungsgemäß eingestellten Atmosphäre angeordnet sind.In Diag. 1, the ratio% H 2 O /% H 2 is plotted against the annealing temperature T G. In this case, by a curve K, the area located below this curve is "E" in which according to the condition % H 2 ⁢ O / % H 2 ≤ 8th ⋅ 10 - 15 ⋅ T G 3 . 529
Figure imgb0002
the ratios% H 2 O /% H 2 maintained in the inventive setting of the annealing atmosphere are separated from the region "N" located above the curve K, in which the ratios% H 2 O /% H 2 of an atmosphere not adjusted according to the invention are arranged.

Abb. 1 zeigt das Ergebnis eines Kugelschlagtests, der an dem aus im Versuch V1.4 gewonnenen, mit dem Zn-Schutzüberzug versehenen Stahlblech durchgeführt worden ist. Die einwandfreie Haftung des Überzugs auch im am stärksten verformten Bereich der in das Stahlblech eingeformten Kalotte ist deutlich zu sehen. Fig. 1 shows the result of a ball impact test, which was carried out on the obtained from the test V1.4, provided with the Zn protective coating steel sheet is. The perfect adhesion of the coating even in the most deformed area of the molded into the steel sheet dome is clearly visible.

Abb. 2 zeigt das Ergebnis eines Kugelschlagtests, der an dem aus Versuch V1.1 hervorgegangenen Stahlblech durchgeführt worden ist. Die Abplatzungen des Überzugs im Bereich der in das Stahlblech eingeformten Kalotte sind klar zu erkennen.Fig. 2 shows the result of a ball impact test, which was carried out on the steel sheet resulting from experiment V1.1. The flaking of the coating in the area of the dome formed in the steel sheet are clearly visible.

Abb. 3 zeigt das Ergebnis eines Kugelschlagtests, der an dem aus im Versuch V1.5 gewonnenen Stahlblech durchgeführt worden ist. Auch bei dieser erfindungsgemäß beschichteten Probe haftet der Überzug über die gesamte in das Blech eingeformte Kalotte einwandfrei.Fig. 3 shows the result of a ball impact test which has been carried out on the steel sheet obtained in experiment V1.5. Also in this invention coated sample, the coating adheres properly over the entire molded into the sheet dome.

Abb. 4 zeigt schließlich das Ergebnis eines Kugelschlagtests, der an dem aus dem im Versuch V1.2 beschichteten Stahlblech durchgeführt worden ist. Die mangelhafte Haftung des Überzugs an dem Stahlsubstrat zeigt sich durch die Risse im am stärksten verformten Bereich der in das Stahlblech eingeformten Kalotte. Tabelle 1 Stahl C Si Mn P Cr Ni V S1 0,60 0,28 22,5 0,021 0,003 0,077 0,006 S2 0,63 0,20 22,2 0,014 0,130 0,046 0,200 S3 0,62 0,30 22,5 0,018 0,600 0,170 0,300 Angaben in Gew.-%, Rest Fe und unvermeidbare Verunreinigungen Tabelle 2 Versuch TG [°C] %H2 [%] TP [°C] %H2O [%] %H2O/%H2 Bewertung der Verzinkung Erfindungsgemäß V1.1 850 50 -31 0,03375 0,0006750 Schlecht Nein V1.2 850 100 -30 0,03747 0,0003747 Schlecht Nein V1.3 900 50 -38 0,01584 0,0003168 Schlecht Nein V1.4 950 50 -46 0,00630 0,0001260 Gut Ja V1.5 950 100 -34 0,02454 0,0002454 Gut Ja Tabelle 3 Versuch TG [°C] %H2 [%] TP [°C] %H2O [%] %H2O/%H2 Bewertung der Verzinkung Erfindungsgemäß V2.1 850 50 -40 0,01266 0,0002532 Schlecht Nein V2.2 850 100 -42 0,01007 0,0001007 Gut Ja V2.3 900 50 -41 0,01130 0,0002260 Schlecht Nein V2.4 950 50 -42 0,01007 0,0002014 Gut Ja V2.5 950 100 -42 0,01007 0,0001007 Gut Ja V2.6 800 5 -60 0,00106 0,0002119 Schlecht Nein V2.7 800 5 -70 0,00025 0,0000509 Gut Ja Tabelle 4 Versuch TG [°C] %H2 [%] TP [°C] %H2O [%] %H2O/%H2 Bewertung der Verzinkung Erfindungsgemäß V3.1 950 50 -56 0,00181 0,0000362 Gut Ja V3.2 950 50 -56 0,00181 0,0000774 Gut Ja V3.3 950 50 -47 0,00559 0,0001118 Gut Ja V3.4 950 50 -44 0,00798 0,0001596 Gut Ja V3.5 950 50 -53 0,00266 0,0000532 Gut Ja V3.6 850 50 -53 0,00266 0,0000532 Gut Ja V3.7 850 50 -49 0,00438 0,0000876 Gut Ja V3.8 850 50 -42 0,01007 0,0002014 Schlecht Nein V3.9 1100 5 -34 0,02454 0,0049080 Schlecht Nein V3.10 1100 10 -50 0,00387 0,0003874 Gut Ja V3.11 1100 5 -56 0,00181 0,0003611 Gut Ja Finally, FIG. 4 shows the result of a ball impact test carried out on the steel sheet coated in experiment V1.2. The poor adhesion of the coating to the steel substrate is evidenced by the cracks in the most deformed area of the cup formed in the steel sheet. Table 1 stole C Si Mn P Cr Ni V S1 0.60 0.28 22.5 0,021 0,003 0.077 0,006 S2 0.63 0.20 22.2 0,014 0.130 0.046 0,200 S3 0.62 0.30 22.5 0,018 0,600 0,170 0,300 Data in wt .-%, balance Fe and unavoidable impurities attempt T G [° C] % H 2 [%] TP [° C] % H 2 O [%] % H 2 O /% H 2 Evaluation of galvanizing According to the invention V1.1 850 50 -31 0.03375 0.0006750 Bad No V1.2 850 100 -30 0.03747 0.0003747 Bad No V1.3 900 50 -38 0.01584 0.0003168 Bad No V1.4 950 50 -46 0.00630 0.0001260 Well Yes V1.5 950 100 -34 0.02454 0.0002454 Well Yes attempt T G [° C] % H 2 [%] TP [° C] % H 2 O [%] % H 2 O /% H 2 Evaluation of galvanizing According to the invention V2.1 850 50 -40 0.01266 0.0002532 Bad No V2.2 850 100 -42 0.01007 0.0001007 Well Yes V2.3 900 50 -41 0.01130 0.0002260 Bad No V2.4 950 50 -42 0.01007 0.0002014 Well Yes V2.5 950 100 -42 0.01007 0.0001007 Well Yes V2.6 800 5 -60 0.00106 0.0002119 Bad No V2.7 800 5 -70 0.00025 0.0000509 Well Yes attempt T G [° C] % H 2 [%] TP [° C] % H 2 O [%] % H 2 O /% H 2 Evaluation of galvanizing According to the invention V3.1 950 50 -56 0.00181 0.0000362 Well Yes V3.2 950 50 -56 0.00181 0.0000774 Well Yes V3.3 950 50 -47 0.00559 0.0001118 Well Yes V3.4 950 50 -44 0.00798 0.0001596 Well Yes V3.5 950 50 -53 0.00266 0.0000532 Well Yes V3.6 850 50 -53 0.00266 0.0000532 Well Yes V3.7 850 50 -49 0.00438 0.0000876 Well Yes V3.8 850 50 -42 0.01007 0.0002014 Bad No V3.9 1100 5 -34 0.02454 0.0049080 Bad No V3.10 1100 10 -50 0.00387 0.0003874 Well Yes V3.11 1100 5 -56 0.00181 0.0003611 Well Yes

Claims (14)

  1. Method for coating hot-rolled or cold-rolled steel strip containing 6 - 30 wt%. Mn with a metallic protective layer, in particular a protective layer based on zinc, wherein the steel strip to be coated is annealed at a temperature of 800 - 1100°C under an annealing atmosphere containing nitrogen, water and hydrogen and is then subjected to hot dip coating, characterized in that in order to produce a metallic protective layer substantially free from oxidic sublayers on the steel strip the %H2O/%H2 ratio of the water content %H2O to the hydrogen content %H2 in the annealing atmosphere is adjusted as a function of the respective annealing temperature TG as follows: % H 2 ⁢ O / % H 2 ≤ 8 ⋅ 10 - 15 ⋅ T G 3 , 529
    Figure imgb0004
  2. Method according to Claim 1, characterized in that rolling of the steel strip is carried out before hot dip coating.
  3. Method according to Claim 2, characterized in that rolling is carried out in several rolling steps and the steel strip is annealed between each rolling step according to Claim 1.
  4. Method according to any one of the preceding claims, characterized in that annealing and hot dip coating take place in a continuous operation.
  5. Method according to any one of the preceding claims, characterized in that the metallic coating consists essentially totally of Zn and unavoidable impurities.
  6. Method according to any one of Claims 1 to 4, characterized in that the metallic coating is a zinc-iron coating with a Zn-content of up to 92 wt%. and an Fe-content of up to 12 wt%.
  7. Method according to any one of Claims 1 to 4, characterized in that the metallic coating is an aluminium-zinc coating with an Al-content of up to 60 wt%. and a Zn-content of up to 50 wt%.
  8. Method according to any one of Claims 1 to 4, characterized in that the metallic coating is an aluminium-silicon coating with an Al-content of up to 92 wt%. and an Si-content of up to 12 wt%.
  9. Method according to any one of Claims 1 to 4, characterized in that the metallic coating is a zinc-aluminium coating, which has an Al-content of up to 10 wt%., remainder zinc and unavoidable impurities.
  10. Method according to any one of Claims 1 to 4, characterized in that the metallic coating is a zinc-magnesium coating, which contains up to 99.5 wt%. Zn and up to 5 wt%. Mg.
  11. Method according to Claim 10, characterized in that the zinc-magnesium coating contains up to 11 wt%. A1, up to 4 wt%. Fe and up to 2 wt%. Si.
  12. Method according to any one of the preceding claims, characterized in that the steel strip contains (in wt%.) C: ≤ 1.6 %, Mn: 6 - 30 %, A1: ≤ 10 %, Ni: ≤ 10 %, Cr: ≤ 10 %, Si: ≤ 8 %, Cu: ≤ 3 %, Nb: ≤ 0.6 %, Ti: ≤ 0.3 %, V: ≤ 0. 3 %, P: ≤ 0. 1 %, B: ≤ 0. 01 %, N: ≤ 1.0 %, remainder iron and unavoidable impurities.
  13. Method according to Claim 12, characterized in that the steel strip contains (in wt%.) C: ≤ 1.00 %, Mn: 20.0 - 30.0 %, Al: ≤ 0.5 %, Si: ≤ 0.5 %, B: ≤ 0.01 %, Ni: ≤ 3.0 %, Cr: ≤ 10.0 %, Cu: ≤ 3.0 %, N: < 0.6 %, Nb: < 0.3 %, Ti: < 0.3 %, V: < 0.3 %, P: < 0.1 %, remainder iron and unavoidable impurities.
  14. Method according to any one of Claims 1 to 12, characterized in that the steel strip contains (in wit%.): C: ≤ 1.00 %, Mn: 7.00 - 30.00 %, B: < 0.01 %, Ni: < 8.00 %, Cu: < 3.00 %, N: < 0.60 %, Nb: < 0.30 %, Ti: < 0.30 %, V: < 0.30 %, P: < 0.01 %, as well as Al: 1.00 - 10.00 % and Si: > 2.50 - 8.00 %, where the Al-content + the Si-content is > 3.50 - 12.00 %, remainder iron and unavoidable impurities.
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ES2353438T3 (en) 2011-03-02
WO2008022980A2 (en) 2008-02-28
ATE486974T1 (en) 2010-11-15
CA2660398C (en) 2013-11-05
PL2054536T3 (en) 2011-04-29
EP2054536A2 (en) 2009-05-06
KR101463221B1 (en) 2014-11-19
US20100065160A1 (en) 2010-03-18
AU2007287602A1 (en) 2008-02-28
DE102006039307B3 (en) 2008-02-21
WO2008022980A3 (en) 2008-10-30
KR20090040349A (en) 2009-04-23
DE502007005570D1 (en) 2010-12-16
CA2660398A1 (en) 2008-02-28
JP2010501725A (en) 2010-01-21
CN101506403B (en) 2011-12-28
AU2007287602B2 (en) 2010-11-25

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