EP1857566B1 - Flat steel product provided with a corrosion protection coating and method of its manufacture - Google Patents
Flat steel product provided with a corrosion protection coating and method of its manufacture Download PDFInfo
- Publication number
- EP1857566B1 EP1857566B1 EP06113962.2A EP06113962A EP1857566B1 EP 1857566 B1 EP1857566 B1 EP 1857566B1 EP 06113962 A EP06113962 A EP 06113962A EP 1857566 B1 EP1857566 B1 EP 1857566B1
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- European Patent Office
- Prior art keywords
- coating
- steel
- steel substrate
- temperature
- layer
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- 229910000831 Steel Inorganic materials 0.000 title claims description 68
- 239000010959 steel Substances 0.000 title claims description 68
- 238000005260 corrosion Methods 0.000 title claims description 29
- 230000007797 corrosion Effects 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000576 coating method Methods 0.000 title description 53
- 239000011248 coating agent Substances 0.000 title description 49
- 239000010410 layer Substances 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 33
- 239000011701 zinc Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 239000011253 protective coating Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000000155 melt Substances 0.000 description 15
- 238000003466 welding Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000009533 lab test Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 2
- 229910003023 Mg-Al Inorganic materials 0.000 description 2
- 229910000742 Microalloyed steel Inorganic materials 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
Definitions
- the invention relates to a method for producing a flat steel product formed from a steel substrate, such as steel strip or sheet, and a zinc-based anticorrosive coating applied to at least one of the sides of the steel substrate.
- metallic coatings are applied, in particular on steel sheets or strips, which are based on zinc or zinc alloys in the majority of applications.
- Such zinc or zinc alloy coatings protect due to their barrier and cathodic protection effect the corresponding coated steel sheet in practical use against corrosion.
- the thickness of the coating required in the prior art for sufficient corrosion resistance poses problems in processing, ie in forming and welding. This applies z. B. when in high-wear highly corrosive flanges to be welded by spot welding. This requirement exists in particular in the field of construction of automobile bodies, in general construction applications or in the construction of housings for building services.
- a metallic protective coating sheet with improved corrosion resistance is from the EP 1 621 645 Al known.
- the one described there Steel sheet is provided with a protective coating by conventional hot-dip galvanizing, containing (in% by weight) 0.3-2.3% Mg, 0.6-2.3% Al, optionally ⁇ 0.2% other active ingredients and balance Zn and unavoidable impurities.
- the steel sheet is passed through a melt bath containing 0.3-2.3% by weight of Mg, 0.5-2.3% by weight of Al, optionally less than 0.2% by weight of others Alloy components and passed as rest Zn and unavoidable impurities.
- a melt bath containing 0.3-2.3% by weight of Mg, 0.5-2.3% by weight of Al, optionally less than 0.2% by weight of others Alloy components and passed as rest Zn and unavoidable impurities.
- the object of the invention was therefore to provide a method for producing a flat steel product, which has an optimum combination of high corrosion resistance and optimized processability and which is particularly suitable for use as a material for automotive body construction, for general construction or for home appliance.
- the invention is based on the recognition that general properties such. As adhesion and also weldability of provided with a corrosion-protective Zn-Mg-Al coating steel sheet or strip decisively depends on the distribution of the aluminum in the coating layer. Thus, it has surprisingly been found that when, as predetermined by the invention, in a near-surface intermediate layer of sufficient thickness according to the invention low Al contents are present, compared to conventionally formed sheets improved weldability is given, although the Al content of the coating on the whole a level is guaranteed by the high corrosion protection. The correspondingly produced according to the invention sheets in the boundary layer at the transition to the steel substrate high Al concentration thereby causes the positive effect of aluminum on the corrosion protection is maintained despite the low proportion of Al in the intermediate layer.
- flat steel products produced according to the invention likewise show a particularly good suitability for phosphating, so that they can be provided with an organic lacquer coating, for example, without any special additional measures.
- Elements from the group Pb, Bi, Cd, Ti, B, Si, Cu, Ni, Co, Cr, Mn, Sn and rare earths can be present up to a total of their contents of 0.8% by weight in the coating produced according to the invention be.
- Pb, Bi and Cd can be used to form a larger crystal structure (zinc flower), Ti, B, Si to improve the formability, Cu, Ni, Co, Cr, Mn to influence the boundary layer reactions, Sn influencing the surface oxidation and rare earths, especially lanthanum and cerium, to improve the flow behavior of the melt.
- the impurities which may be present in a corrosion protection coating according to the invention also include the constituents which, as a result of the hot-dip coating, enter the coating from the steel substrate in quantities which do not affect the properties of the coating.
- the shape of the layer structure desired according to the invention can be directly influenced by a suitable adjustment of the strip inlet and / or bath temperature.
- the process control according to the invention is achieved in that adjacent to the steel substrate Bound layer high Al and Mg contents accumulate, while in the intermediate layer in particular low Al contents are present.
- the difference between the temperature of the strip during immersion and the temperature of the melt bath is of particular importance.
- the inventively minimized presence of Al in the intermediate layer can be set in a safe and targeted manner.
- an advantageous embodiment of the invention provides that the Al content of the intermediate layer is limited to 0.25 wt .-%.
- the layer structure used by the invention then has a particularly positive effect on the weldability and the phosphatability with at the same time still good corrosion protection of the coating, if the thickness of the intermediate layer according to the invention is at least 25% of the total thickness of the anticorrosive coating.
- the information on the structure of the corrosion-coating layer and its individual layers contained herein and in the claims relates to a layer profile determined by a GDOS measurement (glow discharge optical emission spectrometry).
- a GDOS measurement low discharge optical emission spectrometry
- the surface layer is in each case not more than 0.2 .mu.m thick, so that with conventional coating thicknesses of 6 .mu.m and more, the fraction of the surface boundary layer in the total thickness of the coating overlay is approximately 3.5% and wide below it lies.
- the coating has contents of Fe which are more than 0.3% by weight, in particular more than 0.4% by weight or even more than 0.5% by weight.
- the relatively high Fe contents are present in particular in the region of the boundary layer adjacent to the steel substrate.
- a flat steel product obtained according to the invention has Performance characteristics, which are superior to the conventional flat steel products, even if they have high Mg and Al contents in their protective coating.
- the Al content of the anticorrosive coating can be limited to less than 0.6% by weight, in particular less than 0.5% by weight.
- the total thickness of the anticorrosive coating should be at least 5 ⁇ m , in particular at least 7 ⁇ m .
- pad weight distribution of the anticorrosive coating of at least 100 g / m 2 prove to be particularly favorable in terms of its protective effect.
- the weldability is not adversely affected due to the invention prescribed distribution of its Al content.
- the speed with which the steel substrate passes through the melt bath has only a minor influence on the coating result. Therefore, it can be varied in the range of 50 - 200 m / min, for example, in order to achieve the optimum work result at maximum productivity.
- the annealing of the steel strip, which precedes the melt bath, should be carried out under a protective gas atmosphere in order to avoid oxidation of the sheet surface.
- the protective gas atmosphere in a conventional manner contains more than 3.5 vol .-% H 2 and in each case as the radical N 2 .
- the annealing temperature is also in a known manner in the range of 700 - 900 ° C.
- the melt bath maintains its optimum temperature evenly despite the entry of the steel substrate.
- the melt bath itself preferably contains at best traces of iron, since according to the invention the Fe content of the corrosion-coating layer is to be established by alloying in iron originating from the steel substrate. Accordingly, the Fe content of the melt bath is preferably limited to at most 0.1 wt%, more preferably at most 0.07 wt%.
- a steel atmosphere steel strip under a nitrogen atmosphere containing 5% H 2 and having a dew point of -30 ° C ⁇ 2 ° C is annealed for a holding time of 60 s each Service.
- the annealing temperature was 800 ° C at a heating rate of 10 ° C / s.
- the steel strip was quenched at a cooling rate of 5 to 30 ° C / s to a temperature of 470 ° C ⁇ 5 ° C where it was held for 30 seconds. Then the steel strip is with a belt immersion speed of 100 m / min was passed into a melt bath whose bath temperature was 460 ° C ⁇ 5 ° C. The strip inlet temperature of the steel strip was in each case 5 ° C. above the bath temperature of the melt bath.
- a surface boundary layer has formed on the surface of the respective coating whose Al content is high as a result of oxidation.
- the thickness of this surface boundary layer is at most 0.2 ⁇ m and is therefore easily broken in the spot or laser welding, without causing a deterioration in the quality of the welding result.
- the about 2.5 ⁇ m thick intermediate layer to the surface boundary layer includes, whose Al content is below 0.2%, respectively.
- the thickness of the intermediate layer is therefore approximately 36% of the total overlay thickness of the respective anti-corrosion coating of 7 ⁇ m .
- the intermediate layer merges into a boundary layer adjacent to the steel substrate, in which the contents of Al, Mg and Fe have increased significantly compared with the corresponding contents of the intermediate layer.
- the thickness of the superficial oxidation surface boundary layer is max. 0.2 ⁇ m and is based on the determined in a GDOS measurement layer profile in each case in the range of up to 2.7% of the total overlay thicknesses.
- the amount of Al enrichment on the immediate surface is at most about 1 wt .-%. This is followed up to a thickness of at least 25% of the total overlay of the coating, the intermediate layer with a low Al content of not more than 0.25 wt .-% of. In the boundary layer, the Al content rises to 4.5% at the Border to the steel substrate.
- the Mg enrichment on the immediate surface of the coating is significantly greater than the Al enrichment. Mg contents of up to 20% are achieved here.
- the amount of Mg decreases over the intermediate layer and is 0.5 to 2% at a depth of about 25% of the total overlay thickness of the overlay.
- An increase of the Mg content in the direction of the steel substrate then takes place via the boundary layer. At the border to the steel substrate, the Mg content is up to 3.5%.
- Table 1 sample According to the invention? melt bath Layer analysis top Shift analysis bottom al Fe mg al Fe mg Editions weight Thickness al Fe mg Editions weight Thickness % *) % *) g / m 2 ⁇ m % *) g / m 2 ⁇ m E1 YES 0.201 0.011 1,589 1.16 1.06 1.52 41.5 7.0 ne ne ne n.
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Coating With Molten Metal (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines Stahlflachprodukts, das aus einem Stahlsubstrat, wie Stahlband oder -blech, und einem auf mindestens einer der Seiten des Stahlsubstrats aufgebrachten, auf Zink basierenden Korrosionsschutzüberzug gebildet ist.The invention relates to a method for producing a flat steel product formed from a steel substrate, such as steel strip or sheet, and a zinc-based anticorrosive coating applied to at least one of the sides of the steel substrate.
Zur Verbesserung ihrer Beständigkeit gegen Korrosion werden insbesondere auf Stahlblechen oder -bändern metallische Überzüge aufgebracht, die in der überwiegenden Zahl der Anwendungsfälle auf Zink oder Zinklegierungen basieren. Solche Zink- bzw. Zinklegierungsüberzüge schützen aufgrund ihrer Barriere- und kathodischen Schutzwirkung das entsprechend beschichtete Stahlblech im praktischen Einsatz gut gegen Korrosion.To improve their resistance to corrosion, metallic coatings are applied, in particular on steel sheets or strips, which are based on zinc or zinc alloys in the majority of applications. Such zinc or zinc alloy coatings protect due to their barrier and cathodic protection effect the corresponding coated steel sheet in practical use against corrosion.
Die beim Stand der Technik für eine ausreichende Korrosionsbeständigkeit erforderliche Dicke des Überzugs bringt jedoch Probleme bei der Verarbeitung, d. h. beim Umformen und Verschweißen mit sich. Dies gilt z. B. dann, wenn im praktischen Einsatz hoch korrosionsbelastete Flansche mittels Punktschweißen verschweißt werden sollen. Diese Anforderung besteht insbesondere im Bereich des Baus von Automobilkarosserien, bei allgemeinen Bauanwendungen oder beim Bau von Gehäusen für die Haustechnik. Die bei einer solchen Schweißung erzeugte Verbindung soll bei ausreichendem Schweißstrom einen Mindestpunktdurchmesser von
Vor dem Hintergrund der Probleme bei der Verarbeitung von konventionell mit einer Zn-Schicht großer Dicke beschichteten Blechen sind hochkorrosionsbeständige Zn-Mg- bzw. Zn-Mg-Al-Schichtsysteme entwickelt worden, die bei deutlich verminderter Schichtdicke einen mit einer konventionellen, 7,5 µm dicken Zinkbeschichtung vergleichbaren Korrosionsschutz bieten, jedoch eine signifikant bessere Verarbeitbarkeit aufweisen.Against the background of the problems in the processing of conventional coated with a Zn layer of large thickness sheets highly corrosion resistant Zn-Mg and Zn-Mg-Al layer systems have been developed, the one with a significantly reduced layer thickness with a conventional, 7.5 offer μ m thick zinc coating comparable corrosion protection, but have a significantly better processability.
Eine Möglichkeit, solcherart feuerverzinkte Stahlbleche mit erhöhter Korrosionsbeständigkeit bei gleichzeitig vermindertem Auflagengewicht herzustellen, ist in der
Ein weiteres mit einem metallischen Schutzüberzug versehenes Blech mit verbesserter Korrosionsbeständigkeit ist aus der
Beim aus der
Die Aufgabe der Erfindung bestand daher darin, ein Verfahren zur Herstellung eines Stahlflachprodukts anzugeben, das eine optimale Kombination von hoher Korrosionsbeständigkeit und optimierter Verarbeitbarkeit besitzt und welches sich insbesondere für die Verwendung als Werkstoff für den Automobilkarosseriebau, für allgemeine Bauzwecke oder für den Hausgerätebau eignet.The object of the invention was therefore to provide a method for producing a flat steel product, which has an optimum combination of high corrosion resistance and optimized processability and which is particularly suitable for use as a material for automotive body construction, for general construction or for home appliance.
Diese Aufgabe ist erfindungsgemäß durch das in Anspruch 1 angegebene Verfahren gelöst worden.This object has been achieved by the method specified in
Der Erfindung liegt die Erkenntnis zu Grunde, dass allgemeine Eigenschaften wie z. B. Haftung und auch Schweißeignung eines mit einem vor Korrosion schützenden Zn-Mg-Al-Überzug versehenen Stahlblechs oder -bands entscheidend von der Verteilung des Aluminiums in der Überzugsschicht abhängt. So hat sich überraschend herausgestellt, dass dann, wenn, wie von der Erfindung vorgegeben, in einer oberflächennahen Zwischenschicht ausreichender Dicke erfindungsgemäß geringe Al-Gehalte vorhanden sind, eine gegenüber konventionell ausgebildeten Blechen verbesserte Schweißeignung gegeben ist, obwohl der Al-Gehalt des Überzugs insgesamt auf einem Niveau liegt, durch das ein hoher Korrosionsschutz gewährleistet ist. Die dementsprechend bei erfindungsgemäß hergestellten Blechen im Bereich der Grenzschicht am Übergang zum Stahlsubstrat hohe Al-Konzentration bewirkt dabei, dass die positive Wirkung des Aluminiums auf den Korrosionsschutz trotz des geringen Anteils an Al in der Zwischenschicht erhalten bleibt.The invention is based on the recognition that general properties such. As adhesion and also weldability of provided with a corrosion-protective Zn-Mg-Al coating steel sheet or strip decisively depends on the distribution of the aluminum in the coating layer. Thus, it has surprisingly been found that when, as predetermined by the invention, in a near-surface intermediate layer of sufficient thickness according to the invention low Al contents are present, compared to conventionally formed sheets improved weldability is given, although the Al content of the coating on the whole a level is guaranteed by the high corrosion protection. The correspondingly produced according to the invention sheets in the boundary layer at the transition to the steel substrate high Al concentration thereby causes the positive effect of aluminum on the corrosion protection is maintained despite the low proportion of Al in the intermediate layer.
Dabei zeigen erfindungsgemäß hergestellte Stahlflachprodukte ebenfalls in Folge der geringen Gehalte an Al auf ihrer Oberfläche und in der Zwischenschicht eine besonders gute Eignung zur Phosphatierung, so dass sie beispielsweise ohne besondere zusätzliche Maßnahmen mit einer organischen Lackbeschichtung versehen werden können.As a result of the low contents of Al on their surface and in the intermediate layer, flat steel products produced according to the invention likewise show a particularly good suitability for phosphating, so that they can be provided with an organic lacquer coating, for example, without any special additional measures.
Elemente aus der Gruppe Pb, Bi, Cd, Ti, B, Si, Cu, Ni, Co, Cr, Mn, Sn sowie Seltene Erden können bis zu einer Summe ihrer Gehalte von 0,8 Gew.-% im erfindungsgemäß erzeugten Überzug vorhanden sein. Pb, Bi und Cd können dabei zur Ausbildung einer größeren Kristallstruktur (Zinkblume), Ti, B, Si zur Verbesserung der Umformbarkeit, Cu, Ni, Co, Cr, Mn zur Beeinflussung der Grenzschichtreaktionen, Sn Beeinflussung der Oberflächenoxidation und seltene Erden, insbesondere Lanthan und Cer, zur Verbesserung des Fließverhaltens der Schmelze zugegeben werden. Zu den Verunreinigungen, die in einem erfindungsgemäßen Korrosionsschutzüberzug enthalten sein können, zählen auch die Bestandteile, die in Folge des Schmelztauchbeschichtens aus dem Stahlsubstrat in Mengen in den Überzug gelangen, durch die die Eigenschaften des Überzugs nicht beeinflusst werden.Elements from the group Pb, Bi, Cd, Ti, B, Si, Cu, Ni, Co, Cr, Mn, Sn and rare earths can be present up to a total of their contents of 0.8% by weight in the coating produced according to the invention be. Pb, Bi and Cd can be used to form a larger crystal structure (zinc flower), Ti, B, Si to improve the formability, Cu, Ni, Co, Cr, Mn to influence the boundary layer reactions, Sn influencing the surface oxidation and rare earths, especially lanthanum and cerium, to improve the flow behavior of the melt. The impurities which may be present in a corrosion protection coating according to the invention also include the constituents which, as a result of the hot-dip coating, enter the coating from the steel substrate in quantities which do not affect the properties of the coating.
Es hat sich gezeigt, dass bei den relativ niedrigen Al-Gehalten eines zur Durchführung des erfindungsgemäßen Verfahrens verwendeten Schmelzenbades durch eine geeignete Einstellung der Bandeintritts- und / oder der Badtemperatur selbst die Ausprägung des erfindungsgemäß angestrebten Schichtaufbaus direkt beeinflusst werden kann. Durch die erfindungsgemäße Verfahrensführung wird dabei erreicht, dass sich in der zum Stahlsubstrat angrenzenden Grenzschicht hohe Al- und Mg-Gehalte anreichern, während in der Zwischenschicht insbesondere niedrige Al-Gehalte vorhanden sind. Dabei kommt der Differenz zwischen der Temperatur des Bandes beim Eintauchen und der Temperatur des Schmelzenbades eine besondere Bedeutung zu. Indem diese Differenz im Bereich von -10 °C bis 70 °C variiert wird, lässt sich die erfindungsgemäß minimierte Anwesenheit von Al in der Zwischenschicht sicher und gezielt einstellen.It has been found that, given the relatively low Al contents of a melt bath used for carrying out the method according to the invention, the shape of the layer structure desired according to the invention can be directly influenced by a suitable adjustment of the strip inlet and / or bath temperature. By the process control according to the invention is achieved in that adjacent to the steel substrate Bound layer high Al and Mg contents accumulate, while in the intermediate layer in particular low Al contents are present. In this case, the difference between the temperature of the strip during immersion and the temperature of the melt bath is of particular importance. By varying this difference in the range from -10 ° C. to 70 ° C., the inventively minimized presence of Al in the intermediate layer can be set in a safe and targeted manner.
Besonders günstige Schweißeigenschaften stellen sich dann ein, wenn der Aluminiumgehalt der Zwischenschicht so weit wie möglich reduziert ist. Daher sieht eine vorteilhafte Ausgestaltung der Erfindung vor, dass der Al-Gehalt der Zwischenschicht auf 0,25 Gew.-% beschränkt ist.Particularly favorable welding properties occur when the aluminum content of the intermediate layer is reduced as much as possible. Therefore, an advantageous embodiment of the invention provides that the Al content of the intermediate layer is limited to 0.25 wt .-%.
Darüber hinaus wirkt sich der durch die Erfindung genutzte Schichtaufbau dann besonders positiv auf die Schweißeignung und die Phosphatierbarkeit bei gleichzeitig nach wie vor guter Korrosionsschutzwirkung des Überzuges aus, wenn die Dicke der Zwischenschicht erfindungsgemäß mindestens 25 % der Gesamtdicke des Korrosionsschutzüberzugs beträgt. Die hier und in den Ansprüchen enthaltenen Angaben zum Aufbau der Korrosionsüberzugsschicht und ihrer einzelnen Schichten beziehen sich auf ein mit einer GDOS-Messung (glow discharge optical emission spectrometry) ermitteltes Schichtprofil. Bei dem beispielsweise im VDI-Lexikon Werkstofftechnik, hrsg. von Hubert Gräfen, VDI-Verlag GmbH, Düsseldorf 1993 beschriebenen GDOS-Messverfahren handelt es sich um ein Standardverfahren zum schnellen Erfassen eines Konzentrationsprofils von Beschichtungen.In addition, the layer structure used by the invention then has a particularly positive effect on the weldability and the phosphatability with at the same time still good corrosion protection of the coating, if the thickness of the intermediate layer according to the invention is at least 25% of the total thickness of the anticorrosive coating. The information on the structure of the corrosion-coating layer and its individual layers contained herein and in the claims relates to a layer profile determined by a GDOS measurement (glow discharge optical emission spectrometry). For example, in the VDI Lexicon Materials, ed. The GDOS measuring method described by Hubert Gräfen, VDI-Verlag GmbH, Dusseldorf, 1993 is a standard method for rapidly detecting a concentration profile of coatings.
Bei erfindungsgemäß hergestellten Stahlflachprofilen zeigt eine solche GDOS-Messung, dass sich in der unmittelbar an die Oberfläche des Überzugs angrenzenden Oberflächenschicht in Folge von Oxidation herstellungsbedingt unvermeidbar ein erhöhter Al-Gehalt einstellt. Da die Dicke dieser Oberflächenschicht verglichen mit der Gesamtdicke des Überzuges jedoch sehr gering ist, wird die Oberflächenschicht beim Verschweißen eines erfindungsgemäßen Stahlflachprodukts leicht durchbrochen und beeinflusst das Schweißergebnis nur unwesentlich. Um einen möglicherweise negativen Einfluss der höhere Al-Gehalte aufweisenden Oberflächenschicht auszuschließen, sollte die Dicke der Oberflächenschicht auf weniger als 10 %, insbesondere weniger als 1 % der Gesamtdicke des Korrosionsschutzüberzugs beschränkt werden. Praktische Untersuchungen haben bestätigt, dass bei erfindungsgemäß beschaffenen Stahlflachprodukten die Oberflächenschicht jeweils maximal 0,2 µm stark ist, so dass bei üblichen Überzugsdicken von 6 µm und mehr der Anteil der Oberflächengrenzschicht an der Gesamtdicke der Überzugsauflage bei etwa 3,5 % und weit darunter liegt.In the case of flat steel profiles produced according to the invention, such a GDOS measurement shows that in the surface layer immediately adjacent to the surface of the coating, as a result of oxidation, an increased Al content inevitably occurs as a result of oxidation. However, since the thickness of this surface layer is very small compared with the total thickness of the coating, the surface layer is easily broken when welding a flat steel product according to the invention and affects the welding result only insignificantly. In order to exclude a possibly negative influence of the higher Al-containing surface layer, the thickness of the surface layer should be limited to less than 10%, in particular less than 1% of the total thickness of the anticorrosive coating. Practical investigations have confirmed that, in the case of flat steel products produced according to the invention, the surface layer is in each case not more than 0.2 .mu.m thick, so that with conventional coating thicknesses of 6 .mu.m and more, the fraction of the surface boundary layer in the total thickness of the coating overlay is approximately 3.5% and wide below it lies.
Bei erfindungsgemäß hergestellten Stahlflachprodukten weist der Überzug Gehalte an Fe auf, die mehr als 0,3 Gew.-%, insbesondere mehr als 0,4 Gew.-% oder sogar mehr als 0,5 Gew.-% betragen. Die relativ hohen Fe-Gehalte sind dabei insbesondere im Bereich der an das Stahlsubstrat angrenzenden Grenzschicht vorhanden. In dieser kommt es bevorzugt zu einer Legierungsbildung, durch die eine optimierte Haftung des Überzugs auf dem Stahlsubstrat gewährleistet ist. Auf diese Weise weist ein erfindungsgemäß beschaffenes Stahlflachprodukt Gebrauchseigenschaften auf, die den konventionellen Stahlflachprodukten auch dann überlegen sind, wenn sie hohe Mg- und Al-Gehalte in ihrem Schutzüberzug aufweisen.In the case of flat steel products produced according to the invention, the coating has contents of Fe which are more than 0.3% by weight, in particular more than 0.4% by weight or even more than 0.5% by weight. The relatively high Fe contents are present in particular in the region of the boundary layer adjacent to the steel substrate. In this case, it is preferable to form an alloy by which an optimized adhesion of the coating to the steel substrate is ensured. In this way, a flat steel product obtained according to the invention has Performance characteristics, which are superior to the conventional flat steel products, even if they have high Mg and Al contents in their protective coating.
Um zusätzlich zum erfindungsgemäßen Schichtaufbau des Korrosionsschutzüberzugs die Verschweißbarkeit und Phosphatierbarkeit eines erfindungsgemäß hergestellten Stahlflachprodukts weiter zu optimieren, kann der Al-Gehalt des Korrosionsschutzüberzugs auf weniger als 0,6 Gew.-%, insbesondere weniger als 0,5 Gew.-% beschränkt werden.In order to further optimize the weldability and phosphatability of a flat steel product produced according to the invention in addition to the layer structure of the anticorrosive coating according to the invention, the Al content of the anticorrosive coating can be limited to less than 0.6% by weight, in particular less than 0.5% by weight.
Um seine Wirkung zu sichern, sollte die Gesamtdicke des Korrosionsschutzüberzugs mindestens 5 µm, insbesondere mindestens 7 µm betragen. Dabei erweisen sich Auflagengewichtsverteilung des Korrosionsschutzüberzugs von mindestens 100 g/m2 als hinsichtlich seiner Schutzwirkung besonders günstig. Trotz höherer Auflagenstärke und Dicke des Korrosionsschutzüberzugs wird auf Grund der erfindungsgemäß vorgeschriebenen Verteilung seines Al-Gehalts die Schweißbarkeit nicht negativ beeinträchtigt.To ensure its effectiveness, the total thickness of the anticorrosive coating should be at least 5 μm , in particular at least 7 μm . In this case, pad weight distribution of the anticorrosive coating of at least 100 g / m 2 prove to be particularly favorable in terms of its protective effect. Despite higher print run thickness and thickness of the anti-corrosion coating, the weldability is not adversely affected due to the invention prescribed distribution of its Al content.
Besonders gute Produktergebnisse stellen sich ein, wenn die Badtemperatur des Schmelzenbades 440 - 480 °C beträgt.Particularly good product results occur when the bath temperature of the melt bath is 440-480 ° C.
Überraschend hat sich herausgestellt, dass die Geschwindigkeit, mit der das Stahlsubstrat das Schmelzenbad durchläuft, nur einen untergeordneten Einfluss auf das Beschichtungsergebnis hat. Daher kann sie beispielsweise im Bereich von 50 - 200 m/min variiert werden, um das jeweils optimale Arbeitsergebnis bei maximaler Produktivität zu erzielen.Surprisingly, it has been found that the speed with which the steel substrate passes through the melt bath has only a minor influence on the coating result. Therefore, it can be varied in the range of 50 - 200 m / min, for example, in order to achieve the optimum work result at maximum productivity.
Die dem Schmelzenbad vorausgehende Glühung des Stahlbands sollte unter einer Schutzgasatmosphäre durchgeführt werden, um eine Oxidation der Blechoberfläche zu vermeiden. Dazu enthält die Schutzgasatmosphäre in an sich bekannter Weise mehr als 3,5 Vol.-% H2 und jeweils als Rest N2. Die Glühtemperatur liegt dabei in ebenfalls an sich bekannter Weise im Bereich von 700 - 900 °C.The annealing of the steel strip, which precedes the melt bath, should be carried out under a protective gas atmosphere in order to avoid oxidation of the sheet surface. For this purpose, the protective gas atmosphere in a conventional manner contains more than 3.5 vol .-% H 2 and in each case as the radical N 2 . The annealing temperature is also in a known manner in the range of 700 - 900 ° C.
Indem die Bandeintrittstemperatur des Stahlsubstrats im Bereich von -10 °C bis +70 °C von der Temperatur des Schmelzenbades abweicht, wird auch erreicht, dass das Schmelzenbad seine optimale Temperatur trotz des Eintritts des Stahlsubstrats gleichmäßig beibehält.By deviating the strip entrance temperature of the steel substrate in the range of -10 ° C to +70 ° C from the temperature of the melt bath, it is also achieved that the melt bath maintains its optimum temperature evenly despite the entry of the steel substrate.
Das Schmelzenbad selbst enthält bevorzugt allenfalls Spuren von Eisen, da sich erfindungsgemäß der Fe-Gehalt der Korrosionsüberzugsschicht durch Einlegierung von Eisen einstellen soll, der aus dem Stahlsubstrat stammt. Dementsprechend ist der Fe-Gehalt des Schmelzenbades bevorzugt auf höchstens 0,1 Gew.-%, insbesondere höchstens 0,07 Gew.-% beschränkt.The melt bath itself preferably contains at best traces of iron, since according to the invention the Fe content of the corrosion-coating layer is to be established by alloying in iron originating from the steel substrate. Accordingly, the Fe content of the melt bath is preferably limited to at most 0.1 wt%, more preferably at most 0.07 wt%.
Die gute Verarbeitbarkeit, der gleichzeitig gute Korrosionsschutz und die gute Phosphatierbarkeit sind unabhängig von der Art und Beschaffenheit des Stahlsubstrats gegeben. So haben praktische Versuche ergeben, dass keine wesentlichen Unterschiede in den Eigenschaften von erfindungsgemäß hergestellten Stahlflachprodukten eintreten, wenn es sich bei dem Stahlsubstrat um einen IF-Stahl, beispielsweise einen konventionellen mikro-legierten Stahl, oder einen normal legierten Stahl, wie einem konventionellen Qualitätsstahl, handelt.The good processability, the simultaneously good corrosion protection and the good phosphatability are given regardless of the nature and condition of the steel substrate. Thus, practical experiments have shown that there are no significant differences in the properties of flat steel products produced according to the invention when the steel substrate is an IF steel, for example a conventional micro-alloyed steel, or a normal one alloyed steel, like a conventional quality steel.
Nachfolgend wird die Erfindung anhand von Ausführungsbeispielen erläutert. Es zeigen:
- Diag. 1
- die bildliche Darstellung der durch eine GDOS-Messung ermittelten Verteilung der Gehalte an Zn, Mg, Al und Fe über die Dicke eines auf einem Stahlsubstrat aufgebrachten ersten Korrosionsschutzüberzugs;
- Diag. 2
- die bildliche Darstellung der Verteilung der durch eine GDOS-Messung ermittelten Gehalte an Zn, Mg, Al und Fe über die Dicke eines auf einem Stahlsubstrat aufgebrachten zweiten Korrosionsschutzüberzugs.
- Diag. 1
- the pictorial representation of the distribution of the contents of Zn, Mg, Al and Fe over the thickness of a first anticorrosive coating applied to a steel substrate, as determined by a GDOS measurement;
- Diag. 2
- the representation of the distribution of determined by a GDOS measurement levels of Zn, Mg, Al and Fe over the thickness of a deposited on a steel substrate second corrosion protection coating.
Zur Herstellung von gut punktschweißbaren und phosphatierbaren Proben von Stahlflachprodukten mit hoher Korrosionsbeständigkeit ist auf ein als Stahlsubstrat dienendes Stahlband unter einer 5 % H2 enthaltenden Stickstoffatmosphäre, deren Taupunkt bei -30 °C ± 2 °C lag, für eine Haltezeit von jeweils 60 s geglüht worden. Die Glühtemperatur betrug 800 °C bei einer Aufheizrate von 10 °C/s.For the production of good spot-weldable and phosphatizable samples of high corrosion resistant steel flat products, a steel atmosphere steel strip under a nitrogen atmosphere containing 5% H 2 and having a dew point of -30 ° C ± 2 ° C is annealed for a holding time of 60 s each Service. The annealing temperature was 800 ° C at a heating rate of 10 ° C / s.
Nach dem Glühen ist das Stahlband mit einer Abkühlrate von 5 bis 30 °C/s beschleunigt auf eine Temperatur von 470 °C ± 5 °C abgekühlt worden, auf der es für 30 s gehalten worden ist. Anschließend ist das Stahlband mit einer Bandeintauchgeschwindigkeit von 100 m/min in ein Schmelzenbad geleitet worden, dessen Badtemperatur 460 °C ± 5 °C betrug. Die Bandeintrittstemperatur des Stahlbands lag jeweils 5 °C oberhalb der Badtemperatur des Schmelzenbades.After annealing, the steel strip was quenched at a cooling rate of 5 to 30 ° C / s to a temperature of 470 ° C ± 5 ° C where it was held for 30 seconds. Then the steel strip is with a belt immersion speed of 100 m / min was passed into a melt bath whose bath temperature was 460 ° C ± 5 ° C. The strip inlet temperature of the steel strip was in each
Die jeweilige Zusammensetzung des Schmelzenbades sowie die Analysen des sich durch die Feuerverzinkung im Schmelzenbad auf der Ober- und Unterseite des Korrosionsschutzüberzuges sind in Tabelle 1 für zwölf in der voranstehend beschriebenen Weise beschichtete Proben E1 - E12 - soweit ermittelt - zusammengestellt. Es zeigt sich, dass die auf dem Stahlsubstrat jeweils gebildeten Überzüge hohe Anteile an Fe aufweisen. Die im Zuge der Erzeugung des Überzugs eingetretene Auflegierung mit Fe stellt ein besonders hohes Haftungsvermögen des Überzugs auf dem Stahlsubstrat sicher.The respective composition of the melt bath and the analyzes of the hot dip galvanizing in the melt bath on the top and bottom of the anti-corrosion coating are summarized in Table 1 for twelve coated in the manner described above E1 - E12 - as far as determined. It turns out that the coatings formed on the steel substrate each have high levels of Fe. The alloying with Fe which occurs during the production of the coating ensures a particularly high adhesion of the coating to the steel substrate.
Darüber hinaus ergaben Analysen der Verteilung der Gehalte an Zn, Al, Mg und Fe über die Dicke des jeweils auf dem Stahlsubstrat gebildeten Korrosionsschutzüberzugs, dass der Al-Gehalt des Überzugs in einer oberflächennahen Zwischenschicht, deren Dicke jeweils mehr als 25 % der Auflagendicke (Gesamtdicke) des Überzugs beträgt, jeweils unter 0,2 % liegt. Die entsprechende Verteilung über die Dicke D (Oberfläche D = 0 µm) ist für die Proben E1 und E2 in den Diagrammen 1 und 2 bildlich dargestellt.In addition, analysis of the distribution of contents of Zn, Al, Mg and Fe over the thickness of the anticorrosive coating formed on the steel substrate revealed that the Al content of the coating in a near-surface intermediate layer each exceeding 25% of the overlay thickness (total thickness ) of the coating is less than 0.2%. The corresponding distribution across the thickness D (surface D = 0 μ m) is shown pictorially for the samples E1 and E2 in the diagrams 1 and 2.
In den Diagrammen ist zu erkennen, dass sich an der Oberfläche des jeweiligen Überzugs eine Oberflächengrenzschicht gebildet hat, deren Al-Gehalt in Folge von Oxidation hoch ist. Die Dicke dieser Oberflächengrenzschicht liegt jedoch bei maximal 0,2 µm und wird daher beim Punkt- oder Laserschweißen leicht durchbrochen, ohne dass es zu einer Beeinträchtigung der Qualität des Schweißergebnisses kommt.It can be seen in the diagrams that a surface boundary layer has formed on the surface of the respective coating whose Al content is high as a result of oxidation. However, the thickness of this surface boundary layer is at most 0.2 μ m and is therefore easily broken in the spot or laser welding, without causing a deterioration in the quality of the welding result.
An die Oberflächengrenzschicht schließt sich die etwa 2,5 µm dicke Zwischenschicht an, deren Al-Gehalt jeweils unter 0,2 % liegt. Die Dicke der Zwischenschicht liegt somit bei rund 36 % der Gesamtauflagendicke des jeweiligen Korrosionsschutzüberzugs von 7 µm.The about 2.5 μ m thick intermediate layer to the surface boundary layer includes, whose Al content is below 0.2%, respectively. The thickness of the intermediate layer is therefore approximately 36% of the total overlay thickness of the respective anti-corrosion coating of 7 μm .
Die Zwischenschicht geht über in eine am Stahlsubstrat anliegende Grenzschicht, in der die Gehalte an Al, Mg und Fe gegenüber den korrespondierenden Gehalten der Zwischenschicht deutlich angestiegen sind.The intermediate layer merges into a boundary layer adjacent to the steel substrate, in which the contents of Al, Mg and Fe have increased significantly compared with the corresponding contents of the intermediate layer.
Um die Abhängigkeit des Schichtaufbaus und der Zusammensetzung eines erfindungsgemäß erzeugten Korrosionsüberzugs vom jeweils verarbeiteten Stahlsubstrat und von der Bandeintritts- bzw. Badtemperatur zu überprüfen, sind basierend auf einem konventionellen mikro-legierten Stahl IF und einem ebenso konventionellen Qualitätsstahl QS weitere Proben E13 - E22 im Laborversuch mit einem Korrosionsschutzüberzug erzeugt worden. Die Zusammensetzung der Stähle IF und QS sind in Tabelle 3 angegeben.In order to check the dependence of the layer structure and the composition of a corrosion coating produced according to the invention from the respectively processed steel substrate and from the strip inlet or bath temperature, further samples E13-E22 are in laboratory experiment based on a conventional micro-alloyed steel IF and a likewise conventional quality steel QS produced with a corrosion protection coating. The composition of the steels IF and QS are given in Table 3.
Die bei den Laborversuchen eingestellten Betriebsparameter sowie eine Analyse der entsprechend erzeugten Überzugsschicht sind in Tabelle 2 zusammengefasst. Es zeigte sich, dass das Ergebnis der Beschichtung insbesondere im Hinblick auf die Einbindung von hohen aus dem Stahlsubstrat stammenden Fe-Gehalten und die Ausbildung der oberflächennahen Zwischenschicht mit unterhalb von 0,25 Gew.-% liegenden Al-Gehalten unabhängig von der Zusammensetzung des Stahlsubstrats ist.The operating parameters set in the laboratory tests and an analysis of the correspondingly produced coating layer are summarized in Table 2. It was found that the result of the coating, in particular with regard to the incorporation of high Fe contents originating from the steel substrate, and the formation of the near-surface intermediate layer having Al contents below 0.25% by weight, irrespective of the composition of the steel substrate.
Insgesamt haben an den Proben E1 - E22 vorgenommene Untersuchungen bestätigt, dass bei einem erfindungsgemäß erzeugten Korrosionsschutzüberzug in der unmittelbar an die Oberfläche des Überzugs angrenzenden Oberflächengrenzschicht die Elemente Mg und Al als Oxid angereichert vorhanden sind. Daneben liegt Zn-Oxid an der Oberfläche vor.Overall, investigations carried out on samples E1-E22 have confirmed that in the case of a corrosion protection coating produced according to the invention in the surface boundary layer immediately adjacent to the surface of the coating, the elements Mg and Al are enriched in the form of oxide. In addition, Zn oxide is present on the surface.
Zusätzlich sind Betriebsversuche B1 - B19 durchgeführt worden, bei denen als Stahlsubstrat aus dem Qualitätsstahl QS bestehende Stahlbänder verwendet worden sind. Die dabei eingestellten Betriebsparameter, die jeweilige Schmelzenbadzusammensetzung sowie eine Analyse der jeweils auf dem Stahlsubstrat erhaltenen Korrosionsschutzschicht sind in Tabelle 4 angegeben.In addition, operational tests B1 - B19 were carried out, in which existing steel strips were used as steel substrate made of quality steel QS. The operating parameters set, the respective Schmelzenbadzusammensetzung and an analysis of each obtained on the steel substrate corrosion protection layer are given in Table 4.
Die Betriebsversuche haben das Ergebnis der vorangegangenen Laborversuche im vollen Umfang bestätigt. Die Dicke der die oberflächige Oxidation aufnehmenden Oberflächengrenzschicht beträgt bei den untersuchten Proben max. 0,2 µm und liegt bezogen auf das bei einer GDOS-Messung ermittelte Schichtprofil jeweils im Bereich von bis zu 2,7 % der Gesamtauflagendicken. Der Betrag der Al-Anreicherung an der unmittelbaren Oberfläche liegt maximal bei etwa 1 Gew.-%. Daran schließt sich bis zu einer Dicke von mindestens 25 % der Gesamtauflage des Überzuges die Zwischenschicht mit niedrigem Al-Gehalt von maximal 0,25 Gew.-% an. In der Grenzschicht steigt danach der Al-Gehalt bis 4,5 % an der Grenze zum Stahlsubstrat an. Die Mg-Anreicherung an der unmittelbaren Oberfläche des Überzugs ist deutlich größer als die Al-Anreicherung. Es werden hier Mg-Anteile von bis zu 20 % erreicht. Danach nimmt der Mg-Anteil über die Zwischenschicht ab und beträgt in einer Tiefe von etwa 25 % der Gesamtauflagendicke des Überzuges 0,5 bis 2 %. Über die Grenzschicht findet dann ein Anstieg auch des Mg-Gehaltes in Richtung des Stahlsubstrats ab. An der Grenze zum Stahlsubstrat beträgt der Mg-Gehalt bis zu 3,5 %.
Claims (4)
- Method for the production of a flat steel product, in which on the steel substrate, such as a steel belt or a steel sheet, a corrosion protective coating with a total thickness of at least 5 µm is generated, while the steel substrate is annealed under a protective gas atmosphere containing more than 3.5 volume percent H2 and as a residue N2 at an annealing temperature of 700 - 900 °C and starting from the annealing temperature is cooled to a belt entry temperature, with which the steel substrate enters into a molten bath (in weight percent) 0.1 - 0.4 % Al, 0.25 - 2.5 % Mg. up to 0.2 % Fe, containing residue zinc as well as unavoidable impurities and heated to a bath temperature of 420 - 500 °C, wherein the difference "BET-BT" between the belt entry temperature "BET" and the bath temperature "BT" is -10 °C to + 70 °C and is varied such that a corrosion protective coating is formed on the steel substrate, which in (in weight percent)Mg: 0.25 - 2.5 %,Al: 0.2 - 3.0 %,Fe: more than 0.3 - 4.0%,as well as optionally in total up to 0.8% of one or several elements from the group "Pb, Bi, Cd, Ti, B, Si, Cu, Ni, Co, Cr, Mn, Sn as well as rare earths,"
contains residue zinc and unavoidable impurities and which in an intermediate layer, which extends between a surface layer directly abutting the surface of the flat steel product and a boundary layer abutting the steel substrate and the thickness of which is at least 20 % of the total thickness of the corrosion protective layer, has an Al content of at most 0.5 weight percent. - Method according to Claim 1, characterised in that the bath temperature is 440 - 480 °C.
- Method according to any one of the preceding claims, characterised in that the belt entry temperature is 410 - 510 °C.
- Method according to any one of the preceding claims, characterised in that the Fe-content of the molten bath is ≤ 0.1 weight percent.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL06113962T PL1857566T3 (en) | 2006-05-15 | 2006-05-15 | Flat steel product provided with a corrosion protection coating and method of its manufacture |
EP06113962.2A EP1857566B1 (en) | 2006-05-15 | 2006-05-15 | Flat steel product provided with a corrosion protection coating and method of its manufacture |
ES06113962.2T ES2636442T3 (en) | 2006-05-15 | 2006-05-15 | Flat steel product provided with an anticorrosive coating and manufacturing process |
CN2007800176280A CN101454473B (en) | 2006-05-15 | 2007-05-15 | Sheet steel product provided with an anticorrosion coating and process for producing it |
PCT/EP2007/054711 WO2007132007A1 (en) | 2006-05-15 | 2007-05-15 | Sheet steel product provided with an anticorrosion coating and process for producing it |
JP2009510444A JP5586224B2 (en) | 2006-05-15 | 2007-05-15 | Flat steel product with anticorrosion coating and method for producing flat steel product with anticorrosion coating |
AU2007251550A AU2007251550B2 (en) | 2006-05-15 | 2007-05-15 | Sheet steel product provided with an anticorrosion coating and process for producing it |
US12/300,968 US8481172B2 (en) | 2006-05-15 | 2007-05-15 | Steel sheet product provided with an anticorrosion coating and process for producing it |
CA2650800A CA2650800C (en) | 2006-05-15 | 2007-05-15 | Flat steel product with a corrosion protection coating and method for its production |
KR1020087027954A KR101399085B1 (en) | 2006-05-15 | 2007-05-15 | Sheet steel product provided with an anticorrosion coating and process for producing it |
BRPI0711652-7A BRPI0711652B1 (en) | 2006-05-15 | 2007-05-15 | FLAT STEEL PRODUCT WITH A CORROSION PROTECTION COATING AND METHOD FOR YOUR PRODUCTION |
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EP06113962.2A EP1857566B1 (en) | 2006-05-15 | 2006-05-15 | Flat steel product provided with a corrosion protection coating and method of its manufacture |
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EP1857566B1 true EP1857566B1 (en) | 2017-05-03 |
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US (1) | US8481172B2 (en) |
EP (1) | EP1857566B1 (en) |
JP (1) | JP5586224B2 (en) |
KR (1) | KR101399085B1 (en) |
CN (1) | CN101454473B (en) |
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CA (1) | CA2650800C (en) |
ES (1) | ES2636442T3 (en) |
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2006
- 2006-05-15 ES ES06113962.2T patent/ES2636442T3/en active Active
- 2006-05-15 PL PL06113962T patent/PL1857566T3/en unknown
- 2006-05-15 EP EP06113962.2A patent/EP1857566B1/en not_active Not-in-force
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2007
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- 2007-05-15 BR BRPI0711652-7A patent/BRPI0711652B1/en not_active IP Right Cessation
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- 2007-05-15 JP JP2009510444A patent/JP5586224B2/en not_active Expired - Fee Related
- 2007-05-15 KR KR1020087027954A patent/KR101399085B1/en active IP Right Grant
- 2007-05-15 AU AU2007251550A patent/AU2007251550B2/en not_active Ceased
- 2007-05-15 WO PCT/EP2007/054711 patent/WO2007132007A1/en active Application Filing
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Also Published As
Publication number | Publication date |
---|---|
ES2636442T3 (en) | 2017-10-05 |
WO2007132007A1 (en) | 2007-11-22 |
EP1857566A1 (en) | 2007-11-21 |
JP5586224B2 (en) | 2014-09-10 |
BRPI0711652A2 (en) | 2011-11-29 |
CN101454473A (en) | 2009-06-10 |
AU2007251550A1 (en) | 2007-11-22 |
CN101454473B (en) | 2013-09-18 |
PL1857566T3 (en) | 2017-10-31 |
CA2650800C (en) | 2013-12-03 |
BRPI0711652B1 (en) | 2018-03-06 |
US20100024925A1 (en) | 2010-02-04 |
AU2007251550B2 (en) | 2012-05-03 |
KR101399085B1 (en) | 2014-05-27 |
KR20090007597A (en) | 2009-01-19 |
JP2009537697A (en) | 2009-10-29 |
CA2650800A1 (en) | 2007-11-22 |
US8481172B2 (en) | 2013-07-09 |
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