EP3710605B1 - Method for the preoxidation of strip steel in a reaction chamber arranged in a furnace chamber - Google Patents

Method for the preoxidation of strip steel in a reaction chamber arranged in a furnace chamber Download PDF

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Publication number
EP3710605B1
EP3710605B1 EP18807218.5A EP18807218A EP3710605B1 EP 3710605 B1 EP3710605 B1 EP 3710605B1 EP 18807218 A EP18807218 A EP 18807218A EP 3710605 B1 EP3710605 B1 EP 3710605B1
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Prior art keywords
reaction chamber
gas
strip
furnace
atmosphere
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EP18807218.5A
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German (de)
French (fr)
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EP3710605A1 (en
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Frank Maschler
Lutz Kümmel
Jean-Pierre Crutzen
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SMS Group GmbH
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SMS Group 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
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • 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
    • C21D1/767—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material with forced gas circulation; Reheating thereof
    • 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
    • C21D8/0447—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 characterised by the heat treatment
    • C21D8/0457—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 characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
    • 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
    • C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
    • 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
    • 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
    • C23C2/04—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
    • C23C2/34—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
    • 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
    • C23C2/50—Controlling or regulating the coating processes
    • 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
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • 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
    • C23C8/80—After-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
    • 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
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0257—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding

Definitions

  • the invention relates to an improved process for the pre-oxidation of oxidation-sensitive strip steel in a reaction chamber arranged in a furnace chamber, in order to set the surface properties of the strip steel to be coated that are suitable for hot-dip coating that follows immediately thereafter.
  • the reaction chamber has a strongly oxidizing atmosphere inside, in the furnace chamber of a continuous furnace with a hydrogen-containing, reducing atmosphere, the strip inlet and strip outlet in the reaction chamber must be sealed against gas exchange as best as possible.
  • a gas transfer from the furnace into the reaction chamber causes the penetrating hydrogen to at least partially consume the oxygen required for oxidation and impairs the nature of the desired oxide layer on the strip surface. This problem is exacerbated the lower the oxygen content in the reaction chamber.
  • gas transfer from the reaction chamber into the furnace causes a higher water content (dew point) in the furnace and thus an increased oxidation potential. This is particularly disadvantageous for high-strength steels with a higher proportion of alloying elements with an affinity for oxygen.
  • the pamphlets WO 2016/177590 A1 , WO 2012/152508 A1 and DE 10 2011 051731 A1 disclose processes for the pre-oxidation of steel strips in a reaction chamber arranged in a furnace space.
  • the temperature of the strip is the decisive parameter for process control when setting a desired oxide layer. This is preferably between 650 and 750°C. As long as the oxygen content is > 1% and the treatment time > 1 s, their influence on the thickness of the oxide layer formed is negligibly small. An insensitive process can be assumed for oxygen contents in the range of 2 to 5%.
  • this object is achieved by the features specified in claim 1, in particular in that the reaction chamber is sealed at a belt inlet and a belt outlet against gas exchange between the furnace space and the reaction chamber and a gas that creates an oxidizing atmosphere in the reaction chamber is formed, introduced and the gas is permanently circulated within the reaction chamber in a closed circuit, and its composition is regulated and losses due to leaks and consumption are compensated for, with at least one nozzle system assigned to the reaction chamber being controlled and evenly distributed with the gas having a high kinetic energy density with the aid of Nitrogen as a carrier gas is fed to the surface of the strip steel to make it laminar To avoid boundary layer effects on the strip surface and to assign a vent to the reaction chamber to compensate for changes in volume, the vent is preferably regulated in such a way that the internal pressure of the reaction chamber corresponds to the pressure of the surrounding furnace atmosphere and the gas exchange via unavoidable leaks is thus kept to a minimum.
  • the reaction chamber is generally sealed towards the furnace space and in particular at the strip inlet and strip outlet against gas exchange.
  • the atmosphere is constantly changing. To do this, the gas is sucked out of the reaction chamber, cooled, fed to a fan, enriched with fresh air and fed back into the chamber. This achieves a good homogeneity of the atmosphere.
  • a further desired effect is that via nozzle systems (at least one nozzle system) gas with a high kinetic energy density is fed to the strip surface in a controlled and uniform manner with the aid of nitrogen as a carrier gas. This is necessary to avoid laminar boundary layer effects.
  • the oxygen content of the atmosphere in the reaction chamber is a minimum of 1.5 and a maximum of 5% by volume.
  • the reaction chamber has a vent to compensate for changes in volume.
  • This vent is preferably regulated in such a way that the internal pressure of the reaction chamber corresponds to the pressure of the surrounding furnace atmosphere and the gas exchange via the unavoidable leaks is thus minimal.
  • the oxidation-sensitive steel can contain at least a selection of the following alloy components: Mn > 0.5%, Al > 0.2%, Si > 0.1%, Cr > 0.3%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Coating With Molten Metal (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)

Description

Die Erfindung betrifft ein verbessertes Verfahren zur Voroxidation von oxidationsempfindlichem Bandstahl in einer in einem Ofenraum angeordneten Reaktionskammer, um hierdurch für eine sich unmittelbar daran anschließende Schmelztauchbeschichtung geeignete Oberflächeneigenschaften des zu beschichtenden Bandstahls einzustellen.The invention relates to an improved process for the pre-oxidation of oxidation-sensitive strip steel in a reaction chamber arranged in a furnace chamber, in order to set the surface properties of the strip steel to be coated that are suitable for hot-dip coating that follows immediately thereafter.

Übliche hochfeste Bandstähle enthalten als Legierungselemente Mangan, Silicium und /oder Aluminium. Während der möglichen rekristallisierenden Glühung vor der Schmelztauchbeschichtung diffundieren diese Legierungselemente zur Bandoberfläche hin. Da diese Legierungselemente sehr sauerstoffaffin sind, werden sie, soweit sie sich an der Bandoberfläche bzw. in geringer Tiefe im Band befinden, nahezu unvermeidlich oxidiert. Das Grundmaterial Eisen wird dabei allerdings nicht oxidiert. Dieses Phänomen ist auch als selektive Oxidation bekannt. Die an der Oberfläche durch die selektive Oxidation gebildeten Mangan-, Silicium-, und/oder Aluminiumoxide beeinträchtigen jedoch die Benetzbarkeit der Bandoberfläche mit einem schmelzflüssigen Überzugsmetall (beispielsweise Zink), mit der Folge von Fehlstellen (sog. bare spots) bzw. einer schlechten Haftung des Überzugs mit der Bandoberfläche, wobei für die Beschichtungsprobleme am hochfesten Stahl die Legierungszusammensetzung maßgeblich ist, vor allem die Neigung zur Bildung nicht reduzierbarer Oxide an der Oberfläche.Conventional high-strength strip steels contain manganese, silicon and/or aluminum as alloying elements. During possible recrystallizing annealing prior to hot dip coating, these alloying elements diffuse towards the strip surface. Since these alloying elements have a high affinity for oxygen, they are almost inevitably oxidized if they are on the strip surface or at a small depth in the strip. However, the base material iron is not oxidized in the process. This phenomenon is also known as selective oxidation. However, the manganese, silicon and/or aluminum oxides formed on the surface as a result of the selective oxidation impair the wettability of the strip surface with a molten coating metal (e.g. zinc), resulting in defects (so-called bare spots) or poor adhesion of the coating with the strip surface, with the alloy composition being decisive for the coating problems on high-strength steel, above all the tendency to form irreducible oxides on the surface.

Das betrifft beispielsweise folgende Stahlqualitäten: Gruppe C max [%] Si max [%] Mn max [%] Cr+Mo max [%] DP 0,14 - 0,23 0,5 - 1,0 1,8 - 2,9 1,0 - 1,4 CP 0,18 - 0,23 1,0 2,5 - 2,9 1,0 TRIP 0,23 - 0,25 1,8 - 2,2 2,1 - 2,5 0,2 Q&P 0,10 - 0,30 1,0 - 2,0 1,5 - 3,0 This applies to the following steel qualities, for example: group C max [%] Si max [%] Mn max [%] Cr+Mo max [%] DP 0.14 - 0.23 0.5 - 1.0 1.8 - 2.9 1.0 - 1.4 CP 0.18 - 0.23 1.0 2.5 - 2.9 1.0 TRIP 0.23 - 0.25 1.8 - 2.2 2.1 - 2.5 0.2 Q&P 0.10 - 0.30 1.0 - 2.0 1.5 - 3.0

Um die Haftung des Überzugs an der Bandoberfläche zu verbessern, ist in der DE 102 004 059 566 ein Verfahren beschrieben, bei dem das Band voroxidiert wird. Das in dieser Druckschrift beschriebene Verfahren kann wie folgt zusammengefasst wert den:

  1. 1. Erwärmen des Bandes unter reduzierender Atmosphäre, mit 2 bis 3 % Wasserstoffanteil, bis auf 650 bis 750°C;
  2. 2. Oxidieren der weitgehend aus Reineisen bestehenden Bandoberfläche in einer Reaktionskammer mit einer Atmosphäre mit 0,01 bis 1 % Sauerstoffanteil. Dabei wird eine Eisenoxidschicht gebildet, welche die vorher gebildeten Legierungsoxide abdeckt. Die Behandlungsdauer soll 1 bis 10 sec und die Dicke der gebildeten Oxidschicht soll 300 nm betragen;
  3. 3. Glühen des Bandstahls unter reduzierender Atmosphäre mit 2 bis 8% Wasserstoffanteil bis auf maximal 900°C. Dabei wird die Eisenoxidschicht wieder zu Reineisen reduziert, auf der dann das Überzugsmetall gut und sicher haftet.
In order to improve the adhesion of the coating to the belt surface, DE 102 004 059 566 describes a process in which the strip is pre-oxidized. The process described in this publication can be summarized as follows:
  1. 1. Heating of the strip under a reducing atmosphere, with 2 to 3% hydrogen content, up to 650 to 750°C;
  2. 2. Oxidation of the strip surface, which consists largely of pure iron, in a reaction chamber with an atmosphere containing 0.01 to 1% oxygen. In the process, an iron oxide layer is formed which covers the previously formed alloy oxides. The treatment time should be 1 to 10 seconds and the thickness of the oxide layer formed should be 300 nm;
  3. 3. Annealing of the strip steel in a reducing atmosphere with 2 to 8% hydrogen content up to a maximum of 900°C. The iron oxide layer is reduced back to pure iron, to which the coating metal then adheres well and securely.

Dabei befindet sich die Reaktionskammer mit einer im Innern stark oxidierenden Atmosphäre, im Ofenraum eines Durchlaufofens mit einer wasserstoffhaltigen, reduzierenden Atmosphäre, Bandeinlauf und Bandauslauf in die Reaktionskammer müssen bestmöglich gegen Gasaustausch abgedichtet sein. Ein Gasübertritt vom Ofen in die Reaktionskammer bewirkt, dass der eindringende Wasserstoff den zur Oxidation benötigten Sauerstoff zumindest teilweise verbraucht und die Beschaffenheit der angestrebten Oxidschicht auf der Bandoberfläche beeinträchtigt. Dieses Problem verschärft sich, je geringer der Sauerstoffgehalt in der Reaktionskammer ist. Umgekehrt bewirkt ein Gasübertritt aus der Reaktionskammer in den Ofen einen höheren Wassergehalt (Taupunkt) im Ofen und dadurch ein erhöhtes Oxidationspotential. Dieses ist insbesondere für höchstfeste Stähle mit einem höheren Anteil an sauerstoffaffinen Legierungselementen nachteilig.The reaction chamber has a strongly oxidizing atmosphere inside, in the furnace chamber of a continuous furnace with a hydrogen-containing, reducing atmosphere, the strip inlet and strip outlet in the reaction chamber must be sealed against gas exchange as best as possible. A gas transfer from the furnace into the reaction chamber causes the penetrating hydrogen to at least partially consume the oxygen required for oxidation and impairs the nature of the desired oxide layer on the strip surface. This problem is exacerbated the lower the oxygen content in the reaction chamber. Conversely, gas transfer from the reaction chamber into the furnace causes a higher water content (dew point) in the furnace and thus an increased oxidation potential. This is particularly disadvantageous for high-strength steels with a higher proportion of alloying elements with an affinity for oxygen.

Die Druckschriften WO 2016/177590 A1 , WO 2012/152508 A1 und DE 10 2011 051731 A1 offenbaren Verfahren zur Voroxidation von Stahlbändern in einer in einem Ofenraum angeordneten Reaktionskammer.The pamphlets WO 2016/177590 A1 , WO 2012/152508 A1 and DE 10 2011 051731 A1 disclose processes for the pre-oxidation of steel strips in a reaction chamber arranged in a furnace space.

Versuche haben ergeben, dass zur Einstellung einer gewünschten Oxidschicht die Bandtemperatur der zur Prozessführung entscheidende Parameter ist. Diese liegt vorzugsweise zwischen 650 und 750°C. Solange dabei der Sauerstoffgehalt > 1% und die Behandlungszeit > 1 s sind, ist deren Einfluss auf die Dicke der gebildeten Oxidschicht vernachlässigbar klein. Bei Sauerstoffgehalten im Bereich 2 bis 5% kann von einem unempfindlichen Prozess ausgegangen werden.Experiments have shown that the temperature of the strip is the decisive parameter for process control when setting a desired oxide layer. This is preferably between 650 and 750°C. As long as the oxygen content is > 1% and the treatment time > 1 s, their influence on the thickness of the oxide layer formed is negligibly small. An insensitive process can be assumed for oxygen contents in the range of 2 to 5%.

Es ist daher Aufgabe der vorliegenden Erfindung, ein verbessertes Verfahren zur Voroxidation von hochfestem Bandstahl in einer Reaktionskammer innerhalb eines Ofenraums während der rekristallisierenden Glühung vor einer Schmelztauchbeschichtung zur Verfügung zu stellen.It is therefore an object of the present invention to provide an improved process for the pre-oxidation of high-strength strip steel in a reaction chamber within a furnace space during recrystallizing annealing prior to hot-dip coating.

Nach der Lehre der Erfindung wird diese Aufgabe durch die im Anspruch 1 angegebenen Merkmale gelöst, insbesondere dadurch, dass die Reaktionskammer an einem Bandeintritt und einem Bandaustritt gegen Gasaustausch zwischen dem Ofenraum und der Reaktionskammer abgedichtet wird und ein Gas, das eine oxidierende Atmosphäre in der Reaktionskammer ausbildet, eingeleitet und das Gas innerhalb der Reaktionskammer in einem geschlossenen Kreislauf permanent umgewälzt wird, und dessen Zusammensetzung geregelt und Verluste durch Leckagen und Verbrauch ausgeglichen werden, wobei über mindestens ein der Reaktionskammer zugeordnetes Düsensystem kontrolliert und gleichmäßig das Gas mit hoher kinetischer Energiedichte unter Zuhilfenahme von Stickstoff als Trägergas der Oberfläche des Bandstahls zugeführt wird, um laminare Grenzschichteffekte an der Bandoberfläche zu vermeiden und der Reaktionskammer zum Ausgleich von Volumenänderungen ein Abzug zugeordnet wird, der Abzug vorzugsweise so geregelt wird, dass der Innendruck der Reaktionskammer dem Druck der umgebenden Ofenatmosphäre entspricht und so der Gasaustausch über unvermeidliche Undichtigkeiten minimal gehalten wird.According to the teaching of the invention, this object is achieved by the features specified in claim 1, in particular in that the reaction chamber is sealed at a belt inlet and a belt outlet against gas exchange between the furnace space and the reaction chamber and a gas that creates an oxidizing atmosphere in the reaction chamber is formed, introduced and the gas is permanently circulated within the reaction chamber in a closed circuit, and its composition is regulated and losses due to leaks and consumption are compensated for, with at least one nozzle system assigned to the reaction chamber being controlled and evenly distributed with the gas having a high kinetic energy density with the aid of Nitrogen as a carrier gas is fed to the surface of the strip steel to make it laminar To avoid boundary layer effects on the strip surface and to assign a vent to the reaction chamber to compensate for changes in volume, the vent is preferably regulated in such a way that the internal pressure of the reaction chamber corresponds to the pressure of the surrounding furnace atmosphere and the gas exchange via unavoidable leaks is thus kept to a minimum.

Auf diese Weise ist es möglich, eine besonders gleichmäßig ausgebildete Oxidschicht auf der Bandoberfläche zu erzeugen, sodass Fehlstellen bei der sich anschließenden Schmelztauchbeschichtung vermieden werden und so die Qualität des Endprodukts verbessert und Ausschuss verringert wird.In this way, it is possible to produce a particularly uniform oxide layer on the surface of the strip, so that defects are avoided during the subsequent hot-dip coating, thus improving the quality of the end product and reducing rejects.

Die Reaktionskammer ist grundsätzlich zum Ofenraum hin und insbesondere am Bandeintritt und Bandaustritt gegen Gasaustausch abgedichtet.The reaction chamber is generally sealed towards the furnace space and in particular at the strip inlet and strip outlet against gas exchange.

Die Atmosphäre wird permanent umgewälzt. Das Gas wird dazu aus der Reaktionskammer abgesaugt, gekühlt, einem Ventilator zugeführt, mit frischer Luft angereichert und wieder in die Kammer eingespeist. Damit wird eine gute Homogenität der Atmosphäre erreicht.The atmosphere is constantly changing. To do this, the gas is sucked out of the reaction chamber, cooled, fed to a fan, enriched with fresh air and fed back into the chamber. This achieves a good homogeneity of the atmosphere.

Ein weiterer gewünschter Effekt ist, dass über Düsensysteme (mindestens ein Düsensystem) kontrolliert und gleichmäßig Gas mit hoher kinetischer Energiedichte unter Zuhilfenahme von Stickstoff als Trägergas der Bandoberfläche zugeführt wird. Das ist notwendig, um laminare Grenzschichteffekte zu vermeiden.A further desired effect is that via nozzle systems (at least one nozzle system) gas with a high kinetic energy density is fed to the strip surface in a controlled and uniform manner with the aid of nitrogen as a carrier gas. This is necessary to avoid laminar boundary layer effects.

Um einen ausreichenden Puffer gegen eindringenden Wasserstoff zu erreichen, beträgt der Sauerstoffgehalt der Atmosphäre in der Reaktionskammer minimal 1,5 bis maximal 5 vol%.In order to achieve a sufficient buffer against the ingress of hydrogen, the oxygen content of the atmosphere in the reaction chamber is a minimum of 1.5 and a maximum of 5% by volume.

Zum Ausgleich von Volumenänderungen besitzt die Reaktionskammer einen Abzug. Vorzugsweise wird dieser Abzug so geregelt, dass der Innendruck der Reaktionskammer dem Druck der umgebenden Ofenatmosphäre entspricht und so der Gasaustausch über die unvermeidlichen Undichtigkeiten minimal ist.The reaction chamber has a vent to compensate for changes in volume. This vent is preferably regulated in such a way that the internal pressure of the reaction chamber corresponds to the pressure of the surrounding furnace atmosphere and the gas exchange via the unavoidable leaks is thus minimal.

Durch diese Maßnahmen wird ein gutmütig beherrschbarer Oxidationsprozess erreicht und eine Beeinträchtigung der die Reaktionskammer umgebenden Ofenatmosphäre wird verhindert.Through these measures, an easily controllable oxidation process is achieved and an impairment of the furnace atmosphere surrounding the reaction chamber is prevented.

Der oxidationsempfindliche Stahl kann mindestens eine Auswahl folgender Legierungsbestandteile enthalten: Mn > 0,5%, Al > 0,2%, Si > 0,1%, Cr > 0,3%.The oxidation-sensitive steel can contain at least a selection of the following alloy components: Mn > 0.5%, Al > 0.2%, Si > 0.1%, Cr > 0.3%.

Claims (1)

  1. Method for pre-oxidation of oxidation-sensitive steel strip in a reaction chamber arranged in a furnace chamber, preferably between 650 and 750° C, wherein then the oxygen content > 1% and the treatment time > 1 s, characterised in that the reaction chamber is sealed at a strip entrance and a strip exit against gas exchange between the furnace chamber and the reaction chamber and a gas which forms an oxidising atmosphere in the reaction chamber is introd uced and is continuously circulated inside the reaction chamber in a closed circuit, wherein the composition of the gas is regulated and compensation is provided for losses due to leakages and consumption,
    wherein the oxidising gas is evacuated from the reaction chamber, cooled, fed to a fan, enriched with air and fed back into the reaction chamber in order to achieve a good homogeneity of the atmosphere,
    wherein the gas is supplied to the strip surface with high kinetic energy density in a controlled and uniform manner via at least one nozzle system, which is associated with the reaction chamber, with the aid of nitrogen as carrier gas in order to avoid laminar boundary layer effects at the strip surface,
    the oxygen content of the atmosphere in the reaction chamber is kept at a minimum of 1.5 to a maximum of 5 vol % in order to thereby achieve a sufficient buffer against hydrogen ingress from the furnace chamber into the reaction chamber wherein a vent is assigned to the reaction chamber to compensate for changes in volume,
    wherein the vent is preferably regulated so that the internal pressure of the reaction chamber corresponds with the pressure of the furnace ambient atmosphere and thus gas exchange due to inevitable leaks is kept to a minimum and
    wherein the oxidation-sensitive steel contains at least one selection from the following alloying components: Mn > 0.5%, Al > 0.2%, Si > 0.1%, Cr > 0.3%.
EP18807218.5A 2017-11-17 2018-11-06 Method for the preoxidation of strip steel in a reaction chamber arranged in a furnace chamber Active EP3710605B1 (en)

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DE102017220583 2017-11-17
DE102018107435.2A DE102018107435A1 (en) 2017-11-17 2018-03-28 Process for the pre-oxidation of strip steel in a reaction chamber arranged in a furnace chamber
PCT/EP2018/080242 WO2019096616A1 (en) 2017-11-17 2018-11-06 Method for the preoxidation of strip steel in a reaction chamber arranged in a furnace chamber

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EP3816319B1 (en) * 2019-10-29 2022-09-14 Salzgitter Flachstahl GmbH Method for producing a high strength steel strip with improved adhesion of zinc-based hot dip coatings
CN114855108A (en) * 2022-05-24 2022-08-05 山东钢铁集团日照有限公司 Control method for surface plating leakage and zinc ash defects of high-aluminum-silicon-manganese galvanized dual-phase steel

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DE102004059566B3 (en) 2004-12-09 2006-08-03 Thyssenkrupp Steel Ag Process for hot dip coating a strip of high strength steel
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DE102011050243A1 (en) * 2011-05-10 2012-11-15 Thyssenkrupp Steel Europe Ag Apparatus and method for the continuous treatment of a flat steel product
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CN107532270B (en) * 2015-04-22 2019-08-20 考克利尔维修工程 Method and device for reaction controlling
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