EP3749793B1 - Verfahren zur herstellung eines stahlbandes mit verbesserter haftung metallischer schmelztauchüberzüge - Google Patents

Verfahren zur herstellung eines stahlbandes mit verbesserter haftung metallischer schmelztauchüberzüge Download PDF

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Publication number
EP3749793B1
EP3749793B1 EP19703657.7A EP19703657A EP3749793B1 EP 3749793 B1 EP3749793 B1 EP 3749793B1 EP 19703657 A EP19703657 A EP 19703657A EP 3749793 B1 EP3749793 B1 EP 3749793B1
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Prior art keywords
steel strip
annealing
iron
zinc
aluminium
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EP19703657.7A
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German (de)
English (en)
French (fr)
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EP3749793A1 (de
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Marc Debeaux
Nils KÖPPER
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Salzgitter Flachstahl GmbH
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Salzgitter Flachstahl GmbH
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/62—Quenching devices
    • C21D1/673—Quenching devices for die quenching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • 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
    • 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
    • C21D9/573—Continuous furnaces for strip or wire with cooling
    • C21D9/5732—Continuous furnaces for strip or wire with cooling of wires; of rods
    • 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
    • C21D9/573—Continuous furnaces for strip or wire with cooling
    • C21D9/5735—Details
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/003—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0224—Two or more thermal pretreatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
    • 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
    • C23C2/34—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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere

Definitions

  • the invention relates to a method for producing a cold- or hot-rolled steel strip with improved adhesion of metallic hot-dip coatings, which, in addition to iron as the main component and unavoidable impurities, contains one or more of the elements with an affinity for oxygen in % by weight: Al: more than 0.02, Cr: more than 0.1, Mn: more than 1.3 or Si: more than 0.1, wherein the surface of the steel strip is cleaned, the steel strip is annealed, the steel strip is oxidized to have a surface consisting essentially of metallic iron and a reduction and then the steel strip treated and annealed in this way is coated with a hot-dip coating.
  • the invention relates to high-strength and ultra-high-strength steel strip with strengths of approximately 500 MPa to 1700 MPa.
  • aluminium-silicon AS/AISi
  • zinc Z
  • zinc-aluminium ZA
  • zinc-aluminium-iron ZF/Galvannealed
  • zinc-magnesium-aluminium ZM /ZAM
  • zinc-manganese-aluminum aluminum-zinc
  • AZ aluminum-zinc
  • JP H05 171392 A describes a process for applying a zinc coating to a high-strength sheet steel which, in addition to iron and unavoidable impurities, contains one or more elements with an affinity for oxygen, such as P, Si, Mn, Ti, Cr, Al, B, or alloying elements, with the aim of improving surface uniformity of non-coated parts.
  • the steel sheet is cleaned and subjected to an anodic electrolytic treatment at current densities of 20 to 80 A/ cm 2 to form an oxide layer.
  • the patent specification DE 10 2013 105 378 B3 discloses a process for producing a flat steel product which, in addition to iron and unavoidable impurities, contains up to 35% by weight Mn, up to 10 Al, up to 10 Si and up to 5 Cr.
  • the flat steel product After heating in a preheating furnace to a temperature between 600 and 1000°C, in which the flat steel product is exposed to an oxidizing atmosphere at elevated temperatures and recrystallizing annealing in the annealing furnace, in which an annealing atmosphere that has a reducing effect on FeO prevails, the flat steel product is coated in a hot-dip bath.
  • the disclosure document DE 10 2010 037 254 A1 discloses a method for hot-dip coating a flat steel product, the flat steel product being produced from a stainless steel which, in addition to iron and unavoidable impurities, contains in % by weight: 5 to 30 Cr, ⁇ 6 Mn, ⁇ 2 Si and ⁇ 0.2 Al.
  • the flat steel product is first heated to temperatures of 550 to 800° C. and pre-oxidized at this temperature in an oxidizing pre-oxidation atmosphere, then kept in a reducing holding atmosphere and finally passed through a molten bath.
  • the Disclosures U.S. 2016 010 23 79 A1 and U.S. 2013 030 49 82 A1 each disclose a process for producing a coated steel strip containing, by weight percent: 0.5 to 2 Si, 1 to 3 Mn, 0.01 to 0.8 Cr and 0.01 to 0.1 Al. After an oxidation treatment of the steel strip at temperatures above 400° C. in an oxidative atmosphere, the steel strip is subjected to reduction annealing and then hot-dip coated.
  • the document mentioned discloses, inter alia, a method in which, in the course of annealing under oxidizing conditions, the steel strip is pre-oxidized in a first step, with which a specifically covering FeO layer is produced, which prevents selective oxidation. In a second step this layer is then reduced back to metallic iron.
  • the setting of the desired oxide layer thickness during the pre-oxidation - during the annealing - is very demanding and error-prone in particular due to technically caused fluctuations or process fluctuations over the bandwidth and length. In the worst case, if the oxidation or reduction is insufficient, this can lead to local adhesion failure of the coating. In addition, an in-line measurement of the oxide layer thickness is not possible at the high temperatures caused by the process, or only with great effort. Furthermore, adapted parameter sets are required for each steel, which makes the process even more complex. In addition, integration into existing systems is often difficult to implement and therefore very cost-intensive.
  • the object of the invention is therefore to provide a method for producing a steel strip which, in addition to iron and unavoidable impurities, contains one or more of the oxygen-affinity elements aluminum, chromium, manganese or silicon, which is less expensive and provides uniform, reproducible adhesion conditions for the coating. Furthermore, an in-line measurement of the oxide layer thickness should be possible.
  • the teaching of the invention includes a method for producing a steel strip which, in addition to iron as the main component and unavoidable impurities, contains one or more of the elements with an affinity for oxygen in % by weight: Al: more than 0.02, Cr: more than 0.1, Mn: more than 1.3 or Si: more than 0.1, wherein the surface of the steel strip is cleaned, the steel strip is annealed and then the steel strip treated and annealed in this way is coated with a hot-dip coating, which is characterized in that the steel strip before the annealing at temperatures below 200 °C, an oxide layer containing iron oxide being formed on the surface of the steel strip with the formation of oxides with iron from the steel strip, which layer is formed during annealing in a reducing atmosphere to achieve an essentially metallic iron existing surface is reduction-treated, with the oxidation treatment being an anodic oxidation, with an oxide layer having a minimum thickness of at least 5 nm and a maximum of up to 500 nm being formed on the surface of the
  • the oxidation treatment according to the invention is independent of the annealing process step.
  • the ambient temperature of the steel strip corresponds to the temperature at the processing location and can therefore be specified as 15 °C to 50 °C.
  • the oxidation treatment takes place at temperatures below 200° C., preferably below 150° C., particularly preferably below 135° C. (temperatures in each case based on the steel strip).
  • the lower limit of this oxidation temperature is preferably room temperature in the range from 15.degree. C. to 25.degree.
  • oxidation in an oxygen-containing atmosphere with a sufficiently thick layer cannot take place in an economical process because the diffusion rates of the elements involved in the oxidation reaction are too low.
  • the steel strip will also heat up during the oxidation treatment due to the process heat generated, but remains below 200 °C.
  • the steel strip used for the process according to the invention advantageously has, in addition to iron and impurities caused by the melting process, one or more of the elements with an affinity for oxygen in % by weight: Al: 0.02 to 15, Cr: 0.1 to 9, Mn: 1.3 to 35 or Si: 0.1 to 10.
  • the steel strip particularly advantageously has the following contents of one or more of the elements with an affinity for oxygen in % by weight: Al: 0.02 to 3 Cr: 0.2 to 1 Mn: 1.5 to 7 Si: 0.15 to 3 or preferably: Al: 0.02 to 1, Cr: 0.3 to 1, Mn: 1.7 to 3, Si: 0.15 to 1.
  • the oxidation treatment is an anodic oxidation, with an oxide layer having a minimum thickness of at least 5 nm and a maximum of up to 500 nm being formed on the surface of the steel strip. Thinner layers do not lead to the desired improvement in adhesion. Thicker layers show insufficient adhesion to the substrate.
  • Anodizing can be performed either in-line before the annealing furnace of a continuous hot-dip refining line or a continuous annealing line.
  • the anodizing and annealing steps of the method according to the invention can also be carried out in separate systems.
  • oxidation treatment according to the invention is carried out according to the invention as anodic oxidation
  • other oxidation processes such as plasma oxidation or wet-chemical processes in oxygen-releasing media, can also be used in principle.
  • an oxide layer with a thickness of 10 nm to 200 nm is formed on the surface of the steel strip and particularly preferably with a thickness of 30 nm to 150 nm on the surface of the steel strip.
  • the electrolyte temperature is at most 3 K below the boiling point of the electrolyte.
  • the electrolyte can also contain additives (e.g. complexing agents, chelating ligands, wetting agents, inhibitors, pH stabilizers) and unavoidable contamination from the components introduced into the steel strip and their reaction products.
  • the steel strip is actively heated via the electrolyte to temperatures between room temperature and 3°C below the boiling point (the boiling point of concentrated NaOH solutions is well above 100°C to around 135°C).
  • the electrolyte has temperatures of 50°C to 65°C.
  • the great advantage of the oxidation treatment according to the invention - before the annealing treatment - by means of anodic oxidation lies in the very simple and very fast regulation and reliable control of this process, regardless of the required annealing, so that a very uniform layer formation and in-line Measurements of the oxide layer thickness outside the annealing furnace are possible without any problems.
  • the method according to the invention results in an increased range of applications with regard to existing methods on even higher-alloy steels, since the process-related porous structure of the anodizing layer allows complete reduction even with higher layers of the iron oxide layer, since this increases the reduction rate.
  • the annealing of the steel strip preconditioned in this way by anodizing is advantageously carried out in a continuous annealing furnace, at an annealing temperature of 650° C. to 880° C. and a heating rate of 5 K/s to 100 K/s, with a reducing annealing atmosphere consisting of 1 to 30 % H 2 remainder N 2 and a dew point between +15 and -70 °C and a holding time of the steel strip at annealing temperature between 30 s and 650 s with subsequent cooling to a temperature between 30 °C and 500 °C. If the temperature of the strip has been cooled below 400 °C, it is reheated to a temperature between 400 °C and 500 °C before it is immersed in the molten metal bath. The steel strip is then hot-dip coated with the metallic coating.
  • annealing temperature 750 to 850° C. heating rate from 10 to 50 K/s; H 2 from 1 to 10%, remainder N2 and a dew point between -10 to -50 °C and a holding time of the steel strip at the annealing temperature of 60 to 180 s.
  • the one shown in the appendix figure 1 shows an Fe-GDOES spectrum of an anodized and subsequently reducing annealed ungalvanized steel sample of an HCT980XD (annealing conditions: 830°C, 165 s, TP -30 °C) compared to an untreated steel sample of the same grade.
  • HCT980XD annealing conditions: 830°C, 165 s, TP -30 °C
  • the near-surface iron content is significantly higher under the selected conditions compared to the untreated reference sample.
  • it was possible under the given conditions to completely reduce the previously formed iron oxide, and the porous structure of the freshly anodized surface is also no longer observed after the annealing process.
  • the adhesion of the coating is improved by anodizing the sample beforehand.
  • FIG 2 The formation of the internal and external oxides according to the invention is in figure 2 shown schematically.
  • the formation of only a few globular external oxides is achieved by means of the anodization according to the invention with subsequent annealing in an HNx atmosphere. Due to the high proportion of metallic surface, hot-dip finishing can be carried out without affecting adhesion and surface appearance.
  • the reference process is in figure 3 shown. Shown is the scheme of a typical annealing before hot-dip refinement with the formation of an almost covering external oxide layer. This disturbs the subsequent wetting to a considerable extent and leads to ungalvanized areas and adhesion problems of the hot-dip coating.
  • the hot-dip coated steel strips produced by the method according to the invention can be used, preferably but not restrictively, for the production of parts for motor vehicles, such as for the production of cold-formed, hot-formed or press-form-hardened components.
  • Aluminum-silicon (AS/AISi), zinc (Z), zinc-aluminum (ZA), zinc-aluminum-iron (ZF/Galvannealed), zinc-magnesium-aluminum (ZM/ZAM) or Zinc-manganese-aluminum and aluminum-zinc (AZ) into consideration.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochemistry (AREA)
  • Coating With Molten Metal (AREA)
EP19703657.7A 2018-02-06 2019-01-30 Verfahren zur herstellung eines stahlbandes mit verbesserter haftung metallischer schmelztauchüberzüge Active EP3749793B1 (de)

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PCT/EP2019/052191 WO2019154680A1 (de) 2018-02-06 2019-01-30 Verfahren zur herstellung eines stahlbandes mit verbesserter haftung metallischer schmelztauchüberzüge

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DE102020120580A1 (de) 2020-08-04 2022-02-10 Muhr Und Bender Kg Verfahren zum herstellen von beschichtetem stahlband, und verfahren zum herstellen eines gehärteten stahlprodukts
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JP3131003B2 (ja) * 1992-02-28 2001-01-31 川崎製鉄株式会社 高張力鋼板の溶融亜鉛めっき方法
DE102004059566B3 (de) 2004-12-09 2006-08-03 Thyssenkrupp Steel Ag Verfahren zum Schmelztauchbeschichten eines Bandes aus höherfestem Stahl
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DE102010037254B4 (de) * 2010-08-31 2012-05-24 Thyssenkrupp Steel Europe Ag Verfahren zum Schmelztauchbeschichten eines Stahlflachprodukts
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US9257169B2 (en) 2012-05-14 2016-02-09 Samsung Electronics Co., Ltd. Memory device, memory system, and operating methods thereof
JP5962582B2 (ja) * 2013-05-21 2016-08-03 Ｊｆｅスチール株式会社 高強度合金化溶融亜鉛めっき鋼板の製造方法
DE102013105378B3 (de) * 2013-05-24 2014-08-28 Thyssenkrupp Steel Europe Ag Verfahren zur Herstellung eines durch Schmelztauchbeschichten mit einer metallischen Schutzschicht versehenen Stahlflachprodukts und Durchlaufofen für eine Schmelztauchbeschichtungsanlage
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CN105814229B (zh) * 2013-12-13 2018-05-18 杰富意钢铁株式会社 高强度合金化热镀锌钢板的制造方法
JP6164280B2 (ja) * 2015-12-22 2017-07-19 Ｊｆｅスチール株式会社 表面外観および曲げ性に優れるＭｎ含有合金化溶融亜鉛めっき鋼板およびその製造方法

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KR102635881B1 (ko) 2024-02-08
EP3749793A1 (de) 2020-12-16
DE102018102624A1 (de) 2019-08-08
KR20200118079A (ko) 2020-10-14
US11702729B2 (en) 2023-07-18
RU2766611C1 (ru) 2022-03-15
WO2019154680A1 (de) 2019-08-15

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