EP1851352A1 - Coated steel sheet or coil - Google Patents

Coated steel sheet or coil

Info

Publication number
EP1851352A1
EP1851352A1 EP06724846A EP06724846A EP1851352A1 EP 1851352 A1 EP1851352 A1 EP 1851352A1 EP 06724846 A EP06724846 A EP 06724846A EP 06724846 A EP06724846 A EP 06724846A EP 1851352 A1 EP1851352 A1 EP 1851352A1
Authority
EP
European Patent Office
Prior art keywords
coating
steel
steel sheet
case
weight
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.)
Granted
Application number
EP06724846A
Other languages
German (de)
French (fr)
Other versions
EP1851352B8 (en
EP1851352B1 (en
Inventor
Manfred Meurer
Sabine Zeizinger
Rudolf Schönenberg
Wilhelm Warnecke
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 EP06724846.8A priority Critical patent/EP1851352B8/en
Publication of EP1851352A1 publication Critical patent/EP1851352A1/en
Application granted granted Critical
Publication of EP1851352B1 publication Critical patent/EP1851352B1/en
Publication of EP1851352B8 publication Critical patent/EP1851352B8/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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 coat run of 25 g / m 2 , whereas with a coating overlay of 70 g / m 2 red rust only 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 laser welding at high welding speeds through-welding in the lap joint is to be generated without minimum gap, as in particular in the field of construction of
  • the seam produced by such a weld should be free of through holes, have a substantial crater freedom and have no open pores.
  • hot dip coating on a steel substrate comprises 0.2 wt% Al and 0.5 wt% Mg
  • Zinc coating has been applied.
  • the resulting hot dip coated steel strip 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.
  • 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 the individual sheet metal parts formed from sheet metal or strip according to the invention by laser beam welding at high temperatures
  • the corrosion resistance of the invention is based on a salt spray test according to DIN 50021-SS in a
  • 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.
  • SI / nm 050215WO The use in body construction, shows up when such a metal sheet or tape is painted. So one carried out in accordance with DIN EN ISO 6860 Mandrel bending test for inventive sheets or strips at room temperature and -20 0 C gives a good Lackanhaftungshack. In particular, even at a temperature of -20 0 C show no Lackabplatzept and spalling of the coating from the base material.
  • 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 0 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.
  • the sheet or strip to be galvanized is first placed in an oven,
  • SI / nm 050215WO 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 in the course of the annealing are in the range of 720 - 850 0 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 may be surrounded by an enclosure in which an inert atmosphere is maintained. Nitrogen is particularly suitable as inert gas for this purpose.
  • the slag can also be reduced in that the bath temperature to a range of 380-450 0 C is set.
  • the strip temperature can when dipping to 360 to 500 0 C are limited to minimize the oxidation tendency especially in the immersion area.
  • the coated strip After exiting the melt bath, the coated strip is cooled at a cooling rate of at least 10 K / s.
  • 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.
  • a thin-film coating can finally be applied to the coating in a manner known per se.
  • the thus annealed steel strip was then cooled so that it is immersed with a melt bath immersion temperature of 465 0 C held in the housing in a housing under a maximum of 10 ppm oxygen-containing inert gas bath melt.
  • the molten bath consisted of a Zn melt containing, in addition to unavoidable impurities (eg, Fe contents 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 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 invention relates to a coated steel sheet or coil having a base layer which is composed of steel and to whose at least one top face is applied, by hot dip coating, a zinc coating. In the case of such steel sheets or steel coils, the zinc coating ensures a high level of corrosion resistance. The thicker the coating, the greater this resistance. Thus, in the case of a conventionally alloyed zinc coating, in a spraying test performed on a bright, uncoated sample in accordance with DIN 50021, red rust occurs after just 24 hours in the case of a coat add-on of 25 g/m2 , whereas with a coating add-on of 70 g/m2 red rust is formed only after 120 hours. The thickness of the coating that is needed in the prior art for sufficient corrosion resistance, however, brings problems with it in connection with weldability. This is the case in particular when laser welding at high welding speeds is to be used to produce a penetration weld in the lap joint without a minimum joining gap, of the kind required in particular in the field of the construction of car bodies or in the field of household engineering. The seam produced by such welding ought to be free from through-holes, to possess substantially no craters and to have no open pores.

Description

15. Februar 2006February 15th, 2006
BESCHICHTETES STAHLBLECH ODER -BANDCOATED STEEL PLATE OR RIBBON
Die Erfindung betrifft ein beschichtetes Stahlblech oder -band mit einer aus Stahl bestehenden Grundschicht, auf deren mindestens eine Oberseite durch Schmelztauch- Beschichten 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 coat run of 25 g / m 2 , whereas with a coating overlay of 70 g / m 2 red rust only 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 vonHowever, the thickness of the coating required in the prior art for sufficient corrosion resistance involves problems in weldability. This is especially true if by laser welding at high welding speeds through-welding in the lap joint is to be generated without minimum gap, as in particular in the field of construction of
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.Car bodies or in the field of home appliances is required. The seam produced by such a weld should be free of through holes, have a substantial crater freedom and have no open pores.
SI/nm 050215WO Eine Möglichkeit, feuerverzinkte Stahlbleche mit erhöhter Korrosionsbeständigkeit bei gleichzeitig vermindertem Auflagengewicht herzustellen, ist in der EP 0 038 904 Bl beschrieben. Gemäß diesem Stand der Technik ist durch Schmelztauchbeschichten auf ein Stahlsubstrat eine 0,2 Gew.-% Al und 0,5 Gew.-% Mg enthaltendeSI / nm 050215WO 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, hot dip coating on a steel substrate comprises 0.2 wt% Al and 0.5 wt% Mg
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.Zinc coating has been applied. As a result of the magnesium content, the resulting hot dip coated steel strip 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 Bl 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 with simultaneously good corrosion resistance, the hot-dip-coated steel sheets thus obtained still do not meet the requirements for weldability in the field of automotive engineering.
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.
SI/nm 050215WO 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.SI / nm 050215WO 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 hohenA 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 the individual sheet metal parts formed from sheet metal or strip according to the invention by laser beam welding at high temperatures
Schweißgeschwindigkeiten wirtschaftlich und mit optimalem Ergebnis miteinander verschweißt werden.Welding speeds are economically and with optimum results welded together.
Die erfindungsgemäße Korrosionsbeständigkeit wird anhand einer Salzsprühnebelprüfung gemäß DIN 50021-SS in einemThe corrosion resistance of the invention is based on a salt spray test according to DIN 50021-SS in a
SI/nm 050215WO Korrosionskurzzeitprüfverfahren am blanken, unlackierten Stahlblech ermittelt, bei dem kontinuierlich eine neutraleSI / nm 050215WO Corrosion short-time test procedure on bare, unpainted steel sheet determined, in which a continuous neutral
5 %-ige NaCl-Lösung bei einer Temperatur von 35 ± 2 0C 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.5% NaCl solution at a temperature of 35 ± 2 0 C as an attacking agent is sprayed in a chamber. 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 fürAnother surprising feature that makes a flat product according to the invention particularly suitable for
SI/nm 050215WO 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 0C ein gutes Lackanhaftungsvermögen. Insbesondere zeigen sich auch bei einer Temperatur von -20 0C keine Lackabplatzungen und auch Abplatzungen des Überzugs vom Grundmaterial .SI / nm 050215WO The use in body construction, shows up when such a metal sheet or tape is painted. So one carried out in accordance with DIN EN ISO 6860 Mandrel bending test for inventive sheets or strips at room temperature and -20 0 C gives a good Lackanhaftungsvermögen. In particular, even at a temperature of -20 0 C show no Lackabplatzungen 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 0C 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 0 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,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. For this, the sheet or strip to be galvanized is first placed in an oven,
SI/nm 050215WO 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 0C.SI / nm 050215WO 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 in the course of the annealing are in the range of 720 - 850 0 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 may be surrounded by an enclosure in which an inert atmosphere is maintained. Nitrogen is particularly suitable as inert gas for this purpose.
SI/nm 050215WO Die Schlackenbildung kann auch dadurch vermindert werden, dass die Badtemperatur auf einen Bereich von 380 - 450 0C eingestellt wird. Zum selben Zweck kann die Bandtemperatur beim Eintauchen auf 360 - 500 0C beschränkt werden, um insbesondere im Eintauchbereich die Oxidationsneigung zu minimieren .SI / nm 050215WO The slag can also be reduced in that the bath temperature to a range of 380-450 0 C is set. For the same purpose the strip temperature can when dipping to 360 to 500 0 C are limited to minimize the oxidation tendency 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 strip is cooled at a cooling rate of at least 10 K / s.
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 0C 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 passing the coated also in-line to a post-heating in the temperature range 300-600 0 C is subjected is achieved either a redistribution within the ZnMg coating or through alloy into a ZnFeMg- coating. 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 extend the range of applications, a thin-film coating can finally be applied to the coating in a manner known per se.
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.The effects achieved by the invention have been confirmed by an experiment in which a 0.82 mm thick steel strip hard-rolled from conventional IF steel was first subjected to alkaline spray cleaning, brush cleaning and electrolytic cleaning.
SI/nm 050215WO Anschließend erfolgt ein Glühen, bei dem das gereinigte Stahlband unter Schutzgas (5% H2, Rest N2) auf eine Temperatur von 800 0C geglüht worden ist. Die Glühzeit betrug 60 s.SI / nm 050215WO 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 0C 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 with a melt bath immersion temperature of 465 0 C held in the housing in a housing under a maximum of 10 ppm oxygen-containing inert gas bath melt. The molten bath consisted of a Zn melt containing, in addition to unavoidable impurities (eg, Fe contents 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.On samples taken from the finished coated steel strip, the ball impact test was conducted in accordance with Steel Ferrous Test Sheet SEP 1931 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.
SI/nm 050215WO 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.SI / nm 050215WO 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 0C gut. Der Steinschlagtest nach DIN 55996-1B ergab ebenfalls keine Abplatzungen des Überzugs von der Stahlgrundschicht .The paint adhesion determined in accordance with the invention coated samples in the conical mandrel bending test according to DIN EN ISO 6860 was good at both room temperature and at -20 0 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.
SI/nm 050215WO SI / nm 050215WO

Claims

15. Februar 2006P A T E N T AN S P R Ü C H E February 15, 2006P ATENT TO SPR Ü CHE
1. 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 nachA coated steel sheet or strip having a base steel layer having at least one top side thereof by hot dip coating a coating consisting of 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 per side ensures that the steel sheet in after
DIN 50021-SS durchgeführten Salzsprühnebeltest frühestens nach 250 Stunden eine erste Rotrostbildung zeigt .DIN 50021-SS salt spray test shows a first formation of red rust at the earliest after 250 hours.
2. Stahlband nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t, d a s s der Überzug 0,4 - 1,0 Gew.-% Mg enthält.2. A steel strip according to claim 1, wherein the coating contains 0.4 to 1.0 wt.% Mg.
3. Stahlblech oder -band nach Anspruch 2, d a d u r c h g e k e n n z e i c h n e t, d a s s der Überzug mehr als 0,5 Gew.-% Mg enthält.3. Steel sheet or strip according to claim 2, characterized in that the coating contains more than 0.5% by weight of Mg.
4. Stahlblech oder -band nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d a s s der Al-Gehalt der Schmelze 0,12 - 0,14 Gew.-% beträgt .4. 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% by weight.
SI/nm 050215WO SI / nm 050215WO
5. Stahlblech oder -band nach einem der Ansprüche 1 bis 3, d a d u r c h g e k e n n z e i c h n e t, d a s s der Al-Gehalt der Schmelze mindestens 0,15 Gew.-% beträgt.5. The steel sheet or strip according to claim 1, wherein the Al content of the melt is at least 0.15% by weight.
SI/nm 050215WO SI / nm 050215WO
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