• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method for producing a steel product coated with a metallic anti-corrosion layer, in which at least one metallic protective layer in the form of a zinc alloy is applied to a steel substrate, such as steel strip or sheet steel. In order to achieve steel products, in particular flat steel products with improved surface and edge corrosion protection and high heat resistance for improved fire protection, the invention provides that the applied zinc alloy has a magnesium content of at least 0.8 to 5.0% by weight, preferably at least 0. 9 to 3.0% by weight, and that the steel substrate coated with the at least one metallic protective layer is anodized.
    公开号:BE1022108B1
    申请号:E2013/0613
    申请日:2013-09-18
    公开日:2016-02-16
    发明作者:Böger Thorsten；Peter Klauke；Anastasia Schübler
    申请人:Thyssenskrupp Steel Europe Ag；
    IPC主号:
    专利说明:

    Method of producing a metallic anticorrosive coating
    Steel product.
    The invention relates to a method for producing a metal product coated with a metallic corrosion protection layer, in which at least one metallic protective layer in the form of a zinc alloy is applied to a steel substrate, such as steel strip or sheet steel.
    To improve their resistance to corrosion, in particular steel sheets and steel strips are coated with metallic coatings, which in the majority of applications are based on zinc or zinc alloys. Due to their barrier and cathodic protective action, such zinc or zinc alloy coatings protect the correspondingly coated steel substrate against corrosion in practical use.
    The corrosion resistance of galvanized steel sheets can be further improved by applying an additional organic coating, in particular a paint coating. A corresponding process in which a zinc-based coating is applied to a strip-shaped steel substrate by means of hot dip coating and in which an organic coating, typically serving as a primer and then a lacquer, is applied to the zinc-based coating is known, for example from US Pat EP 1 857 567 A1. Such coated with a metallic coating and an organic coating corrosion protection system flat steel products have basically proven in practice and are usually characterized by a particularly good corrosion protection. Unsatisfactory, however, is the relatively low temperature resistance of such a coating structure (corrosion protection system) and the behavior of the organic coating in case of fire, in which it can lead to smoke and thus negative, harmful emissions.
    A further requirement for components made of sheet steel or steel strip and provided with a corrosion-protection coating is that reliable corrosion protection at the cutting edge is ensured even after machining or post-processing on the construction site, for example after trimming.
    Against this background, the present invention has the object to provide a method that allows an economical production of highly corrosion-resistant steel products, especially flat steel products with improved surface and edge corrosion protection and improved behavior in case of fire.
    To solve this problem, a method with the features of claim 1 is proposed.
    The abovementioned object is thus achieved in a method for producing a steel product coated with a metallic corrosion protection layer, in which at least one metallic protective layer in the form of a zinc alloy is applied to a steel substrate, such as steel strip or sheet steel, by at least 0.8 - 5.0 wt .-% Mg, preferably at least 0.9 - 3.0 wt .-% Mg, and that the coated with the at least one metallic protective layer steel substrate is anodized.
    The zinc-containing protective layer achieves an advantageous cathodic corrosion protection effect on surfaces and on cut edges. In this case, the zinc-containing protective layer is gradually sacrificed in the presence of an electrolyte due to the different electrochemical potential. Moreover, by anodizing the steel substrate coated with at least one such metallic protective layer, a metal oxide layer is produced which has high temperature resistance and additionally primarily protects the areal areas against corrosion. As a result, steel products produced according to the invention are thus distinguished by improved corrosion protection and, moreover, by the prevention of smoke development in the event of fire, offer improved fire protection. Furthermore, the inventive
    Implement method also economically advantageous, for example by 2 strip-shaped steel sheet is treated according to the invention in a continuous flow.
    Improved surface corrosion resistance and improved heat and fire resistance of a zinc alloy-coated steel substrate can be achieved in particular if, according to a preferred embodiment of the method according to the invention, the applied zinc alloy at least 0.05 to 10.0 wt .-% Al, preferably at least 0.2 to 10.0 wt .-% Al has.
    A further advantageous embodiment of the method according to the invention is characterized in that at least one further metallic protective layer is applied to the at least one metallic protective layer before the coated steel substrate is anodized, wherein the at least one further metallic protective layer of aluminum or an Al alloy (eg Aluminum-silicon alloy) is formed. This refinement offers process engineering advantages with regard to optimum, weight-reduced thickness adjustment of the zinc-based protective layer on the one hand and the formation of a particularly effective aluminum or aluminum-based oxide layer against corrosion on the other hand.
    The at least one (first) metallic corrosion protection layer is preferably applied by hot-dip galvanizing (hot dipping). However, the application of this metallic protective layer can also be effected by other suitable coating methods, for example by electrolytic methods, chemical vapor deposition (CVD), physical vapor deposition (PVD), etc.
    The anodizing of the zinc-coated steel substrate may optionally be preceded or subordinated by a preliminary or intermediate treatment, in particular a temper rolling and / or heat treatment.
    A further preferred embodiment of the method according to the invention provides that the hot-dip galvanized steel substrate in another
    Hot dip coating process (hot dip coating process) is coated with an aluminum-based protective layer before it is anodized. In the course of heating (annealing) the galvanized steel substrate, preferably steel strip, to molten bath dipping temperature, iron diffuses from the steel substrate into the zinc layer, so that the zinc layer is converted into a zinc-iron alloy layer which is highly wettable for the second Al-based coating is. However, other coating methods for applying the second metallic protective layer, i. the aluminum-based protective layer for realizing the method according to the invention conceivable.
    A further advantageous embodiment of the method according to the invention is characterized in that the coated steel substrate is selectively colored during the anodization by adding at least one additive to the electrolyte. As a result, the visual impression of the steel product to be produced can be variably influenced or adjusted in a very wide range according to the wishes of the customer or end user, and thus expensive painting processes can be dispensed with.
    With regard to the technical implementation of the method according to the invention and its economy, it is also advantageous if according to a further preferred embodiment, the coated and anodized steel substrate is wound into a coil, and if for the production of three-dimensionally shaped components from the coated and anodized steel substrate partial lengths of the coil unwound and / or cut to length and then reshaped.
    An alternative embodiment of the method according to the invention provides, however, that for the production of three-dimensionally shaped components from the coated steel substrate, the same or a blank formed from the steel substrate and the resulting component is then anodized. In this embodiment, the anodizing thus takes place only on the three-dimensionally shaped component. This variant of the method is particularly advantageous if the component coated with at least one metallic corrosion protection layer, in particular steel strip, has a component with a complex three-dimensional shape
    Geometry is to be formed, which may possibly lead to an impairment of the metal oxide layer produced by the anodization. This risk is eliminated by the anodizing (piece-anodizing) performed temporally after the forming of the coated steel substrate according to the invention.
    The invention will be explained in more detail by means of exemplary embodiments. Show it:
    1 shows a sequence of the working steps of a first variant of a method for producing a steel product coated with a metallic corrosion protection layer;
    FIG. 2 shows a sequence of the working steps of a second variant of a method for producing a steel product coated with a metallic corrosion protection layer; FIG.
    3 shows a layer structure of a steel flat product provided with a corrosion protection coating; and
    Fig. 4 shows a layer structure of another provided with a corrosion protective cover flat steel product.
    In FIGS. 1 and 2, the sequences of working steps of the method according to the invention for producing a steel product coated with a metallic corrosion protection layer are shown by way of example in two variants.
    In the variant illustrated in FIG. 1, preferably all working steps are carried out in a continuous pass. In this case, the respective steel substrate (steel sheet or steel strip) is first preheated, then galvanized by immersion in a zinc alloy containing melt bath and then fed to a stripping device in which the layer thickness of the zinc-based corrosion protection coating is adjusted by stripping excess coating material.
    Depending on the steel grade, it is preheated to a maximum temperature of approx. 720 ° C to 850 ° C in order to optimally prepare the steel substrate for galvanizing in the zinc bath. The preheating can typically take place in a directly fired or indirectly heated annealing furnace. In order to avoid oxidation of the surface of the steel substrate during preheating, the heating (annealing) is carried out under protective gas. After preheating, the steel substrate is moved under exclusion of air through the zinc bath. For this purpose, it can be conducted into the melt bath in a manner known per se, for example, by means of a trunk connected to the annealing furnace and opening below the melt bath level.
    The zinc bath (molten bath) contains a molten zinc alloy which, in addition to zinc and the usual manufacturing impurities, contains magnesium and optionally aluminum. The composition of the melt is chosen so that forms on the steel substrate, a metallic corrosion protection layer having a magnesium content in the range of 0.8 and 5.0 wt .-%, preferably between 0.9 and 3.0 wt. -% having. Preferably, the melt also contains aluminum, wherein the composition of the melt is then selected so that the applied on the steel substrate metallic corrosion protection layer has an aluminum content in the range of 0.05 and 10.0 wt .-%, preferably between 0.2 and 10.0 wt .-%.
    After passing through the melt bath, the thickness of the metallic anticorrosive layer is adjusted to a value in the range of, for example, 3 to 20 .mu.m, which corresponds to a surface weight of the metallic protective layer of about 20 to 140 g / m.sup.2 per side of the steel substrate. The outstanding corrosion protection effect of protective layers produced according to the invention makes it possible to limit the thickness of the metallic corrosion protection layer to values of 4 to 12 μm, which corresponds to a coating weight of about 30 to 85 g / m 2 per side. With such thin coatings coated steel substrates can be particularly well processed.
    The stripping of excess coating material carried out to adjust the thickness of the metallic corrosion protection layer can be carried out, for example, in a manner known per se by blowing off by means of stripping nozzles. Nitrogen is preferably used as the gas for the gas jets emitted by the wiping nozzles.
    After the steel substrate provided with the zinc-based, Mg-containing and optionally Al-containing metallic anticorrosive coating has been removed from the zinc bath and the thickness of the anticorrosive coating has been adjusted by stripping off excess coating material, the steel substrate is anodized according to the invention.
    For this purpose, the steel substrate provided with the zinc-based, Mg-containing and optionally Al-containing corrosion protection coating is immersed in an electrolyte, wherein the steel substrate is poled as the anode and by applying an electrical voltage a relatively thin metal oxide layer (Mg and optional Al) on the surface of coated steel substarts is generated. The metal oxide layer produced in this way is characterized by a high temperature resistance and, in addition, improves the surface corrosion resistance of the steel substrate coated with the zinc-based corrosion protection coating.
    Before the anodizing of the zinc-coated steel substrate, this may optionally be subjected to a preliminary or intermediate treatment in order to achieve an optimum texturing of its surface for subsequent anodization and / or further processing, in particular reshaping. For example, it is within the scope of the present invention to subject the zinc-coated steel substrate before and / or after anodising a temper rolling. The resulting texturing defines small depressions which, for example, act as lubricant pockets and can improve the forming behavior of the steel substrate coated with the metallic corrosion protection coating. The optional pre-treatment or intermediate treatment, in particular the temper rolling, is preferably carried out in one line and in a continuous pass with the galvanizing process.
    In principle, however, it is also conceivable to carry out the anodizing and / or the optional pre-treatment or intermediate treatment discontinuously in separate processing stations.
    In the process sequence shown in FIG. 2, the steps "preheating", "galvanizing" and "thickness setting" are carried out in a continuous pass as in the case of the method illustrated in FIG. In turn, an optional pre-treatment or intermediate treatment, in particular a skin-pass rolling and / or heat treatment (cooling and / or heating), can follow the thickness adjustment.
    After the thickness adjustment of the zinc-based, metallic corrosion protection coating or the optional pre-treatment or intermediate treatment, the hot-dip galvanized steel substrate is coated in an additional step with an aluminum-based coating. The application of the aluminum-based coating is preferably carried out by means of fire coating. In the course of heating the galvanized steel substrate (steel strip) to melt bath immersion temperature, iron from the steel substrate diffuses into the zinc-based, Mg-containing corrosion protection coating. As a result, this metallic anticorrosive coating is converted into a zinc-iron alloy layer suitable for the
    Al-based coating material for forming the second
    Corrosion protection layer is excellent wettable. In principle, however, other coating methods for applying the aluminum-based layer can also be used in the implementation of the method according to the invention.
    The anodization of the steel substrate coated with at least one metallic corrosion protection layer (see in particular Fig. 1) leads to the formation of a closed, heat-resistant metal oxide layer (magnesium or aluminum oxide layer), which gives the steel substrate improved surface corrosion resistance and improved fire resistance without harmful smoke development. The components produced from the steel substrate treated according to the invention are outstandingly suitable in particular for applications in the construction sector or as building elements, for example as facade cladding elements, roofing elements, garage door elements, wall and ceiling elements for commercial vehicle, rail vehicle and shipbuilding.
    By means of anodising, the hot-dip galvanized steel substrate can also be colored. For this purpose, the hot-dip galvanized steel substrate is selectively colored during the anodization by adding at least one additive to the electrolyte. The color design are virtually unlimited. It is thus possible to dispense with the application of organic coatings, which sometimes require expensive painting processes.
    The galvanized and anodized steel strip according to the invention is preferably wound into a coil. To produce three-dimensionally shaped components, partial lengths can then be unwound from the coil, cut to length and then shaped. Alternatively, blanks can be cut from galvanized steel strip according to the invention and formed into three-dimensionally shaped components. In order not to run the risk of damaging the metal oxide layer in the case of complex geometries, anodizing can, if necessary, only take place on the three-dimensionally shaped component.
    3 does not show to scale a section of a steel flat product produced and obtained in accordance with the invention in cross-section. Accordingly, a metallic corrosion protection coating K, for example, approximately 7.5 μm thick, which consists essentially of Zn, Mg and optionally Al, is applied to a steel sheet or steel strip S first. The magnesium content of the applied zinc alloy K is in the range of 0.8 to 5.0 wt .-%, preferably in the range of 0.9 to 3.0 wt .-%. If the applied zinc alloy K also contains aluminum, the Al content is for example in the range of 0.05 and 10.0 wt .-%, preferably between 0.2 and 10.0 wt .-%. On the metallic zinc-based
    Corrosion protection coating K is a closed, heat-resistant oxide layer O formed by anodizing. The thickness of the oxide layer O is for example about 5 pm.
    Flat steel products of the type shown in Fig. 3 are particularly suitable for applications in the construction sector and in vehicle and shipbuilding. 2
    Fig. 4 does not show to scale a portion of a second in accordance with the invention produced and procured, also for applications in the construction sector and in vehicle and shipbuilding particularly suitable steel flat product in cross section. Accordingly, a metallic anticorrosive coating K which is approximately 7.5 μm thick and which consists essentially of Zn, Mg and optionally Al, is applied in turn to a steel sheet or steel strip S, in turn. On the anticorrosive coating K is an aluminum-based layer A, for example, applied an aluminum-silicon layer. The layer thickness of the aluminum-based layer is for example about 5 to 8 pm. Finally, on the second metallic protective layer A, a closed, heat-resistant oxide layer O is formed by anodizing the coated steel substrate S. The thickness of the oxide layer O is for example about 5 pm.
    权利要求:
    Claims (8)
    [1]
    claims
    Anspruch [en] A method for producing a steel product coated with a metallic corrosion protection layer, wherein at least one metallic protective layer in the form of a zinc alloy is applied to a steel substrate, such as steel strip or sheet steel, characterized in that the applied zinc alloy is at least 0.8 to 5.0 Wt .-% Mg, preferably at least 0.9 to 3.0 wt .-% Mg, and that the coated with the at least one metallic protective layer steel substrate is anodized.
    [2]
    2. The method according to claim 1, characterized in that the applied zinc alloy has at least 0.05 to 10.0 wt .-% AI.
    [3]
    3. The method according to claim 1 or 2, characterized in that at least one further metallic protective layer is applied to the at least one metallic protective layer before the coated steel substrate is anodized, wherein the at least one further metallic protective layer of aluminum or an Al alloy is formed ,
    [4]
    4. The method according to any one of claims 1 to 3, characterized in that the at least one metallic protective layer is applied by hot-dip galvanizing.
    [5]
    5. The method according to claim 4, characterized in that the hot-dip galvanized steel substrate is coated in a further fire-coating process with an aluminum-based protective layer before it is anodized.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that the coated steel substrate is selectively dyed during the anodization by adding at least one additive to the electrolyte.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that the coated and anodized steel substrate is wound into a coil, and that for producing three-dimensionally shaped components from the coated and anodized steel substrate unwound from the coil unwound and / or cut to length and then be reshaped.
    [8]
    8. The method according to any one of claims 1 to 6, characterized in that for the production of three-dimensionally shaped components from the coated steel substrate, the same or a blank formed from the steel substrate and the resulting component is then anodized.
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    同族专利:
    公开号 | 公开日
    DE102012109855A1|2014-04-17|
    DE102012109855B4|2015-07-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20050106403A1|2003-11-13|2005-05-19|Fujitsu Limited|Shaped metal article and method of producing shaped metal article having oxide coating|
    FR2864552A1|2003-12-24|2005-07-01|Usinor|Utilisation of an aqueous treatment solution containing sulphate ions for treating the surface of galvanised steel sheet to provide temporary corrosion protection and lubrication during shaping|
    WO2013104835A1|2012-01-10|2013-07-18|Arcelormittal Investigación Y Desarrollo Sl|Use of a solution containing sulphate ions for reducing the blackening or tarnishing of a metal sheet during the storage thereof and metal sheet treated with such a solution|
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    US20100055344A1|2006-05-15|2010-03-04|Thyssenkrupp Steel Ag|Process for Producing a Sheet Steel Product Coated with an Anticorrosion System|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE102012109855.7A|DE102012109855B4|2012-10-16|2012-10-16|Process for producing a metal corrosion protection coated steel product|
    DE102012109|2013-09-18|
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