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EP1693477A1 - Coated steel plate - Google Patents

Coated steel plate Download PDF

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Publication number
EP1693477A1
EP1693477A1 EP05003762A EP05003762A EP1693477A1 EP 1693477 A1 EP1693477 A1 EP 1693477A1 EP 05003762 A EP05003762 A EP 05003762A EP 05003762 A EP05003762 A EP 05003762A EP 1693477 A1 EP1693477 A1 EP 1693477A1
Authority
EP
European Patent Office
Prior art keywords
coating
steel
weight
strip
melt
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.)
Withdrawn
Application number
EP05003762A
Other languages
German (de)
French (fr)
Inventor
Manfred Meurer
Wilhelm Dr. Warnecke
Rudolf Schönenberg
Sabine Zeizinger
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.)
ThyssenKrupp Steel Europe AG
Original Assignee
ThyssenKrupp Steel AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ThyssenKrupp Steel AG filed Critical ThyssenKrupp Steel AG
Priority to EP05003762A priority Critical patent/EP1693477A1/en
Priority to ES06724846.8T priority patent/ES2650741T3/en
Priority to JP2007556589A priority patent/JP5270172B2/en
Priority to CN2006800056157A priority patent/CN101128614B/en
Priority to KR1020077021513A priority patent/KR101268570B1/en
Priority to PCT/EP2006/050955 priority patent/WO2006089854A1/en
Priority to AU2006218005A priority patent/AU2006218005B2/en
Priority to US11/816,799 priority patent/US20080142125A1/en
Priority to CA2596825A priority patent/CA2596825C/en
Priority to EP06724846.8A priority patent/EP1851352B8/en
Publication of EP1693477A1 publication Critical patent/EP1693477A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • 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
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates
    • 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
    • C23C2/30—Fluxes or coverings on molten baths
    • 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
    • C23C2/38—Wires; Tubes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

Definitions

  • the invention relates to a coated steel sheet or strip with a base layer consisting of steel, on whose at least one upper side by hot dip coating a zinc coating is applied.
  • the zinc coating ensures high corrosion resistance. This is the larger, the thicker the coating is.
  • the red test carried out on a bare, unpainted sample in accordance with DIN 50021 results in red rust already after 24 hours at a coating run of 25 g / m 2 , while red coating occurs at a coating application of 70 g / m 2 after 120 hours arises.
  • the thickness of the coating required in the prior art for sufficient corrosion resistance involves problems in weldability. This is especially true if, by means of laser welding at high welding speeds, a through-welding in the lap joint is to be produced without a minimum gap, as required, in particular, in the field of building automobile bodies or in the field of household technology.
  • the seam produced by such a weld should be free of through holes, have a substantial crater freedom and have no open pores.
  • the object of the invention was therefore to provide a flat steel product which has an optimum combination of high corrosion resistance and optimized weldability and which is particularly suitable for use as a material for automotive body construction or for the construction of household appliances.
  • a coated steel sheet or strip which has a base layer made of steel, on the at least one upper side of which a hot dip coating is applied, which consists of a layer of 0.05-0.30% by weight of Al and 0.2-2.0% by weight of Mg, balance zinc and unavoidable impurities existing melt is formed and each side with a coating thickness of at most 3.5 microns and a maximum coating weight of 25 g / m 2 ensures that the steel sheet shows the first formation of red rust at the earliest after 250 hours in the salt spray test carried out according to DIN 50021-SS.
  • a hot-dip-coated flat steel product according to the invention has surprisingly good corrosion resistance at a maximum coating weight of 25 g / m 2 per side, minimized in comparison with the prior art.
  • the low coating weight and the associated low thickness of the coating of a maximum of 3.5 microns each side in combination with the high corrosion resistance makes inventive sheet or strip particularly suitable for the production of components that are produced by welding of individual sheet metal elements.
  • elements for automobile bodies or home appliance technology can be produced with sheet steel produced according to the invention by welding the individual sheet metal parts formed from sheet metal or strip according to the invention by laser welding at high welding speeds economically and with optimum results.
  • the corrosion resistance of the invention is based on a salt spray test according to DIN 50021-SS in a Corrosion short-time test method on bare, unpainted steel sheet determined, in which a neutral 5% NaCl solution is continuously sprayed in a chamber at a temperature of 35 ⁇ 2 ° C as an attacking agent.
  • the steel sheet samples are placed in the chamber with an inclination angle of 65 to 75 ° to the horizontal. In practical tests carried out in this way, it has been found that sheets and strips coated according to the invention regularly show first red rust formation only after a test duration of 300 hours.
  • the magnesium content contained in the melt intended for the coating is found essentially unchanged in the coating.
  • the Al content of the coating in the finished steel strip according to the invention is generally 1.8 to 3.2, in particular 2 to 3 times, higher than in the melt.
  • Optimum corrosion protection is achieved if the coating has a Mg content of 0.4-1.0% by weight, in particular at least 0.5% by weight.
  • the melt preferably contains less than 0.15% by weight of aluminum. Practical Al contents of the melt in this case are in the range of 0.12-0.14% by weight.
  • the Al content of the melt is preferably at least 0.15% by weight.
  • a full-scale coating comprising a 20 ⁇ m thick cathodic dip coating, a 32 ⁇ m thick surfacer coat layer applied thereto and a 40 ⁇ m thick basecoat film was applied to a steel sheet sample after alkaline cleaning and phosphating.
  • the bending over the conical mandrel performed neither at room temperature nor at -20 ° C to a detachment of the paint layer.
  • sheets or tapes according to the invention have excellent resistance to stone chipping.
  • DIN 65996-1B it was possible to demonstrate that, in the case of steel sheets according to the invention, no flaking of the coating from the base layer is caused by rockfall.
  • a steel fine strip in a galvanizing plant which is traversed at a strip speed of typically 60 to 150 m / min, is subjected to a continuously running strip hot-dip galvanizing process.
  • This will be too galvanizing sheet or strip first in an oven, for example a DFF furnace (Direct Fired Furnace) or, preferably, a RTF furnace (Radiant Type Furnace) annealed. Following the oven, the sheet or strip passes through the reduction furnace section, where it is maintained under a protective gas atmosphere of 3.5-75% hydrogen.
  • the temperatures achieved during annealing are in the range of 720 - 850 ° C.
  • the thus annealed strip or sheet is then passed through a so-called proboscis under exclusion of air in the zinc bath, by a 0.05 to 0.30 wt .-% Al and 0.2 to 2.0 wt .-% Mg, in particular 0.4 to 1.0 wt .-% or 0.5 to 1.0 wt .-%, remainder zinc and unavoidable impurities containing melt is formed.
  • the thickness of the coating is limited in a conventional manner by means of stripping nozzles to a value of 3.5 microns maximum page, so that the resulting flat product according to the invention, the maximum coating weight of 25 g / m 2 per side is limited.
  • an inert gas stream may originate from the wiping nozzles used to adjust the coating thickness, or may be discharged from separate nozzles which disperse the inert gas over the bath surface.
  • the entire melt bath can be surrounded by an enclosure in which an inert atmosphere is maintained. Nitrogen is particularly suitable as inert gas for this purpose.
  • Slag formation can also be reduced by adjusting the bath temperature to a range of 380-450 ° C.
  • the belt temperature during immersion can be limited to 360 - 500 ° C in order to minimize the tendency to oxidation, especially in the immersion area.
  • the coated tape After exiting the melt bath, the coated tape is at a cooling rate of at least 10 K / s. cooled.
  • the melts used to produce such a layer preferably have an Al content of less than 0.15% by weight, in particular 0.12-0.14% by weight.
  • the thus annealed steel strip was then cooled so that it is immersed in the molten bath immersion temperature of 465 ° C in the molten bath held in an enclosure under a maximum of 10 ppm oxygen containing inert gas atmosphere.
  • the molten bath consisted of a Zn melt containing, in addition to unavoidable impurities (e.g., Fe levels being dragged through the belt into the molten bath), 0.2 wt% Al, 0.8 wt% Mg.
  • the dive time was two seconds.
  • the layer thickness of the coating applied on both sides of the steel strip has been adjusted within the Schmelzenbadeinhausung by means also arranged in the housing Abstreifdüsen to a coating thickness of 3 microns per side (corresponding to a weight of 21 g / m 2 each side) ,
  • the stripping was also done by means of nitrogen gas.
  • the steel band has been trained.
  • the resulting hot dip coated steel strip had Ra values of 1.8 ⁇ m at Pc values of 46 cm -1 determined according to SEP 1940 Steel Iron Test Sheet.
  • the samples taken from the finished coated steel strip were subjected to the ball impact test according to the steel-iron test sheet SEP 1931 was performed to determine the adhesion of the cover and its formability. The result could be assigned to the level 1, which corresponds to a good adhesion and also good formability.
  • thermoforming test in which a hat-shaped component was drawn from a round sheet-steel plate obtained according to the invention in a suitable tool, a very low abrasion of not more than 0.45 g / m 2 resulted.
  • the salt spray test carried out on a unpainted blank in the manner described in accordance with DIN 50021 SS gave a first formation of red rust only after a spraying time of 312 hours.
  • a conventional Zn coating with a coating weight of 25 g / m 2 per side provided sheets showed after 24 hours, a red rust formation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating With Molten Metal (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The coated steel plate or strip is covered by immersion in molten metal alloy. The alloy is composed of 0.05-0.30 wt.% aluminum, 0.2-2.0 wt.% magnesium with the remainder zinc and unavoidable impurities. The coating thickness is a maximum of 3.5 mu m on both sides with a coating weight at a maximum of 25 g/m 2> on each side.

Description

Die Erfindung betrifft ein beschichtetes Stahlblech oder -band mit einer aus Stahl bestehenden Grundschicht, auf deren mindestens eine Oberseite durch SchmelztauchBeschichten ein Zink-Überzug aufgetragen ist.The invention relates to a coated steel sheet or strip with a base layer consisting of steel, on whose at least one upper side by hot dip coating a zinc coating is applied.

Bei Stahlblechen oder Stahlbändern dieser Art stellt die Zink-Beschichtung eine hohe Korrosionsbeständigkeit sicher. Diese ist umso größer, je dicker der Überzug ist. So tritt bei einem konventionell legierten Zink-Überzug im an einer blanken, nicht lackierten Probe vorgenommenen Sprühtest nach DIN 50021 bei einer Schichtauflage von 25 g/m2 bereits nach 24 Stunden Rotrost auf, während bei einer Überzugauflage von 70 g/m2 Rotrost erst nach 120 Stunden entsteht.For steel sheets or steel strips of this type, the zinc coating ensures high corrosion resistance. This is the larger, the thicker the coating is. For example, in a conventionally alloyed zinc coating the red test carried out on a bare, unpainted sample in accordance with DIN 50021 results in red rust already after 24 hours at a coating run of 25 g / m 2 , while red coating occurs at a coating application of 70 g / m 2 after 120 hours arises.

Die beim Stand der Technik für eine ausreichende Korrosionsbeständigkeit erforderliche Dicke des Überzugs bringt jedoch Probleme bei der Verschweißbarkeit mit sich. Dies gilt insbesondere dann, wenn mittels Laserschweißen bei hohen Schweißgeschwindigkeiten eine Durchschweißung im Überlappstoß ohne Mindestfügespalt erzeugt werden soll, wie sie insbesondere im Bereich des Baus von Automobilkarosserien oder im Bereich der Haushaltstechnik gefordert wird. Die durch eine solche Schweißung erzeugte Naht soll frei von Durchgangslöchern sein, eine weitgehende Kraterfreiheit besitzen und keine offenen Poren aufweisen.However, the thickness of the coating required in the prior art for sufficient corrosion resistance involves problems in weldability. This is especially true if, by means of laser welding at high welding speeds, a through-welding in the lap joint is to be produced without a minimum gap, as required, in particular, in the field of building automobile bodies or in the field of household technology. The seam produced by such a weld should be free of through holes, have a substantial crater freedom and have no open pores.

Eine Möglichkeit, feuerverzinkte Stahlbleche mit erhöhter Korrosionsbeständigkeit bei gleichzeitig vermindertem Auflagengewicht herzustellen, ist in der EP 0 038 904 B1 beschrieben. Gemäß diesem Stand der Technik ist durch Schmelztauchbeschichten auf ein Stahlsubstrat eine 0,2 Gew.-% Al und 0,5 Gew.-% Mg enthaltende Zinkbeschichtung aufgebracht worden. Infolge des Magnesium-Gehaltes wies das so erhaltene schmelztauchbeschichtete Stahlband bei einem Auflagengewicht von 44 g/m2 pro Seite im lackierten Zustand in einem Salzsprühtest, bei dem die jeweilige Probe unter den im japanischen Industriestandard JIS Z 2371 vorgegebenen Bedingungen mit einer NaCl-Lösung besprüht worden ist, erst nach einer Sprühdauer von mehr als 2.000 h eine erste Rostbildung auf. Diese lange Dauer bis zur Entstehung von Rost wurde durch die kombinierte korrosionsschützende Wirkung von Zinkbeschichtung und Lackierung erreicht.One possibility for producing hot-dip galvanized steel sheets with increased corrosion resistance and simultaneously reduced coating weight is described in EP 0 038 904 B1. According to this prior art, a zinc coating containing 0.2% by weight of Al and 0.5% by weight of Mg has been applied to a steel substrate by hot dip coating. As a result of the magnesium content, the hot-dip coated steel strip thus obtained at a coating weight of 44 g / m 2 per side in the painted state in a salt spray test in which the respective sample sprayed with a NaCl solution under the conditions specified in Japanese Industrial Standard JIS Z 2371 has been, after a spraying time of more than 2,000 h, a first rust formation on. This long period until the formation of rust was achieved by the combined anti-corrosive effect of zinc coating and painting.

Trotz der gemäß der EP 0 038 904 B1 erzielten Verminderung des Auflagengewichts bei gleichzeitig guter Korrosionsbeständigkeit erfüllen die derart beschaffenen schmelztauchbeschichteten Stahlbleche immer noch nicht die im Bereich des Automobilbaus an die Verschweißbarkeit gestellten Anforderungen.Despite the reduction of the coating weight achieved in accordance with EP 0 038 904 B1, combined with good corrosion resistance, the hot-dip-coated steel sheets obtained in this way still do not meet the requirements imposed on the weldability in the field of automobile construction.

Die Aufgabe der Erfindung bestand daher darin, ein Stahlflachprodukt zu schaffen, das eine optimale Kombination von hoher Korrosionsbeständigkeit und optimierter Schweißbarkeit besitzt und welches sich insbesondere für die Verwendung als Werkstoff für den Automobilkarosseriebau oder für den Bau von Hausgeräten eignet.The object of the invention was therefore to provide a flat steel product which has an optimum combination of high corrosion resistance and optimized weldability and which is particularly suitable for use as a material for automotive body construction or for the construction of household appliances.

Diese Aufgabe ist erfindungsgemäß durch ein beschichtetes Stahlblech oder -band gelöst worden, dass eine aus Stahl bestehenden Grundschicht aufweist, auf deren mindestens eine Oberseite durch Schmelztauchbeschichten ein Überzug aufgetragen ist, der aus einer aus 0,05 - 0,30 Gew.-% Al und 0,2 - 2,0 Gew.-% Mg, Rest Zink und unvermeidbare Verunreinigungen bestehenden Schmelze gebildet ist und je Seite bei einer Überzugsdicke von höchstens 3,5 µm und einem Auflagengewicht von höchstens 25 g/m2 gewährleistet, dass das Stahlblech im nach DIN 50021-SS durchgeführten Salzsprühnebeltest frühestens nach 250 Stunden eine erste Rotrostbildung zeigt.This object is achieved according to the invention by a coated steel sheet or strip which has a base layer made of steel, on the at least one upper side of which a hot dip coating is applied, which consists of a layer of 0.05-0.30% by weight of Al and 0.2-2.0% by weight of Mg, balance zinc and unavoidable impurities existing melt is formed and each side with a coating thickness of at most 3.5 microns and a maximum coating weight of 25 g / m 2 ensures that the steel sheet shows the first formation of red rust at the earliest after 250 hours in the salt spray test carried out according to DIN 50021-SS.

Ein erfindungsgemäßes schmelztauchbeschichtetes Stahlflachprodukt besitzt bei einem gegenüber dem Stand der Technik minimierten Auflagengewicht von maximal 25 g/m2 je Seite eine überraschend gute Korrosionsbeständigkeit. Das geringe Auflagengewicht und die damit einhergehende geringe Stärke der Beschichtung von maximal 3,5 µm je Seite in Kombination mit der hohen Korrosionsbeständigkeit macht erfindungsgemäßes Blech oder Band besonders geeignet für die Erzeugung von Bauteilen, die durch Verschweißen von einzelnen Blechelementen hergestellt werden. So lassen sich mit erfindungsgemäß beschaffenen Stahlblechen insbesondere Elemente für Automobilkarosserien oder die Hausgerätetechnik herstellen, indem die einzelnen aus erfindungsgemäßem Blech oder Band geformten Blechteile durch Laserstrahlschweißen bei hohen Schweißgeschwindigkeiten wirtschaftlich und mit optimalem Ergebnis miteinander verschweißt werden.A hot-dip-coated flat steel product according to the invention has surprisingly good corrosion resistance at a maximum coating weight of 25 g / m 2 per side, minimized in comparison with the prior art. The low coating weight and the associated low thickness of the coating of a maximum of 3.5 microns each side in combination with the high corrosion resistance makes inventive sheet or strip particularly suitable for the production of components that are produced by welding of individual sheet metal elements. Thus, in particular, elements for automobile bodies or home appliance technology can be produced with sheet steel produced according to the invention by welding the individual sheet metal parts formed from sheet metal or strip according to the invention by laser welding at high welding speeds economically and with optimum results.

Die erfindungsgemäße Korrosionsbeständigkeit wird anhand einer Salzsprühnebelprüfung gemäß DIN 50021-SS in einem Korrosionskurzzeitprüfverfahren am blanken, unlackierten Stahlblech ermittelt, bei dem kontinuierlich eine neutrale 5 %-ige NaCl-Lösung bei einer Temperatur von 35 ± 2 °C als angreifendes Mittel in einer Kammer versprüht wird. Die Stahlblechproben werden dabei in der Kammer mit einem Neigungswinkel von 65 bis 75° zur Waagerechten aufgestellt. In derart durchgeführten praktischen Test hat sich erwiesen, dass erfindungsgemäß beschichtete Bleche und Bänder regelmäßig erst nach 300 Stunden Testdauer eine erste Rotrostbildung zeigen.The corrosion resistance of the invention is based on a salt spray test according to DIN 50021-SS in a Corrosion short-time test method on bare, unpainted steel sheet determined, in which a neutral 5% NaCl solution is continuously sprayed in a chamber at a temperature of 35 ± 2 ° C as an attacking agent. The steel sheet samples are placed in the chamber with an inclination angle of 65 to 75 ° to the horizontal. In practical tests carried out in this way, it has been found that sheets and strips coated according to the invention regularly show first red rust formation only after a test duration of 300 hours.

Der in der für die Beschichtung vorgesehenen Schmelze enthaltene Magnesium-Gehalt findet sich im Wesentlichen unverändert im Überzug wieder. Der Al-Gehalt des Überzugs liegt beim fertigen erfindungsgemäßen Stahlband dagegen in der Regel 1,8- bis 3,2-, insbesondere 2- bis 3-mal, höher als in der Schmelze. Ein optimaler Korrosionsschutz wird erreicht, wenn der Überzug einen Mg-Gehalt von 0,4 - 1,0 Gew.-%, insbesondere mindestens 0,5 Gew.-%, aufweist.The magnesium content contained in the melt intended for the coating is found essentially unchanged in the coating. By contrast, the Al content of the coating in the finished steel strip according to the invention is generally 1.8 to 3.2, in particular 2 to 3 times, higher than in the melt. Optimum corrosion protection is achieved if the coating has a Mg content of 0.4-1.0% by weight, in particular at least 0.5% by weight.

Soll die Beschichtung des Stahlgrundmaterials im Galvanealed-Prozess vorgenommen werden, so enthält die Schmelze bevorzugt weniger als 0,15 Gew.-% Aluminium. Praxisgerechte Al-Gehalte der Schmelze liegen in diesem Fall im Bereich 0,12 - 0,14 Gew.-%.If the coating of the steel base material is to be carried out in the galvanic sealed process, the melt preferably contains less than 0.15% by weight of aluminum. Practical Al contents of the melt in this case are in the range of 0.12-0.14% by weight.

Soll dagegen ein konventionell feuerverzinktes erfindungsgemäßes Stahlblech zur Verfügung gestellt werden, so beträgt der Al-Gehalt der Schmelze vorzugsweise mindestens 0,15 Gew.-%.If, on the other hand, a conventionally hot-dip galvanized steel sheet according to the invention is provided, the Al content of the melt is preferably at least 0.15% by weight.

Eine weitere überraschende Eigenschaft, die ein erfindungsgemäßes Flachprodukt besonders geeignet macht für die Verwendung im Karosseriebau, zeigt sich, wenn ein solches Blech oder Band lackiert wird. So ergibt ein in Anlehnung an DIN EN ISO 6860 durchgeführter Dornbiegetest für erfindungsgemäße Bleche oder Bändern bei Raumtemperatur und -20 °C ein gutes Lackanhaftungsvermögen. Insbesondere zeigen sich auch bei einer Temperatur von -20 °C keine Lackabplatzungen und auch Abplatzungen des Überzugs vom Grundmaterial.Another surprising feature that makes a flat product according to the invention particularly suitable for The use in body construction, shows up when such a metal sheet or tape is painted. Thus, a mandrel bending test carried out on the basis of DIN EN ISO 6860 for sheets or strips according to the invention at room temperature and -20 ° C. results in good paint adhesion. In particular, even at a temperature of -20 ° C no paint chipping and spalling of the coating from the base material.

Für den zur Bestimmung des Lackhaftungsvermögens durchgeführten Test ist auf eine erfindungsgemäß Stahlblechprobe nach einer alkalischen Reinigung und einer Phosphatierung ein Volllackaufbau aufgebracht worden, der eine 20 µm dicke kathodische Tauchlackierung, einen darauf aufgetragene, 32 µm dicke Füllerlackschicht und eine 40 µm dicke Basislackschicht umfasste. Die durchgeführten Biegung über den konischen Dorn führte weder bei Raumtemperatur noch bei -20 °C zu einer Ablösung der Lackschicht.For the test carried out to determine the paint adhesion capability, a full-scale coating comprising a 20 μm thick cathodic dip coating, a 32 μm thick surfacer coat layer applied thereto and a 40 μm thick basecoat film was applied to a steel sheet sample after alkaline cleaning and phosphating. The bending over the conical mandrel performed neither at room temperature nor at -20 ° C to a detachment of the paint layer.

Neben einer hohen Korrosionsbeständigkeit und einem guten Lackhaftungsvermögen besitzen erfindungsgemäße Bleche oder Bänder eine hervorragende Beständigkeit gegen Steinschlag. So konnte im nach DIN 65996-1B durchgeführten Steinschlagtest nachgewiesen werden, dass bei erfindungsgemäßen Stahlblechen durch Steinschlag keine Abplatzungen des Überzugs von der Grundschicht verursacht werden.In addition to a high corrosion resistance and good paint adhesion, sheets or tapes according to the invention have excellent resistance to stone chipping. Thus, in the stone impact test carried out in accordance with DIN 65996-1B, it was possible to demonstrate that, in the case of steel sheets according to the invention, no flaking of the coating from the base layer is caused by rockfall.

Zur Herstellung erfindungsgemäßer Bleche wird ein Stahlfeinband in einer Verzinkungsanlage, die mit einer Bandgeschwindigkeit von typischerweise 60 bis 150 m/min durchlaufen wird, einem kontinuierlich ablaufenden Bandfeuerverzinkungsprozess unterzogen. Dazu wird das zu verzinkende Blech oder Band zunächst in einem Ofen, beispielsweise einem DFF-Ofen (Direct Fired Furnace) oder, vorzugsweise, einem RTF-Ofen (Radiant Type Furnace) geglüht. Im Anschluss an den Ofen durchläuft das Blech oder Band den Reduktionsofenteil, in dem es unter einer Schutzgasatmosphäre mit 3,5 - 75 % Wasserstoff gehalten wird. Die im Zuge der Glühung erzielten Temperaturen liegen im Bereich von 720 - 850 °C.To produce sheets according to the invention, a steel fine strip in a galvanizing plant, which is traversed at a strip speed of typically 60 to 150 m / min, is subjected to a continuously running strip hot-dip galvanizing process. This will be too galvanizing sheet or strip first in an oven, for example a DFF furnace (Direct Fired Furnace) or, preferably, a RTF furnace (Radiant Type Furnace) annealed. Following the oven, the sheet or strip passes through the reduction furnace section, where it is maintained under a protective gas atmosphere of 3.5-75% hydrogen. The temperatures achieved during annealing are in the range of 720 - 850 ° C.

Das derart geglühte Band oder Blech wird anschließend über einen so genannten Rüssel unter Luftabschluss in das Zinkbad geleitet, das durch eine 0,05 - 0,30 Gew.-% Al und 0,2 - 2,0 Gew.-% Mg, insbesondere 0,4 - 1,0 Gew.-% bzw. 0,5 - 1,0 Gew.-%, Rest Zink und unvermeidbare Verunreinigungen enthaltende Schmelze gebildet ist.The thus annealed strip or sheet is then passed through a so-called proboscis under exclusion of air in the zinc bath, by a 0.05 to 0.30 wt .-% Al and 0.2 to 2.0 wt .-% Mg, in particular 0.4 to 1.0 wt .-% or 0.5 to 1.0 wt .-%, remainder zinc and unavoidable impurities containing melt is formed.

Nach dem Austritt des Bandes oder Blechs aus dem Schmelzenbad wird die Dicke des Überzugs in an sich bekannter Weise mittels Abstreifdüsen auf einen Wert von höchsten 3,5 µm je Seite beschränkt, so dass das bei dem erhaltenen erfindungsgemäßen Flachprodukt das Auflagengewicht auf höchstens 25 g/m2 pro Seite beschränkt ist.After the exit of the strip or sheet from the melt bath, the thickness of the coating is limited in a conventional manner by means of stripping nozzles to a value of 3.5 microns maximum page, so that the resulting flat product according to the invention, the maximum coating weight of 25 g / m 2 per side is limited.

Um eine übermäßige Bildung von Schlacken und intermetallischen Phasen auf dem Schmelzenbad zu verhindern, kann es zweckmäßig sein, einen Inertgasstrom über die Badoberfläche zu leiten. Dieser Inertgasstrom kann von den Abstreifdüsen ausgehen, die zum Einstellen der Überzugdicke eingesetzt werden, oder von separaten Düsen ausgebracht werden, die das inerte Gas schleierartig über der Badoberfläche verteilen. Alternativ kann das gesamte Schmelzenbad von einer Einhausung umgeben werden, in der eine inerte Atmosphäre aufrechterhalten wird. Als inertes Gas eignet sich für diesen Zweck insbesondere Stickstoff.To prevent excessive formation of slags and intermetallic phases on the melt bath, it may be desirable to pass an inert gas stream over the bath surface. This inert gas stream may originate from the wiping nozzles used to adjust the coating thickness, or may be discharged from separate nozzles which disperse the inert gas over the bath surface. Alternatively, the entire melt bath can be surrounded by an enclosure in which an inert atmosphere is maintained. Nitrogen is particularly suitable as inert gas for this purpose.

Die Schlackenbildung kann auch dadurch vermindert werden, dass die Badtemperatur auf einen Bereich von 380 - 450 °C eingestellt wird. Zum selben Zweck kann die Bandtemperatur beim Eintauchen auf 360 - 500 °C beschränkt werden, um insbesondere im Eintauchbereich die Oxidationsneigung zu minimieren.Slag formation can also be reduced by adjusting the bath temperature to a range of 380-450 ° C. For the same purpose, the belt temperature during immersion can be limited to 360 - 500 ° C in order to minimize the tendency to oxidation, especially in the immersion area.

Nach Austritt aus dem Schmelzenbad wird das beschichtete Band mit einer Abkühlgeschwindigkeit von mindestens 10 K/s. abgekühlt.After exiting the melt bath, the coated tape is at a cooling rate of at least 10 K / s. cooled.

Durch In-Line-Nachwalzen bei Walzgraden von 0,3 - 1,5 % kann dann erforderlichenfalls die gewünschte Texturierung der Oberfläche vorgenommen werden.By in-line re-rolling at rolling degrees of 0.3 - 1.5%, if necessary, the desired texturing of the surface can be made.

Indem das beschichtete ebenfalls in-line einer Nacherwärmung im Temperaturbereich von 300 - 600 °C unterzogen wird, wird entweder eine Umverteilung innerhalb der ZnMg-Überzug oder eine Durchlegierung in eine ZnFeMg-Überzug erreicht. Die zur Erzeugung einer solchen Schicht eingesetzten Schmelzen weisen bevorzugt einen Al-Gehalt von weniger als 0,15 Gew.-%, insbesondere 0,12 - 0,14 Gew.-%, auf.By also subjecting the coated to in-line reheating in the temperature range of 300-600 ° C, either redistribution within the ZnMg coating or alloying into a ZnFeMg coating is achieved. The melts used to produce such a layer preferably have an Al content of less than 0.15% by weight, in particular 0.12-0.14% by weight.

Zur Erweiterung des Anwendungsspektrums kann abschließend auf der Überzug in an sich bekannter Weise noch eine Dünnfilmbeschichtung aufgetragen werden.To expand the range of applications can finally be applied to the coating in a conventional manner nor a thin film coating.

Die durch die Erfindung erzielten Effekte sind anhand eines Versuchs bestätigt worden, bei dem ein aus konventionellem IF-Stahl hartgewalztes, 0,82 mm dickes Stahlband zunächst einer alkalischen Spritzreinigung, einer Bürstenreinigung und einer elektrolytischen Reinigung unterzogen worden ist. Anschließend erfolgt ein Glühen, bei dem das gereinigte Stahlband unter Schutzgas (5% H2, Rest N2) auf eine Temperatur von 800 °C geglüht worden ist. Die Glühzeit betrug 60 s.The effects achieved by the invention have been confirmed by an experiment in which a conventional IF steel hard-rolled, 0.82 mm thick steel strip was first subjected to an alkaline spray cleaning, a brush cleaning and an electrolytic cleaning. This is followed by annealing, in which the cleaned steel strip has been annealed to a temperature of 800 ° C. under protective gas (5% H 2 , remainder N 2 ). The annealing time was 60 s.

Das so geglühte Stahlband ist dann abgekühlt worden, so dass es mit einer Schmelzbadeintauchtemperatur von 465 °C in das in einer Einhausung unter einer maximal 10 ppm Sauerstoff enthaltenden Schutzgasatmosphäre gehaltene Schmelzbad eingetaucht ist. Das Schmelzbad bestand aus einer Zn-Schmelze, die neben unvermeidbaren Verunreinigungen (z.B. Fe-Gehalte, die durch das Band in das Schmelzenbad geschleppt werden) 0,2 Gew.-% Al, 0,8 Gew.-% Mg enthielt. Die Tauchzeit betrug zwei Sekunden.The thus annealed steel strip was then cooled so that it is immersed in the molten bath immersion temperature of 465 ° C in the molten bath held in an enclosure under a maximum of 10 ppm oxygen containing inert gas atmosphere. The molten bath consisted of a Zn melt containing, in addition to unavoidable impurities (e.g., Fe levels being dragged through the belt into the molten bath), 0.2 wt% Al, 0.8 wt% Mg. The dive time was two seconds.

Nach dem Ausleiten aus dem Schmelzenbad ist die Schichtdicke der auf dem Stahlband beidseitig aufgebrachten Überzug noch innerhalb der Schmelzenbadeinhausung mittels ebenfalls in der Einhausung angeordneter Abstreifdüsen auf eine Überzugdicke von 3 µm je Seite (entsprechend einem Auflagegewicht von 21 g/m2 je Seite) eingestellt worden. Das Abstreifen erfolgte ebenfalls mittels Stickstoffgas.After discharging from the melt bath, the layer thickness of the coating applied on both sides of the steel strip has been adjusted within the Schmelzenbadeinhausung by means also arranged in the housing Abstreifdüsen to a coating thickness of 3 microns per side (corresponding to a weight of 21 g / m 2 each side) , The stripping was also done by means of nitrogen gas.

Abschließend ist das Stahlband dressiert worden. Das erhaltene schmelztauchbeschichtete Stahlband wies Ra-Werte von 1,8 µm bei gemäß dem StahlEisen-Prüfblatt SEP 1940 ermittelten Pc-Werten von 46 cm-1.Finally, the steel band has been trained. The resulting hot dip coated steel strip had Ra values of 1.8 μm at Pc values of 46 cm -1 determined according to SEP 1940 Steel Iron Test Sheet.

An von dem fertig beschichteten Stahlband genommenen Proben wurde der Kugelschlagtest gemäß StahlEisen-Prüfblatt SEP 1931 durchgeführt, um die Haftung des Bezuges und seine Umformbarkeit zu ermitteln. Das Ergebnis konnte der Stufe 1 zugeordnet werden, was einer guten Haftung und ebenso guten Umformeignung entspricht.The samples taken from the finished coated steel strip were subjected to the ball impact test according to the steel-iron test sheet SEP 1931 was performed to determine the adhesion of the cover and its formability. The result could be assigned to the level 1, which corresponds to a good adhesion and also good formability.

Bei einem Tiefziehversuch, bei dem in einem geeigneten Werkzeug aus einer runden erfindungsgemäß beschaffenen Stahlblechplatine ein hutförmiges Bauteil gezogen worden ist, ergab sich ein sehr geringer Abrieb von maximal 0,45 g/m2.In a thermoforming test in which a hat-shaped component was drawn from a round sheet-steel plate obtained according to the invention in a suitable tool, a very low abrasion of not more than 0.45 g / m 2 resulted.

Die Beurteilung der Schweißbarkeit ergab für eine laserstrahlgeschweißte Naht jeweils ein sehr gutes Ergebnis. So konnten beim Laserstrahlschweißen mit einem Fügespalt "0" bei Schweißgeschwindigkeiten bis 5 m/min fehlerfreie Ergebnisse erzielt werden.The assessment of weldability showed a very good result for a laser-welded seam. For example, in laser beam welding with a joint gap "0" at welding speeds of up to 5 m / min, error-free results could be achieved.

Der an einer unlackierten blanken in der erläuterten Weise beschichteten Probe gemäß DIN 50021 SS durchgeführte Salzsprühtest ergab erst nach einer Sprühdauer von 312 Stunden eine erste Rotrostbildung. Mit einer konventionell Zn-Beschichtung bei einem Auflagegewicht von 25 g/m2 pro Seite versehene Bleche zeigten schon nach 24 Stunden eine Rotrostbildung.The salt spray test carried out on a unpainted blank in the manner described in accordance with DIN 50021 SS gave a first formation of red rust only after a spraying time of 312 hours. With a conventional Zn coating with a coating weight of 25 g / m 2 per side provided sheets showed after 24 hours, a red rust formation.

Die an erfindungsgemäß beschichteten Proben im konischen Dornbiegetest in Anlehnung an DIN EN ISO 6860 ermittelte Lackhaftung war sowohl bei Raumtemperatur als auch bei -20 °C gut. Der Steinschlagtest nach DIN 55996-1B ergab ebenfalls keine Abplatzungen des Überzugs von der Stahlgrundschicht.The paint adhesion determined on inventive coated samples in the conical mandrel bending test based on DIN EN ISO 6860 was good both at room temperature and at -20 ° C. The stone impact test according to DIN 55996-1B likewise did not result in any spalling of the coating from the steel base layer.

Claims (5)

Beschichtetes Stahlblech oder -band mit einer aus Stahl bestehenden Grundschicht, auf deren mindestens eine Oberseite durch Schmelztauchbeschichten ein Überzug aufgetragen ist, der aus einer aus 0,05 - 0,30 Gew.-% Al und 0,2 - 2,0 Gew.-% Mg, Rest Zink und unvermeidbare Verunreinigungen bestehenden Schmelze gebildet ist und bei einer Überzugsdicke von höchstens 3,5 µm je Seite und einem Auflagengewicht von höchstens 25 g/m2 je Seite gewährleistet, dass das Stahlblech im nach DIN 50021-SS durchgeführten Salzsprühnebeltest frühestens nach 250 Stunden eine erste Rotrostbildung zeigt.A coated steel sheet or strip having a base steel layer having at least one upper surface thereof, by hot dip coating, a coating composed of a 0.05-0.30 wt.% Al and 0.2-2.0 wt. -% Mg, remainder zinc and unavoidable impurities existing melt is formed and with a coating thickness of at most 3.5 microns per side and a maximum coating weight of 25 g / m 2 ensures that the sheet steel in accordance with DIN 50021-SS salt spray test at the earliest after 250 hours shows a first red rust formation. Stahlband nach Anspruch 1, dadurch gekennzeichnet, dass der Überzug 0,4 - 1,0 Gew.-% Mg enthält.Steel strip according to claim 1, characterized in that the coating contains 0.4-1.0% by weight of Mg. Stahlblech oder -band nach Anspruch 2, dadurch gekennzeichnet, dass der Überzug mehr als 0,5 Gew.-% Mg enthält.Steel sheet or strip according to claim 2, characterized in that the coating contains more than 0.5% by weight of Mg. Stahlblech oder -band nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, dass der Al-Gehalt der Schmelze 0,12 - 0,14 Gew.-% beträgt.Steel sheet or strip according to one of the preceding claims, characterized in that the Al content of the melt is 0.12 to 0.14 wt .-%. Stahlblech oder -band nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Al-Gehalt der Schmelze mindestens 0,15 Gew.-% beträgt.Steel sheet or strip according to one of claims 1 to 3, characterized in that the Al content of the melt is at least 0.15 wt .-%.
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JP2007556589A JP5270172B2 (en) 2005-02-22 2006-02-15 Coated steel plate or strip
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PCT/EP2006/050955 WO2006089854A1 (en) 2005-02-22 2006-02-15 Coated steel sheet or coil
AU2006218005A AU2006218005B2 (en) 2005-02-22 2006-02-15 Coated steel sheet or coil
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CA2596825A CA2596825C (en) 2005-02-22 2006-02-15 Coated steel sheet or strip
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CN101128614A (en) 2008-02-20
KR20070105371A (en) 2007-10-30
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EP1851352A1 (en) 2007-11-07
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CN101128614B (en) 2012-07-18
EP1851352B1 (en) 2017-09-06
WO2006089854A1 (en) 2006-08-31
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AU2006218005B2 (en) 2011-11-17
US20080142125A1 (en) 2008-06-19

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