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WO2011054571A1 - Manufacturing galvannealed sheets by heat-treating electrolytically finished sheets - Google Patents

Manufacturing galvannealed sheets by heat-treating electrolytically finished sheets Download PDF

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Publication number
WO2011054571A1
WO2011054571A1 PCT/EP2010/063351 EP2010063351W WO2011054571A1 WO 2011054571 A1 WO2011054571 A1 WO 2011054571A1 EP 2010063351 W EP2010063351 W EP 2010063351W WO 2011054571 A1 WO2011054571 A1 WO 2011054571A1
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WO
WIPO (PCT)
Prior art keywords
zinc
steel strip
rolled
sheets
annealing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2010/063351
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German (de)
French (fr)
Inventor
Josef Faderl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Voestalpine Stahl GmbH
Original Assignee
Voestalpine Stahl GmbH
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Filing date
Publication date
Application filed by Voestalpine Stahl GmbH filed Critical Voestalpine Stahl GmbH
Priority to EP10751954.8A priority Critical patent/EP2496721B8/en
Priority to JP2012535712A priority patent/JP2013510233A/en
Priority to KR1020127011679A priority patent/KR20130004234A/en
Priority to US13/505,253 priority patent/US20120279868A1/en
Priority to CN2010800496469A priority patent/CN102712961A/en
Publication of WO2011054571A1 publication Critical patent/WO2011054571A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • 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
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/72—Temporary coatings or embedding materials applied before or during heat treatment during chemical change of surfaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment
    • 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
    • C21D9/663—Bell-type furnaces
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • 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
    • C21D2221/00—Treating localised areas of an article
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

  • the invention relates to a method for producing coated steel sheets.
  • barrier protective layers In principle, a distinction is made between so-called barrier protective layers and cathodically active protective layers.
  • Barrier protection layers are, in particular, protective layers which consist of aluminum, tin or chromium, for which purpose, for example, an aluminum alloy is applied to a steel strip by so-called hot-dip coating.
  • the most widespread corrosion protection layer with ka ⁇ thodischer effect is a zinc coating, the effect is based in particular on the fact that in a damage of the zinc layer on the steel down to the steel substrate herun ⁇ ter first the zinc is corroded as a chemically base metal and so the steel substrate protects.
  • the zinc coatings again contain pure zinc coatings, zinc coatings with a low aluminum content, Zinc coatings with an aluminum content of about 5% (Gal ⁇ fan) and zinc-aluminum coatings with about half each shares of zinc and aluminum.
  • These coatings are also applied in the hot-dip process, wherein a preheated steel strip is passed through a zinc bath ⁇ or zinc alloy bath.
  • Galvanealed layers in which first a Zink upon. Zinc alloy layer is applied to a steel substrate and then annealing is performed such that there is a diffusion reaction between the iron of the steel substrate and the zinc, so that forms a zinc-iron alloy layer.
  • a Zink By a layer is referred to as Galvanealed layer.
  • Such a Galvannealed layer is produced at annealing temperatures of 480 ° C to 600 ° C in continuous flow furnaces, in which the band passes through after galvanizing.
  • the DE 10 2007 031 91 96 AI relates to a method Erzeu ⁇ gene of flexibly rolled band material with a cathodic corrosion protection layer, said flexibly rolled in this method, material, ie, steel strip over the length is plated under ⁇ different union steel strip thicknesses, inter alia, electrolytically, followed by annealing, with the annealing treatment at
  • a method and an apparatus for finishing of a flexibly rolled band material are known from DE 10 2004 023 886 B4, the cold strip is to have a on its thickness profile dressing ⁇ -determined characteristic profile, wherein a first annealing treatment at temperature between 500 ° C and 600 ° C is carried out, then the cold strip is rolled to predetermined thickness- ⁇ runs such that the flexible-rolled cold-rolled strip having in the rolling direction at least one region of greater thickness and an area of lesser thickness and a second Glühbehand ⁇ lung follows, in which the temperature is higher than the first annealing treatment he follows.
  • galvannealed layer is encountered on such flexibly rolled strips.
  • the application of the galvannealed coating is usually by way of hot dip galvanizing followed by a continuous inline heat treatment.
  • this steel grades that can not be produced by a hot-dip galvanizing or with great effort, not be provided with a galvannealed coating. This includes isotropic steels, high strength steels with strengths
  • the object of the invention is to provide a method for producing flexibly rolled or isotropic or higher-strength galvannel-coated steel strips.
  • the object is achieved by a method having the features of claim 1.
  • the problems are avoided by different temperatures in the flexible rolled strip in that the strip is not galvanized but electrolytically galvanized, so that different heights of zinc-iron phases due to temperature differences of the strip during hot-dip galvanizing are already avoided.
  • the problems of hot-dip galvanizing of isotropic or higher-strength steels avoided the problems of hot-dip galvanizing of isotropic or higher-strength steels.
  • the galvannealed layer is not continuously generated in ⁇ line, but the galvannealed-layer formation takes place under protective gas in an annealer.
  • the temperature of the annealing is reduced, according to the invention, temperatures of about 300 ° C are maintained at holding ⁇ times of about 20 hours.
  • a strip is flexibly cold rolled, a recrystallization anneal is carried out in a bell annealer at about 650 ° C. for 24 hours, subsequently the strip is subjected to striping and electrolytic zinc plating and subsequently the galvannealing step is carried out in the annealing annealing.
  • a steel strip with periodically changing sheet thickness can be provided with a high-grade cathodic corrosion protection, which has a good weldability, advantageously both isotropic and higher-strength steels and other steel grades can also be provided with a Galvanealed layer.
  • Galvanea- sheets can be prepared with very low galvannealed layer pads, which is made possible firstly by the electrolytically ⁇ diagram zinc coating and the other by the gentle cooling.
  • isotropic and higher-strength steels which are difficult to access for hot-dip galvanizing, can also be provided with a galvannealed layer if the described glow annealing step according to the invention is followed by electrolytic galvanizing.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The invention relates to a process for producing A steel strip having a cathodic anti-corrosion coating, wherein the steel strip is hot-rolled and then cold-rolled, wherein the steel strip is subjected to electrolytic galvanizing and, following the electrolytic galvanizing, is heat-treated in a hood-type annealing furnace at temperatures ranging from 250°C to 350°C for a time period of 4 to 48 hours and, as a result, a zinc-iron layer is produced.

Description

Herstellung von Galvannealed-Blechen durch Wärmebehandlung elektrolytisch veredelter Bleche  Production of galvannealed sheets by heat treatment of electrolytically finished sheets

Die Erfindung betrifft ein Verfahren zum Herstellen von beschichteten Stahlblechen. The invention relates to a method for producing coated steel sheets.

Es ist bekannt, Stahlbleche mit einem Überzug eines Metalls herzustellen, um das Stahlblech von Korrosion zu schützen. It is known to produce steel sheets with a coating of a metal to protect the steel sheet from corrosion.

Man unterscheidet hierbei grundsätzlich zwischen sogenannten Barriereschutzschichten und kathodisch wirkenden Schutzschichten . In principle, a distinction is made between so-called barrier protective layers and cathodically active protective layers.

Barriereschutzschichten sind insbesondere Schutzschichten, die aus Aluminium, Zinn oder Chrom bestehen, wobei hierfür beispielsweise eine Aluminiumlegierung durch sogenanntes Schmelztauchbeschichten auf ein Stahlband aufgebracht wird. Barrier protection layers are, in particular, protective layers which consist of aluminum, tin or chromium, for which purpose, for example, an aluminum alloy is applied to a steel strip by so-called hot-dip coating.

Die am weitesten verbreitete Korrosionsschutzschicht mit ka¬ thodischer Wirkung ist eine Zinkbeschichtung, wobei die Wirkung insbesondere darauf beruht, dass bei einer Beschädigung der Zinkschicht auf dem Stahl bis auf das Stahlsubstrat herun¬ ter zunächst das Zink als chemisch unedleres Metall korrodiert wird und so das Stahlsubstrat schützt. The most widespread corrosion protection layer with ka ¬ thodischer effect is a zinc coating, the effect is based in particular on the fact that in a damage of the zinc layer on the steel down to the steel substrate herun ¬ ter first the zinc is corroded as a chemically base metal and so the steel substrate protects.

Bei den Zinkbeschichtungen gibt es wiederum Reinzinkbeschich- tungen, Zinkbeschichtungen mit einem geringen Aluminiumanteil, Zinkbeschichtungen mit einem Aluminiumanteil von etwa 5% (Gal¬ fan) und Zink-Aluminiumbeschichtungen mit etwa je hälftigen Anteilen von Zink und Aluminium. The zinc coatings again contain pure zinc coatings, zinc coatings with a low aluminum content, Zinc coatings with an aluminum content of about 5% (Gal ¬ fan) and zinc-aluminum coatings with about half each shares of zinc and aluminum.

Diese Beschichtungen werden ebenfalls im Schmelztauchverfahren aufgebracht, wobei ein vorerwärmtes Stahlband durch ein Zink¬ bad bzw. Zinklegierungsbad geführt wird. These coatings are also applied in the hot-dip process, wherein a preheated steel strip is passed through a zinc bath ¬ or zinc alloy bath.

Eine Besonderheit stellen sogenannte Galvannealed-Schichten dar, bei denen zunächst mit einer Feuerverzinkung eine Zinkbzw. Zink-Legierungsschicht auf eine Stahlsubstrat aufgebracht wird und anschießend eine Glühung derart vorgenommen wird, dass es zu einer Diffusionsreaktion zwischen dem Eisen des Stahlsubstrats und dem Zink kommt, so dass sich eine Zink- Eisen-Legierungsschicht bildet. Eine solche Schicht wird als Galvanealed-Schicht bezeichnet. A special feature are so-called galvannealed layers, in which first a Zinkbzw. Zinc alloy layer is applied to a steel substrate and then annealing is performed such that there is a diffusion reaction between the iron of the steel substrate and the zinc, so that forms a zinc-iron alloy layer. Such a layer is referred to as Galvanealed layer.

Eine solche Galvannealed-Schicht wird bei Glühtemperaturen von 480°C bis 600°C in kontinuierlichen DurchlaufÖfen erzeugt, in denen das Band nach dem Verzinken durchläuft. Such a Galvannealed layer is produced at annealing temperatures of 480 ° C to 600 ° C in continuous flow furnaces, in which the band passes through after galvanizing.

Die DE 10 2007 031 91 96 AI betrifft ein Verfahren zum Erzeu¬ gen von flexibel gewalztem Bandmaterial mit einer kathodischen Korrosionsschutzschicht, wobei bei diesem Verfahren flexibel gewalztes Material, d.h. Stahlband mit über die Länge unter¬ schiedlichen Stahlbanddicken u.a. elektrolytisch verzinkt und anschließend geglüht wird, wobei die Glühbehandlung bei The DE 10 2007 031 91 96 AI relates to a method Erzeu ¬ gene of flexibly rolled band material with a cathodic corrosion protection layer, said flexibly rolled in this method, material, ie, steel strip over the length is plated under ¬ different union steel strip thicknesses, inter alia, electrolytically, followed by annealing, with the annealing treatment at

< 420°C durchgeführt wird. <420 ° C is performed.

Aus der DE 10 2007 013 739 ist ein Verfahren zum flexiblen Walzen von beschichteten Stahlbändern bekannt, wobei diese Stahlbänder auch elektrolytisch verzinkt sein können und kontinuierlich geglüht werden. Aus der DE 10 2004 023 886 B4 ist ein Verfahren und eine Vorrichtung zur Veredelung von flexibel gewalztem Bandmaterial bekannt, bei dem flexibel gewalztes Bandmaterial mit perio¬ disch veränderlicher Materialdicke kontinuierlich durch eine Behandlungslinie aus Glühstrecke, Abschreckeinheit, Vorheiz¬ einheit und Zinkpott geführt und dadurch wärmebehandelt und feuerverzinkt wird, wobei die Eintrittstemperatur für den Zinkpott am flexibel gewalztem Band durch Variation der Heizenergie in der Vorheizeinheit in Abhängigkeit von der Banddi¬ cke auf einen konstanten Wert geregelt wird und die Zinkauf¬ tragsdicke durch Abstandsvariation von Ablassdüsen zum flexibel gewalztem Band in Abhängigkeit von der Banddicke auf einen konstanten Wert geregelt wird. From DE 10 2007 013 739 a method for flexible rolling of coated steel strips is known, wherein these steel strips can also be electrolytically galvanized and continuously annealed. From DE 10 2004 023 886 B4 discloses a method and apparatus for finishing of flexibly rolled strip material is known, wherein the flexibly rolled strip material out continuously with perio ¬ disch variable thickness of material through a treatment line of annealing, quenching unit, preheating ¬ unit and zinc pot and thereby is heat-treated and hot-dip galvanized, wherein the inlet temperature for the zinc pot to the flexibly rolled strip by varying the heat energy in the preheating function of the Banddi ¬ bridge is controlled to a constant value and the Zinkauf ¬ contract thick distance variation of discharge nozzles for flexibly rolled strip in dependence is controlled by the strip thickness to a constant value.

Aus der DE 10 2004 023 886 B4 sind ein Verfahren und eine Vorrichtung zu Veredelung von flexibel gewalztem Bandmaterial bekannt, wobei das Kaltband ein auf seinen Dickenverlauf abge¬ stimmtes Eigenschaftsprofil besitzen soll, wobei eine erste Glühbehandlung bei Temperatur zwischen 500°C und 600°C erfolgt, anschließend das Kaltband auf vordefinierte Dickenver¬ läufe derart gewalzt wird, dass das flexibel gewalzte Kaltband in Walzrichtung zumindest ein Bereich höherer Dicke und ein Bereich geringerer Dicke aufweist und eine zweite Glühbehand¬ lung folgt, bei der die Temperatur höher als bei der ersten Glühbehandlung erfolgt. A method and an apparatus for finishing of a flexibly rolled band material are known from DE 10 2004 023 886 B4, the cold strip is to have a on its thickness profile abge ¬-determined characteristic profile, wherein a first annealing treatment at temperature between 500 ° C and 600 ° C is carried out, then the cold strip is rolled to predetermined thickness-¬ runs such that the flexible-rolled cold-rolled strip having in the rolling direction at least one region of greater thickness and an area of lesser thickness and a second Glühbehand ¬ lung follows, in which the temperature is higher than the first annealing treatment he follows.

Auf derart flexibel gewalzten Bändern eine sogenannte Galvan- nealed-Schicht aufzubringen, stößt jedoch auf Probleme. Das Aufbringen der Galvannealed-Beschichtung erfolgt üblicherweise über den Weg einer Feuerverzinkung mit einer anschließenden kontinuierlichen Inline-Wärmebehandlung . Hiermit könnten jedoch Stahlgüten, die über eine Schmelztauchverzinkung nicht oder mit großem Aufwand hergestellt werden können, nicht mit einer Galvannealed-Beschichtung versehen werden. Hierzu gehö- ren isotrope Stähle, hoherfeste Stähle mit Festigkeiten However, a so-called galvannealed layer is encountered on such flexibly rolled strips. The application of the galvannealed coating is usually by way of hot dip galvanizing followed by a continuous inline heat treatment. However, this steel grades that can not be produced by a hot-dip galvanizing or with great effort, not be provided with a galvannealed coating. This includes isotropic steels, high strength steels with strengths

> 1.000 MPa und die zuvor genannten flexibel gewalzten Bänder. Gerade bei flexibel gewalzten Bändern ergibt sich aufgrund der unterschiedlichen Blechdicke in einer Schmelztauchverzinkungs- anlage sowohl innenhomogene mechanische Eigenschaften als auch unterschiedliche Zink-Eisen-Wachstumsfortschritte, da sich bei Inline-Verfahren selbstverständlich die dicken Bereiche anders aufheizen als die dünnen Bereiche und dementsprechend andere Diffusionsgeschwindigkeiten zwischen Zink und Eisen vorliegen müssen . > 1,000 MPa and the previously mentioned flexibly rolled strips. Especially with flexibly rolled strips results due to the different sheet thickness in a hot-dip galvanizing both internally homogeneous mechanical properties and different zinc-iron growth progress, since in inline process of course, the thick areas heat up differently than the thin areas and correspondingly different diffusion rates between Zinc and iron must be present.

Die Herstellung eines flexibel gewalzten Bandes mit einer Gal- vannealingbeschichtung an einer FVZ-Anlage erscheint jedoch auch aus anderen Gründen kaum machbar. Selbst bei einer Induk- tions-Galvannealing-Anlage wäre die Leistungssteuerung in der geforderten Exaktheit (Variation der Spulenleistung um einen Faktor bis zu zwei und mehr innerhalb weniger Zentimeter Positioniergenauigkeit) schwer darstellbar. The production of a flexibly rolled strip with a galvannealing coating on an FVZ plant, however, seems hardly feasible for other reasons. Even with an induction galvannealing system, the power control would be difficult to represent in the required accuracy (variation of coil power by a factor of up to two and more within a few centimeters of positioning accuracy).

Aufgabe der Erfindung ist es ein Verfahren zum Herstellen von flexibel gewalzten oder isotropen oder höherfesten, galvannea- led-beschichteten Stahlbändern zu schaffen. Die Aufgabe wird mit einem Verfahren mit den Merkmalen des Anspruchs 1 gelöst. The object of the invention is to provide a method for producing flexibly rolled or isotropic or higher-strength galvannel-coated steel strips. The object is achieved by a method having the features of claim 1.

Vorteilhafte Weiterbildungen sind in Unteransprüchen gekennzeichnet . Advantageous developments are characterized in the subclaims.

Erfindungsgemäß werden die Probleme durch unterschiedliche Temperaturen im flexibel gewalzten Band dadurch umgangen, dass das Band nicht feuerverzinkt sondern elektrolytisch verzinkt wird, so dass unterschiedliche Aufbauhöhen von Zink-Eisen- Phasen aufgrund von Temperaturunterschieden des Bandes beim Feuerverzinken schon vermieden werden. In gleicher Weise wer- den Probleme beim Feuerverzinken von isotropen oder höherfesten Stählen vermieden. According to the invention, the problems are avoided by different temperatures in the flexible rolled strip in that the strip is not galvanized but electrolytically galvanized, so that different heights of zinc-iron phases due to temperature differences of the strip during hot-dip galvanizing are already avoided. In the same way avoided the problems of hot-dip galvanizing of isotropic or higher-strength steels.

Erfindungsgemäß wird zudem die Galvannealed-Schicht nicht in¬ line kontinuierlich erzeugt, sondern die Galvannealed-Schicht- Bildung erfolgt unter Schutzgas in einer Haubenglühe . Zudem wird erfindungsgemäß die Temperatur der Glühung herabgesetzt, wobei erfindungsgemäß Temperaturen von etwa 300 °C bei Halte¬ zeiten von etwa 20 Stunden eingehalten werden. According to the invention also the galvannealed layer is not continuously generated in ¬ line, but the galvannealed-layer formation takes place under protective gas in an annealer. In addition, according to the invention, the temperature of the annealing is reduced, according to the invention, temperatures of about 300 ° C are maintained at holding ¬ times of about 20 hours.

Aufgrund der langsamen Aufheizung in der Haubenglühe erfolgt eine gleichmäßige Erwärmung des Bandes, so dass die Zink- Eisen-Reaktion auch in unterschiedlich dicken Bandbereichen sehr gleichmäßig erfolgt. Due to the slow heating in the annealing annealing, a uniform heating of the strip takes place, so that the zinc-iron reaction takes place very evenly in different thickness band regions.

Erfindungsgemäß wird somit ein Band flexibel kalt gewalzt, in einer Haubenglühe eine Rekristallisierungsglühe durchgeführt, bei etwa 650°C für 24 Stunden, nachfolgend das Band dressiert und elektrolytisch verzinkt und nachfolgend der Galvannealing- Schritt in der Haubenglühe durchgeführt. Thus, according to the invention, a strip is flexibly cold rolled, a recrystallization anneal is carried out in a bell annealer at about 650 ° C. for 24 hours, subsequently the strip is subjected to striping and electrolytic zinc plating and subsequently the galvannealing step is carried out in the annealing annealing.

Bei der Erfindung ist somit von Vorteil, dass ein Stahlband mit periodisch wechselnder Blechdicke (flexibel gewalztes Band (tailor rolled blank) ) mit einem hochwertigen kathodischen Korrosionsschutz versehen werden kann, der eine gute Schweißeignung besitzt, wobei in vorteilhafter Weise sowohl isotrope und höherfeste Stähle und andere Stahlsorten ebenso mit einer Galvanealed-Schicht versehen werden können. In the invention, it is therefore advantageous that a steel strip with periodically changing sheet thickness (flexible rolled strip) can be provided with a high-grade cathodic corrosion protection, which has a good weldability, advantageously both isotropic and higher-strength steels and other steel grades can also be provided with a Galvanealed layer.

Darüber hinaus ist von Vorteil, dass erfindungsgemäß Galvanea- led-Bleche mit sehr niedrigen Galvannealed-Schichtauflagen hergestellt werden können, was einerseits durch die elektroly¬ tische Verzinkung und andererseits durch die schonende Kühlung ermöglicht wird. Erfindungsgemäß können auch isotrope und höherfeste Stähle, die einer Feuerverzinkung nur schwer zugänglich sind, mit einer Galvannealed-Schicht versehen werden, wenn sich an die elektrolytische Verzinkung der beschriebene erfindungsgemäße Haubenglühschritt anschließt. In addition, it is advantageous that according to the invention led Galvanea- sheets can be prepared with very low galvannealed layer pads, which is made possible firstly by the electrolytically ¬ diagram zinc coating and the other by the gentle cooling. According to the invention, isotropic and higher-strength steels, which are difficult to access for hot-dip galvanizing, can also be provided with a galvannealed layer if the described glow annealing step according to the invention is followed by electrolytic galvanizing.

Claims

Patentansprüche claims 1. Verfahren zum Herstellen von Stahlband mit einer kathodischen Korrosionsschutzbeschichtung, wobei das Stahlband warmgewalzt und anschließend kaltgewalzt wird, wobei das Stahlband einer elektrolytischen Verzinkung unterzogen wird und das Stahlband nach der elektrolytischen Verzinkung in einem Haubenglühofen bei Temperaturen von 250°C bis 350°C für einen Zeitraum von 4 bis 48 Stunden wärmebehandelt und dadurch eine Zink-Eisen-Schicht erzeugt wird. A process for producing steel strip with a cathodic anti-corrosive coating, wherein the steel strip is hot rolled and then cold rolled, wherein the steel strip is subjected to electrolytic galvanizing and the steel strip after electrolytic galvanizing in a crucible annealing furnace at temperatures of 250 ° C to 350 ° C for heat treated for a period of 4 to 48 hours, thereby producing a zinc-iron layer. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Stahlband flexibel kaltgewalzt derart ist, dass das Stahl¬ band über die Länge und/oder Breite periodisch unterschied¬ liche Dicken aufweist und/oder ein Stahlband mit isotropen oder höherfesten Eigenschaften verwendet wird. 2. The method according to claim 1, characterized in that the steel strip cold-rolled flexible is such that the steel ¬ ribbon across the length and / or width which periodically differed ¬ Liche thicknesses and / or a steel strip with isotropic or higher strength properties is used. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das flexibel gewalzte Band vor der elektrolytischen Verzinkung einer Rekristallisationsglühung im Haubenofen bei 550°C bis 650°C oder in einer Kontiglühe unterzogen wird. 3. The method according to claim 1 or 2, characterized in that the flexibly rolled strip is subjected before the electrolytic galvanizing a recrystallization annealing in the hood furnace at 550 ° C to 650 ° C or in a continuous annealing. 4. Verfahren nach Anspruch 1,2 oder 3, dadurch gekennzeichnet, dass die Schichtdicke der elektrolytisch aufgebrachten Zinkschicht zwischen 2 μιη und 10 μιη liegt. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Glühung zur Umwandlung der Zink- i eine Zink-Eisenschicht so durchgeführt wird, dass die Zink- Eisen-Schicht maximal 30% Eisen enthält. 4. The method according to claim 1,2 or 3, characterized in that the layer thickness of the electrolytically applied zinc layer is between 2 μιη and 10 μιη. Method according to one of the preceding claims, characterized in that the annealing for the conversion of zinc i a zinc-iron layer is performed so that the zinc-iron layer contains a maximum of 30% iron.
PCT/EP2010/063351 2009-11-03 2010-09-13 Manufacturing galvannealed sheets by heat-treating electrolytically finished sheets Ceased WO2011054571A1 (en)

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KR1020127011679A KR20130004234A (en) 2009-11-03 2010-09-13 Manufacturing galvannealed sheets by heat-treating electrolytically finished sheets
US13/505,253 US20120279868A1 (en) 2009-11-03 2010-09-13 Manufacturing galvannealed sheets by heat-treating electrolytically finished sheets
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012085256A3 (en) * 2010-12-24 2012-08-16 Voestalpine Stahl Gmbh Method for producing hardened structural elements

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012110972B3 (en) * 2012-11-14 2014-03-06 Muhr Und Bender Kg A method of making a product from flexibly rolled strip material and product from flexibly rolled strip material
DE102013010025A1 (en) * 2013-06-17 2014-12-18 Muhr Und Bender Kg Method for producing a product from flexibly rolled strip material
FI20135775A7 (en) 2013-07-16 2014-09-03 Rautaruukki Oyj Method of manufacturing a galvannealed steel strip product for hot press forming, method of manufacturing a hot-pressed steel component, and galvannealed steel strip product
RU2661313C2 (en) * 2014-01-17 2018-07-16 Аперам Method of manufacturing belt of variable thickness and belt produced by this method
DE102015112889A1 (en) * 2015-08-05 2017-02-09 Salzgitter Flachstahl Gmbh High-strength manganese-containing steel, use of the steel for flexibly rolled flat steel products and production methods together with flat steel product for this purpose
DE102015116619B4 (en) 2015-09-30 2018-11-29 Thyssenkrupp Ag Production of semi-finished products and structural components with regionally different material thicknesses
DE102016102723B3 (en) 2016-02-16 2017-06-01 Salzgitter Flachstahl Gmbh Tempering roller, method for applying a flat product hereby and flat product thereof
CN112292468A (en) * 2018-05-08 2021-01-29 塔塔钢铁艾默伊登有限责任公司 Variably rolled steel strip, sheet or blank and method for the production thereof
CN109487307A (en) * 2018-12-28 2019-03-19 凡登（常州）新型金属材料技术有限公司 A kind of zinc-coated wire and preparation method thereof
CN111719131A (en) * 2019-03-22 2020-09-29 宝山钢铁股份有限公司 Production process of variable-thickness steel plate with coating
WO2020221628A1 (en) * 2019-04-30 2020-11-05 Tata Steel Ijmuiden B.V. Process for producing batch annealed tailor rolled strip
EP3872231A1 (en) * 2020-02-28 2021-09-01 voestalpine Stahl GmbH Method for conditioning the surface of a metal strip coated with a zinc alloy corrosion protection layer
LU101954B1 (en) * 2020-07-24 2022-01-24 Phoenix Contact Gmbh & Co Process for producing a friction-optimized zinc coating on a steel component
CN119352122B (en) * 2024-12-25 2025-05-23 邹平奥力普金属科技有限公司 Steel wire electroplating processing method and equipment

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1624093A1 (en) * 2004-08-04 2006-02-08 Aluminal Oberflächentechnik GmbH & Co. KG Coating of substrates of light metals or light metal alloys
EP1767670A1 (en) * 2005-09-23 2007-03-28 ThyssenKrupp Steel AG Method for producing a corrosion protected steel flat product
DE102004023886B4 (en) 2004-05-12 2007-04-12 Muhr Und Bender Kg Method and device for finishing flexibly rolled strip material
DE102006001628A1 (en) * 2006-01-11 2007-07-26 Thyssenkrupp Steel Ag Galvanized hard-rolled cold-rolled flat product and process for its preparation
DE102007013739B3 (en) 2007-03-22 2008-09-04 Voestalpine Stahl Gmbh Flexible rolling process to manufacture sheet metal component after hot or cold dipping and further mechanical and/or chemical treatment
DE102007019196A1 (en) * 2007-04-20 2008-10-23 Muhr Und Bender Kg Rolling process to make a flexible ribbon with a cathode anti-corrosion coating on hot dipped or electro-galvanized steel
EP2045360A1 (en) * 2007-10-02 2009-04-08 ThyssenKrupp Steel AG Method for manufacturing a steel part by hot forming and steel part manufactured by hot forming

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS609895A (en) * 1983-06-27 1985-01-18 Sumitomo Metal Ind Ltd Manufacturing method of alloyed electrogalvanized steel sheet
JPS62240791A (en) * 1986-04-14 1987-10-21 Nippon Kokan Kk <Nkk> Treatment for alloying steel strip electrically-galvanized on one side
JPH0621348B2 (en) * 1986-07-22 1994-03-23 日新製鋼株式会社 Alloyed zinc plated steel sheet and its manufacturing method
JPH0432538A (en) * 1990-05-28 1992-02-04 Nippon Steel Corp High r-value electrogalvanized composite steel sheet with excellent burr resistance and plating adhesion, and its manufacturing method
JP2950199B2 (en) * 1995-06-12 1999-09-20 株式会社神戸製鋼所 Electrogalvanized steel sheet and electrogalvanized steel sheet having excellent wood grain resistance, and methods for producing them
WO1997031131A1 (en) * 1996-02-22 1997-08-28 Sumitomo Metal Industries, Ltd. Galvannealed sheet steel and process for producing the same
DE19840898C2 (en) * 1998-09-08 2000-06-29 Thyssenkrupp Stahl Ag Process for producing load-optimized steel strips
JP2000096148A (en) * 1998-09-25 2000-04-04 Nkk Corp Manufacturing method of galvanized steel sheet with excellent surface appearance
DE10041280C2 (en) * 2000-08-22 2003-03-06 Muhr & Bender Kg Method and device for flexible rolling of a metal strip
DE10055338C1 (en) * 2000-11-08 2002-03-07 Thyssenkrupp Stahl Ag Production of cold strip comprises hot rolling pre-material produced from steel, cold rolling hot strip to form cold strip, annealing at temperature which is lower than recrystallization temperature, cold deforming, and further annealing
DE10102932C1 (en) * 2001-01-23 2002-08-22 Salzgitter Ag Process for producing a cold-rolled steel strip or sheet and strip or sheet which can be produced by the process
DE10259230B4 (en) * 2002-12-17 2005-04-14 Thyssenkrupp Stahl Ag Method for producing a steel product
JP4296785B2 (en) * 2003-01-20 2009-07-15 Ｊｆｅスチール株式会社 Bell type annealing furnace
MXPA06000826A (en) * 2003-07-29 2006-08-23 Voestalpine Stahl Gmbh Method for producing hardened parts from sheet steel.
CN100473738C (en) * 2006-05-25 2009-04-01 宝山钢铁股份有限公司 Solution strengthening isotropical steel and preparation method thereof
DE102006039307B3 (en) * 2006-08-22 2008-02-21 Thyssenkrupp Steel Ag Process for coating a 6-30 wt.% Mn-containing hot or cold rolled steel strip with a metallic protective layer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004023886B4 (en) 2004-05-12 2007-04-12 Muhr Und Bender Kg Method and device for finishing flexibly rolled strip material
EP1624093A1 (en) * 2004-08-04 2006-02-08 Aluminal Oberflächentechnik GmbH & Co. KG Coating of substrates of light metals or light metal alloys
EP1767670A1 (en) * 2005-09-23 2007-03-28 ThyssenKrupp Steel AG Method for producing a corrosion protected steel flat product
DE102006001628A1 (en) * 2006-01-11 2007-07-26 Thyssenkrupp Steel Ag Galvanized hard-rolled cold-rolled flat product and process for its preparation
DE102007013739B3 (en) 2007-03-22 2008-09-04 Voestalpine Stahl Gmbh Flexible rolling process to manufacture sheet metal component after hot or cold dipping and further mechanical and/or chemical treatment
DE102007019196A1 (en) * 2007-04-20 2008-10-23 Muhr Und Bender Kg Rolling process to make a flexible ribbon with a cathode anti-corrosion coating on hot dipped or electro-galvanized steel
EP2045360A1 (en) * 2007-10-02 2009-04-08 ThyssenKrupp Steel AG Method for manufacturing a steel part by hot forming and steel part manufactured by hot forming

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012085256A3 (en) * 2010-12-24 2012-08-16 Voestalpine Stahl Gmbh Method for producing hardened structural elements

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