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EP1819840B1 - Method for hot dip coating a strip of heavy-duty steel - Google Patents

Method for hot dip coating a strip of heavy-duty steel Download PDF

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Publication number
EP1819840B1
EP1819840B1 EP05812469A EP05812469A EP1819840B1 EP 1819840 B1 EP1819840 B1 EP 1819840B1 EP 05812469 A EP05812469 A EP 05812469A EP 05812469 A EP05812469 A EP 05812469A EP 1819840 B1 EP1819840 B1 EP 1819840B1
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EP
European Patent Office
Prior art keywords
strip
atmosphere
heat treatment
oxide layer
continuous furnace
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EP05812469A
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German (de)
French (fr)
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EP1819840A1 (en
Inventor
Ronny Leuschner
Manfred Meurer
Wilhelm Warnecke
Sabine Zeizinger
Gernot Nothacker
Michael Ullmann
Norbert Schaffrath
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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
    • C23C2/04—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
    • C23C2/003—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
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • C23C2/004—Snouts
    • 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
    • C23C2/34—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

  • hot-rolled or cold-rolled, surface-treated steel sheets are used.
  • the demands placed on such sheets are many. They should on the one hand be well deformable and on the other hand have a high strength.
  • the high strength is achieved by adding certain alloying constituents, such as Mn, Si, Al and Cr, to the iron.
  • alloying constituents such as Mn, Si, Al and Cr
  • the solution to this problem consists in the method specified in claim 1.
  • the method according to the invention is in the max. 250 s first step prevents the heating of significant alloying constituents diffuse to the surface of the strip. It would be optimal if diffusion of alloy components to the surface of the strip could be completely prevented, which is hardly possible for practical reasons. What matters is that the diffusion of alloying constituents to the surface is suppressed to such an extent that, in the following step, an effective iron oxide layer can be formed which prevents further alloying constituents from diffusing to the surface at the elevated annealing temperature.
  • a pure iron layer can be formed during the longer than 50 s annealing treatment, which is very well suited for a full-surface and firmly adhering coating of zinc and / or aluminum.
  • the result is optimal if the iron oxide layer produced in the oxidizing atmosphere is completely reduced to pure iron, because then the coating is also optimized with respect to its deformation and strength properties.
  • the thickness of the forming oxide layer is measured and adjusted depending on this thickness and dependent on the passage speed of the belt treatment time of the O 2 content such that the Oxide layer can then be completely reduced.
  • the change in the throughput speed of the belt for example as a result of disturbances can be considered in this way without detriment to the surface quality of the hot dip coated strip.
  • the high-strength steel should contain at least one of the following constituents: Mn> 0.5%, Al> 0.2%, Si> 0.1%, Cr> 0.3%. Other components such as Mo, Ni, V, Ti, Nb and P can be added.
  • An essential feature of the invention is that the heat treatment of the strip in the reducing atmosphere takes much longer in both the warm-up and the subsequent annealing as compared to the heat treatment in the oxidizing atmosphere.
  • the volume of the oxidizing atmosphere is very small compared to the remaining volume of the reducing atmosphere.
  • This has the advantage that it is possible to react quickly to changes in the treatment process, in particular the throughput speed and the formation of the oxidation layer.
  • the heat treatment of the strip takes place in the reducing atmosphere in a continuous furnace with an integrated chamber with the oxidizing atmosphere, wherein the volume of the chamber to the remaining volume of the continuous furnace is many times smaller.
  • the cleaned belt 1 then passes into a continuous furnace 5. From the continuous furnace 5, the belt 1 passes through a locked to the atmosphere lock 6 in a hot dip 7 with zinc. From there it passes via a cooling section 8 or a device for heat treatment to a winding station 9 in the form of a coil.
  • the band 1 in reality does not run in a straight line through the continuous furnace 5, but meandering, in order to achieve sufficiently long treatment times at practical length of the continuous furnace 5 can.
  • the continuous furnace 5 is divided into three zones 5a, 5b, 5c.
  • the middle zone 5b forms a reaction chamber and is atmospherically closed with respect to the first and last zones 5a, 5c.
  • Their length is only about 1/100 of the total length of the continuous furnace 5. For better illustration, the drawing is not to scale extent. According to the different lengths of the zones and the treatment times of the continuous belt 1 in the individual zones 5a, 5b, 5c are different.
  • the first zone 5a there is a reducing atmosphere.
  • a typical composition of this atmosphere consists of 2% to 8% H 2 and balance N 2 .
  • the strip is heated to 650 to 750 ° C. At this temperature, the stated alloying constituents diffuse only in small amounts to the surface of the strip 1.
  • the temperature of the first zone 5a is essentially kept only.
  • Their atmosphere is oxygenated.
  • the O 2 content is between 0.01% to 1%. He can be hired. It depends on how long the treatment time is. If the treatment time is short, the O 2 content is high, while it is low with long treatment time.
  • an iron oxide layer is formed on the surface of the belt. The thickness of this iron oxide layer can be measured by optical means. Depending on the measured thickness and the flow rate of the O 2 content the atmosphere set. Since the central zone 5b is very short in comparison to the entire furnace length, the chamber volume is correspondingly small. Therefore, the reaction time for a change in the composition of the atmosphere is small.
  • a further heating up to about 900 ° C takes place, in which the strip 1 is annealed.
  • This heat treatment is carried out in a reducing atmosphere with an H 2 content of 2% to 8% and balance N 2 .
  • the iron oxide layer prevents alloying constituents from diffusing to the strip surface. Since the annealing treatment takes place in a reducing atmosphere, the iron oxide layer is converted into a pure iron layer.
  • the strip 1 is further cooled on its further way in the direction of the hot dip bath 7, so that when leaving the continuous furnace 5, it has about the temperature of the hot dip bath 7 of about 480 ° C. Since the strip 1 is made of pure iron after leaving the continuous furnace 5 on its surface, it provides the zinc of the hot-dip bath 7 an optimal basis for a strong bond.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Description

Im Automobilkarosseriebau werden aus Gründen des Korrosionsschutzes warm- oder kaltgewalzte, oberflächenveredelte Bleche aus Stahl eingesetzt. Die an solche Bleche gestellten Anforderungen sind vielfältig. Sie sollen einerseits gut verformbar sein und andererseits eine hohe Festigkeit haben. Die hohe Festigkeit erreicht man durch Zusatz von bestimmten Legierungsbestandteilen, wie Mn, Si, A1 und Cr, zum Eisen. Um das Eigenschaftsprofil solcher Stähle zu optimieren, ist es üblich, die Bleche unmittelbar vor dem Beschichten mit Zink und/oder Aluminium im Schmelzbad zu glühen. Während das Schmelztauchbeschichten von Stahlbändern, die nur geringe Anteile an den genannten Legierungsbestandteilen enthalten, unproblematisch ist, gibt es beim Schmelztauchbeschichten von Stahlblech mit höheren Legierungsanteilen Schwierigkeiten. An der Oberfläche des Stahlbleches ergeben sich Haftungsmängel des Überzugs, und es bilden sich sogar unbeschichtete Stellen.In automotive body construction, for reasons of corrosion protection, hot-rolled or cold-rolled, surface-treated steel sheets are used. The demands placed on such sheets are many. They should on the one hand be well deformable and on the other hand have a high strength. The high strength is achieved by adding certain alloying constituents, such as Mn, Si, Al and Cr, to the iron. In order to optimize the property profile of such steels, it is common to anneal the sheets in the molten bath immediately prior to coating with zinc and / or aluminum. While hot dip coating of steel strips containing only low levels of said alloying ingredients is straightforward, there are difficulties in hot dip coating steel sheets with higher alloy levels. On the surface of the steel sheet there are liability deficiencies of the coating, and even uncoated areas are formed.

Im Stand der Technik gibt es eine Vielzahl von Versuchen, diese Schwierigkeiten zu vermeiden. Eine optimale Lösung des Problems scheint es allerdings noch nicht zu geben.There are many attempts in the prior art to avoid these difficulties. However, an optimal solution of the problem does not seem to exist yet.

Bei einem bekannten Verfahren zum Schmelztauchbeschichten eines Bandes aus Stahl mit Zink durchläuft das zu beschichtende Band einen direkt beheizten Vorwärmer (DFF = Direct Fired Furnace). An den eingesetzten Gasbrennern kann durch Veränderung des Gas-Luft-Gemisches eine Erhöhung des Oxidationspotentials in der das Band umgebenden Atmosphäre erzeugt werden. Das erhöhte Sauerstoffpotential führt zu einer Oxidation des Eisens an der Bandoberfläche. In einer anschließenden Ofenstrecke wird die so gebildete Eisenoxidschicht reduziert. Eine gezielte Einstellung der Oxidschichtdicke an der Bandoberfläche ist sehr schwierig. Bei großer Bandgeschwindigkeit ist sie dünner als bei kleiner Bandgeschwindigkeit. Folglich lässt sich in der reduzierenden Atmosphäre keine eindeutig definierte Beschaffenheit der Bandoberfläche erzeugen. Das kann wiederum zu Haftungsproblemen des Überzugs an der Bandoberfläche führen.In a known process for hot dip coating a steel strip with zinc, the strip to be coated passes through a directly heated pre-heater (DFF = Direct Fired Furnace). By changing the gas-air mixture, an increase in the oxidation potential in the atmosphere surrounding the band can be produced at the gas burners used. The increased oxygen potential leads to oxidation of the iron at the strip surface. In a subsequent furnace section, the iron oxide layer thus formed is reduced. A targeted adjustment of the oxide layer thickness at the strip surface is very difficult. At high belt speed, it is thinner than at low belt speed. Consequently, in the reducing atmosphere, no clearly defined condition of the tape surface can be produced. This in turn can lead to adhesion problems of the coating on the strip surface.

In modernen Schmelztauchbeschichtungslinien mit einem RTF-Vorwärmer (RTF = Radiant Tube Furnace) werden im Gegensatz zur vorbeschriebenen bekannten Anlage keine gasbeheizten Brenner verwendet. Eine Voroxidation des Eisens über eine Veränderung des Gas-Luft-Gemisches kann daher nicht erfolgen. In diesen Anlagen erfolgt vielmehr die komplette Glühbehandlung des Bandes in einer Schutzgasatmosphäre. Bei einer solchen Glühbehandlung eines Bandes aus Stahl mit höheren Legierungsbestandteilen können jedoch diese Legierungsbestandteile an die Bandoberfläche diffundieren und hier nicht reduzierbare Oxide bilden. Diese Oxide behindern eine einwandfreie Beschichtung mit Zink und/oder Aluminium im Schmelzbad.
Aus der Patentliteratur sind verschiedene Verfahren zum Schmelztauchbeschichten eines Stahlbandes mit verschiedenen Beschichtungsmaterialien bekannt.In modern hot-dip coating lines with a RTF preheater (RTF = Radiant Tube Furnace), in contrast to the previously described known system, no gas-fired burners are used. A pre-oxidation of the iron via a change in the gas-air mixture can therefore not take place. In these systems, rather, the complete annealing of the strip takes place in a protective gas atmosphere. In such an annealing of a strip of steel with higher alloying constituents, however, these alloying constituents can diffuse to the strip surface and form non-reducible oxides here. These oxides hinder a perfect coating with zinc and / or aluminum in the molten bath.
The patent literature discloses various methods of hot dip coating a steel strip with various coating materials.

Aus der DE 689 12 243 T2 ist ein Verfahren zur kontinuierlichen Heisstauchbeschichtung eines Stahlbandes mit Aluminium bekannt, bei dem das Band in einem Durchlaufofen erwärmt wird. In einer ersten Zone werden Oberflächenverunreinigungen entfernt. Dafür hat die Ofenatmosphäre eine sehr hohe Temperatur. Da das Band diese Zone aber mit hoher Geschwindigkeit durchläuft, wird es nur etwa auf die halbe Temperatur der Atmosphäre erwärmt. In der anschließenden zweiten Zone, die unter Schutzgas steht, wird das Band auf die Temperatur des Beschichtungsmaterials Aluminium erwärmt.From the DE 689 12 243 T2 discloses a process for the continuous hot dip coating of a steel strip with aluminum, in which the strip is heated in a continuous furnace. In a first zone, surface contaminants are removed. But the furnace atmosphere has a very high temperature. However, as the belt passes through this zone at high speed, it is only heated to about half the temperature of the atmosphere. In the subsequent second zone, which is under protective gas, the strip is heated to the temperature of the coating material aluminum.

Aus der DE 695 07 977 T2 ist ein zweistufiges Heisstauchbeschichtungsverfahren eines Chrom enthaltenden Stahllegierungsbandes bekannt, hier wird das Band in einer ersten Stufe geglüht, um an der Bandoberfläche eine Eisenanreicherung zu erhalten. Anschließend wird das Band in einer nicht oxydierenden Atmosphäre auf die Temperatur des Beschichtungsmetalls erhitzt.From the DE 695 07 977 T2 A two-stage hot dip coating process of a chromium-containing steel alloy strip is known, here the strip is annealed in a first stage to obtain an iron enrichment at the strip surface. Subsequently, the tape is heated in a non-oxidizing atmosphere to the temperature of the coating metal.

Aus der JP 02285057 A ist bekannt, ein Stahlband in einem mehrstufigen Verfahren zu verzinken. Dafür wird das zuvor gereinigte Band in einer nicht oxydierenden Atmosphäre bei einer Temperatur von etwa 820 ° C behandelt. Dann wird das Band bei etwa 400 ° C bis 700 ° C in einer schwach oxydierenden Atmosphäre behandelt, bevor es an seiner Oberfläche in einer reduzierenden Atmosphäre reduziert wird. Abschließend wird das auf etwa 420 ° C bis 500 ° C abgekühlte Band in üblicher Weise verzinkt.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zum Schmelztauchbeschichten eines Bandes aus höherfestem Stahl mit Zink und/oder Aluminium zu entwickeln, mit dem ein Stahlband mit einer optimal veredelten Oberfläche in einer RTF-Anlage produziert wird.From the JP 02285057 A It is known to galvanize a steel strip in a multi-stage process. For this, the previously cleaned band is treated in a non-oxidizing atmosphere at a temperature of about 820 ° C. Then that will be Strip treated at about 400 ° C to 700 ° C in a weakly oxidizing atmosphere before it is reduced on its surface in a reducing atmosphere. Finally, the cooled to about 420 ° C to 500 ° C strip is galvanized in the usual way.
The invention has for its object to develop a process for hot dip coating a strip of high strength steel with zinc and / or aluminum, with which a steel strip is produced with an optimally finished surface in a RTF plant.

Die Lösung dieser Aufgabe besteht in dem in Anspruch 1 angegebenen Verfahren.
Bei dem erfindungsgemäßen Verfahren wird im max. 250 s dauernden ersten Schritt verhindert, dass bei der Erwärmung wesentliche Legierungsbestandteile an die Oberfläche des Bandes diffundieren. Optimal wäre es, wenn eine Diffusion von Legierungsbestandteilen an die Oberfläche des Bandes ganz verhindert werden könnte, was allerdings aus praktischen Gründen kaum möglich ist. Entscheidend ist, dass die Diffusion von Legierungsbestandteilen an die Oberfläche so weit unterdrückt wird, dass im folgenden Schritt eine wirksame Eisenoxidschicht gebildet werden kann, die verhindert, dass bei der erhöhten Glühtemperatur weitere Legierungsbestandteile an die Oberfläche diffundieren. So kann bei der länger als 50 s dauernden Glühbehandlung in der reduzierenden Atmosphäre eine Reineisenschicht entstehen, die für eine vollflächige und fest haftende Beschichtung aus Zink und/oder Aluminium sehr gut geeignet ist.The solution to this problem consists in the method specified in claim 1.
In the method according to the invention is in the max. 250 s first step prevents the heating of significant alloying constituents diffuse to the surface of the strip. It would be optimal if diffusion of alloy components to the surface of the strip could be completely prevented, which is hardly possible for practical reasons. What matters is that the diffusion of alloying constituents to the surface is suppressed to such an extent that, in the following step, an effective iron oxide layer can be formed which prevents further alloying constituents from diffusing to the surface at the elevated annealing temperature. Thus, in the reducing atmosphere, a pure iron layer can be formed during the longer than 50 s annealing treatment, which is very well suited for a full-surface and firmly adhering coating of zinc and / or aluminum.

Optimal ist das Ergebnis dann, wenn die in der oxidierenden Atmosphäre erzeugte Eisenoxidschicht vollständig in Reineisen reduziert wird, weil dann der Überzug auch bezüglich seiner Verformungs- und Festigkeitseigenschaften optimiert ist.The result is optimal if the iron oxide layer produced in the oxidizing atmosphere is completely reduced to pure iron, because then the coating is also optimized with respect to its deformation and strength properties.

Nach einer Ausgestaltung der Erfindung wird bei der Behandlung des Bandes auf der Strecke mit der oxidierenden Atmosphäre die Dicke der sich bildenden Oxidschicht gemessen und in Abhängigkeit von dieser Dicke und der von der Durchlaufgeschwindigkeit des Bandes abhängigen Behandlungszeit der O2-Gehalt derart eingestellt, dass die Oxidschicht anschließend vollständig reduziert werden kann. Die Änderung der Durchlaufgeschwindigkeit des Bandes z.B. infolge von Störungen lässt sich auf diese Art und Weise ohne Nachteil für die Oberflächenqualität des schmelztauchbeschichteten Bandes berücksichtigen.According to one embodiment of the invention, in the treatment of the strip on the route with the oxidizing atmosphere, the thickness of the forming oxide layer is measured and adjusted depending on this thickness and dependent on the passage speed of the belt treatment time of the O 2 content such that the Oxide layer can then be completely reduced. The change in the throughput speed of the belt, for example as a result of disturbances can be considered in this way without detriment to the surface quality of the hot dip coated strip.

Gute Ergebnisse bei der Durchführung des Verfahrens wurden erzielt, wenn eine Oxidschicht mit einer Dicke von maximal 300 Nanometer erzeugt wird.Good results have been achieved in carrying out the method when an oxide layer with a maximum thickness of 300 nanometers is produced.

Als Legierungsbestandteile sollte der höherfeste Stahl mindestens eine Auswahl folgender Bestandteile enthalten: Mn > 0,5%, Al > 0,2%, Si >0,1%, Cr > 0,3%. Weitere Bestandteile wie z.B. Mo, Ni, V, Ti, Nb und P können beigefügt werden.As alloying constituents, the high-strength steel should contain at least one of the following constituents: Mn> 0.5%, Al> 0.2%, Si> 0.1%, Cr> 0.3%. Other components such as Mo, Ni, V, Ti, Nb and P can be added.

Ein wesentliches Charakteristikum der Erfindung ist, dass die Wärmebehandlung des Bandes in der reduzierenden Atmosphäre sowohl beim Aufwärmen als auch späteren Glühen im Vergleich zur Wärmebehandlung in der oxidierenden Atmosphäre um ein Vielfaches länger dauert. Das führt dazu, dass das Volumen der oxidierenden Atmosphäre im Vergleich zum übrigen Volumen der reduzierenden Atmosphäre sehr klein ist. Das hat den Vorteil, dass auf Veränderungen des Behandlungsprozesses, insbesondere der Durchlaufgeschwindigkeit und der Bildung der Oxidationsschicht schnell reagiert werden kann. In diesem Sinne erfolgt die Wärmebehandlung des Bandes in der reduzierenden Atmosphäre in einem Durchlaufofen mit einer integrierten Kammer mit der oxidierenden Atmosphäre, wobei das Volumen der Kammer zu dem übrigen Volumen des Durchlaufofens um ein Vielfaches kleiner ist.An essential feature of the invention is that the heat treatment of the strip in the reducing atmosphere takes much longer in both the warm-up and the subsequent annealing as compared to the heat treatment in the oxidizing atmosphere. As a result, the volume of the oxidizing atmosphere is very small compared to the remaining volume of the reducing atmosphere. This has the advantage that it is possible to react quickly to changes in the treatment process, in particular the throughput speed and the formation of the oxidation layer. In this sense, the heat treatment of the strip takes place in the reducing atmosphere in a continuous furnace with an integrated chamber with the oxidizing atmosphere, wherein the volume of the chamber to the remaining volume of the continuous furnace is many times smaller.

Das erfindungsgemäße Verfahren ist besonders gut für das Feuerverzinken geeignet. Das Schmelzbad kann aber auch aus Zink-Aluminium oder Aluminium mit Silizium-Zusätzen bestehen. In jedem Fall, ob Zink oder Aluminium allein oder gemeinsam, sollte deren Anteil an der Schmelze in der Summe mindestens 85% ausmachen. Dafür bekannte, charakteristische Überzüge sind z.B. :

  • Z: 99%Zn
  • ZA: 95%Zn + 5%Al
  • AZ: 55%Al + 43,4%Zn + 1,6%Si
  • AS: 89-92%Al + 8-11%Si
The inventive method is particularly well suited for hot dip galvanizing. The molten bath may also consist of zinc-aluminum or aluminum with silicon additives. In any case, whether zinc or aluminum alone or together, their share in the melt should total at least 85%. Known, characteristic coatings are for example:
  • Z: 99% Zn
  • ZA: 95% Zn + 5% Al
  • AZ: 55% Al + 43.4% Zn + 1.6% Si
  • AS: 89-92% Al + 8-11% Si

Im Falle eines Zinküberzugs (Z) kann dieser durch Wärmebehandlung (Diffusionsglühen) in eine verformungsfähige Zink-Eisenschicht (galvanealed Überzug) umgewandelt werden.In the case of a zinc coating (Z), this can be converted by heat treatment (diffusion annealing) in a ductile zinc-iron layer (galvanized coating).

Im folgenden wird die Erfindung anhand einer Skizze näher erläutert, die eine Verzinkungsanlage mit einem Durchlaufofen schematisch zeigt, wobei für den Durchlaufofen über der Durchlaufzeit die Temperatur aufgetragen ist.In the following the invention will be explained in more detail with reference to a sketch which schematically shows a galvanizing plant with a continuous furnace, wherein the temperature is plotted for the continuous furnace over the cycle time.

Ein warmgewalztes oder kaltgewalztes Band 1 aus höherfestem Stahl mit Gehalten an Mn, Al, Si und Cr oder einigen dieser Legierungsbestandteile, gegebenenfalls aber auch mit weiteren Legierungsbestandteilen, insbesondere TRIP-Stahl, wird von einem Coil 2 abgezogen und durch eine Beize 3 und/oder eine andere Anlage 4 zur Oberflächenreinigung geleitet. Das gereinigte Band 1 gelangt dann in einen Durchlaufofen 5. Aus dem Durchlaufofen 5 gelangt das Band 1 über eine zur Atmosphäre abgeschlossene Schleuse 6 in ein Schmelztauchbad 7 mit Zink. Von dort gelangt es über eine Kühlstrecke 8 oder eine Einrichtung zur Wärmebehandlung zu einer Aufwickelstation 9 in Form eines Coils. Anders als in der Skizze dargestellt, durchläuft das Band 1 in Wirklichkeit nicht in gerader Linie den Durchlaufofen 5, sondern mäanderförmig, um bei praktikabler Länge des Durchlaufofens 5 ausreichend lange Behandlungszeiten erreichen zu können.A hot-rolled or cold-rolled strip 1 of high-strength steel with contents of Mn, Al, Si and Cr or some of these alloying constituents, but optionally also with other alloying constituents, in particular TRIP steel, is drawn off from a coil 2 and through a pickling 3 and / or passed another unit 4 for surface cleaning. The cleaned belt 1 then passes into a continuous furnace 5. From the continuous furnace 5, the belt 1 passes through a locked to the atmosphere lock 6 in a hot dip 7 with zinc. From there it passes via a cooling section 8 or a device for heat treatment to a winding station 9 in the form of a coil. Unlike shown in the diagram, the band 1 in reality does not run in a straight line through the continuous furnace 5, but meandering, in order to achieve sufficiently long treatment times at practical length of the continuous furnace 5 can.

Der Durchlaufofen 5 ist in drei Zonen 5a, 5b, 5c aufgeteilt. Die mittlere Zone 5b bildet eine Reaktionskammer und ist gegenüber der ersten und letzten Zone 5a, 5c atmosphärisch abgeschlossen. Ihre Länge beträgt nur etwa 1/100 der gesamten Länge des Durchlaufofens 5. Aus Gründen der besseren Darstellung ist die Zeichnung insoweit nicht maßstabgerecht. Entsprechend der unterschiedlichen Längen der Zonen sind auch die Behandlungszeiten des durchlaufenden Bandes 1 in den einzelnen Zonen 5a, 5b, 5c unterschiedlich.The continuous furnace 5 is divided into three zones 5a, 5b, 5c. The middle zone 5b forms a reaction chamber and is atmospherically closed with respect to the first and last zones 5a, 5c. Their length is only about 1/100 of the total length of the continuous furnace 5. For better illustration, the drawing is not to scale extent. According to the different lengths of the zones and the treatment times of the continuous belt 1 in the individual zones 5a, 5b, 5c are different.

In der ersten Zone 5a herrscht eine reduzierende Atmosphäre. Eine typische Zusammensetzung dieser Atmosphäre besteht aus 2% bis 8% H2 und Rest N2. In dieser Zone 5a des Durchlaufofens 1 erfolgt eine Erwärmung des Bandes auf 650 bis 750°C. Bei dieser Temperatur diffundieren die genannten Legierungsbestandteile in nur geringen Mengen an die Oberfläche des Bandes 1.In the first zone 5a there is a reducing atmosphere. A typical composition of this atmosphere consists of 2% to 8% H 2 and balance N 2 . In this zone 5a of the continuous furnace 1, the strip is heated to 650 to 750 ° C. At this temperature, the stated alloying constituents diffuse only in small amounts to the surface of the strip 1.

In der mittleren Zone 5b wird die Temperatur der ersten Zone 5a im wesentlichen nur gehalten. Ihre Atmosphäre ist aber sauerstoffhaltig. Der O2-Gehalt liegt zwischen 0,01% bis 1%. Er kann eingestellt werden. Er hängt davon ab, wie lang die Behandlungszeit ist. Ist die Behandlungszeit kurz, ist der O2-Gehalt hoch, während er bei langer Behandlungszeit gering ist. Bei dieser Behandlung bildet sich an der Oberfläche des Bandes eine Eisenoxidschicht. Die Dicke dieser Eisenoxidschicht kann durch optische Mittel gemessen werden. In Abhängigkeit von der gemessenen Dicke und der Durchlaufgeschwindigkeit wird der O2-Gehalt der Atmosphäre eingestellt. Da die mittlere Zone 5b im Vergleich zur gesamten Ofenlänge sehr kurz ist, ist das Kammervolumen entsprechend klein. Deshalb ist die Reaktionszeit für eine Änderung der Zusammensetzung der Atmosphäre klein.In the middle zone 5b, the temperature of the first zone 5a is essentially kept only. Their atmosphere is oxygenated. The O 2 content is between 0.01% to 1%. He can be hired. It depends on how long the treatment time is. If the treatment time is short, the O 2 content is high, while it is low with long treatment time. In this treatment, an iron oxide layer is formed on the surface of the belt. The thickness of this iron oxide layer can be measured by optical means. Depending on the measured thickness and the flow rate of the O 2 content the atmosphere set. Since the central zone 5b is very short in comparison to the entire furnace length, the chamber volume is correspondingly small. Therefore, the reaction time for a change in the composition of the atmosphere is small.

In der anschließenden letzten Zone 5c findet eine weitere Erwärmung bis auf ca. 900°C statt, bei der das Band 1 geglüht wird. Diese Wärmebehandlung erfolgt in einer reduzierenden Atmosphäre mit einem H2-Gehalt von 2% bis 8% und Rest N2. Während dieser Glühbehandlung verhindert die Eisenoxidschicht, dass Legierungsbestandteile an die Bandoberfläche diffundieren. Da die Glühbehandlung in einer reduzierenden Atmosphäre erfolgt, wird die Eisenoxidschicht in eine Reineisenschicht umgewandelt. Das Band 1 wird dabei auf seinem weiteren Weg in Richtung des Schmelztauchbades 7 weiter abgekühlt, so dass es bei Verlassen des Durchlaufofens 5 etwa die Temperatur des Schmelztauchbades 7 von etwa 480°C hat. Da das Band 1 nach Verlassen des Durchlaufofens 5 an seiner Oberfläche aus Reineisen besteht, bietet es für das Zink des Schmelztauchbades 7 eine optimale Grundlage für eine haftfeste Verbindung.In the subsequent last zone 5c, a further heating up to about 900 ° C takes place, in which the strip 1 is annealed. This heat treatment is carried out in a reducing atmosphere with an H 2 content of 2% to 8% and balance N 2 . During this annealing treatment, the iron oxide layer prevents alloying constituents from diffusing to the strip surface. Since the annealing treatment takes place in a reducing atmosphere, the iron oxide layer is converted into a pure iron layer. The strip 1 is further cooled on its further way in the direction of the hot dip bath 7, so that when leaving the continuous furnace 5, it has about the temperature of the hot dip bath 7 of about 480 ° C. Since the strip 1 is made of pure iron after leaving the continuous furnace 5 on its surface, it provides the zinc of the hot-dip bath 7 an optimal basis for a strong bond.

Claims (5)

  1. Process for melt dip coating a strip of higher-tensile steel with various alloy constituents, in particular Mn, Al, Si and/or Cr, in a molten bath of in total at least 85% zinc and/or aluminium in a through-feed method involving the following process steps and conditions:
    a) the strip is heated in a reductive atmosphere having an H2 content of at least 2% to 8% to a temperature of from 650°C to 750°C within at most 250 sec, at which the alloy constituents have not yet diffused to the surface or have done so merely in small amounts;
    b) the surface, consisting predominantly of pure iron, is converted into an iron oxide layer by heat treatment, lasting from 1 to 10 sec, of the strip at a temperature of from 650°C to 750°C in a reaction chamber which is integrated in the continuous furnace and has an oxidising atmosphere having an O2 content of from 0.01% to 1%;
    c) the strip is then annealed in a reductive atmosphere having an H2 content of from 2% to 8% by further heating up to at most 900°C and then cooled down to the temperature of the molten bath, in order to reduce the iron oxide layer to pure iron at least at its surface, wherein further heating up with subsequent cooling down of the strip lasts longer than 50 sec.
    d) the heat treatment of the strip in the reductive atmosphere lasts longer by a multiple, during both the heating process (Work step a)) and the subsequent annealing (Work step c)), compared to the heat treatment in the oxidising atmosphere (Work step b)).
  2. Process according to claim 1, characterised in that the iron oxide layer produced is reduced completely to pure iron.
  3. Process according to claim 1 or 2, characterised in that
    the higher-tensile steel contains at least a selection of the following alloy constituents: Mn > 0.5%, Al > 0.2%, Si > 0.1%, Cr > 0.3%.
  4. Process according to any one of claims 1 to 3,
    characterised in that the heat treatment of the strip in the reductive atmosphere is carried out in a continuous furnace with an integrated chamber having the oxidising atmosphere, the volume of the chamber being smaller by a multiple than the remaining volume of the continuous furnace.
  5. Process according to any one of claims 1 to 4,
    characterised in that the strip is heat-treated after the hot dip galvanising process.
EP05812469A 2004-12-09 2005-12-02 Method for hot dip coating a strip of heavy-duty steel Expired - Lifetime EP1819840B1 (en)

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DE102004059566A DE102004059566B3 (en) 2004-12-09 2004-12-09 Process for hot dip coating a strip of high strength steel
PCT/EP2005/012942 WO2006061151A1 (en) 2004-12-09 2005-12-02 Method for hot dip coating a strip of heavy-duty steel

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CN101103133B (en) 2011-04-20
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BRPI0518623A2 (en) 2008-12-02
CN101103133A (en) 2008-01-09

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