• 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 process for the surface treatment of a metallic substrate, in particular steel sheet, with a Zn-based protective coating, in particular with a Zn-Al-Mg protective coating, in which a chloride-containing solution is applied to this protective coating, thereby at least partially having a corrosion protection layer Hydrozincite and Simonkolleit and hydrotalcite in particular, is formed. In order to increase the corrosion resistance of the Zn-Al-Mg protective coating or to improve the process in terms of processability and reproducibility, it is proposed that the protective-coated substrate be adjusted with the aid of an acid to a pH in the range of 4 to 6 and reacting a solution containing 1.8 to 18.5% by weight of chloride to form a Simon collagen component in the anticorrosive layer which is increased relative to the hydrozinc titanium portion.
    公开号:AT514229A1
    申请号:T50294/2013
    申请日:2013-04-29
    公开日:2014-11-15
    发明作者:Gerald Luckeneder；Karl-Heinz Dr Stellnberger
    申请人:Voestalpine Stahl Gmbh；
    IPC主号:
    专利说明:

    -1 -
    The invention relates to a process for the surface treatment of a metallic substrate, in particular steel sheet, with a Zn-based protective coating, in particular with a Zn-Al-Mg protective coating, in which a chloride-containing solution is applied to this protective coating and thereby at least partially a Korrosiönsschutzschicht comprising hydrozincite and Simonkolleit and in particular hydrotalcite is formed
    From the prior art it is known to provide steel sheet with a protective coating based on Zn-Al-lVlg in order to increase the corrosion resistance of the steel sheet. Surprisingly, these protective-coated steel sheets nevertheless showed a comparatively strongly fluctuating corrosion resistance.
    Corrosion tests according to DIN EN ISO 9227 (NSS) carried out on these protective coated steel sheets using an aqueous, 5% NaCl solution, pH VV-regulated with NaOH, showed the formation of a corrosion layer with hydrotalcite, hydrozincite and Simonkolleit as constituents (" XPS investigation on the surface chemistry of ZnMgAI-coated Steel ", Duchoslav et al., AOFA 2012). In the corrosion layer, the concentration of hydrozincite Zn5 (CQ3) 2 (OH) 6 was significantly higher than that of Simonkolleit Zn5 (0H) 8CI2 * H20. In addition, hydrotalcite (Zn, Mg) 6Al2 (OH) 16CO3 · 4H20 was found in the corrosion layer. Simonkolleit is also known to have an over hydrozincite increased corrosion resistance.
    In order to increase the concentration of Simonkolleit, WO2012 / 091385A2 proposes to adjust the weight ratios of Al and Mg in the Zn-based protective coating in such a way that the formation of Simonkolleit is facilitated in the event of corrosion. It is proposed that in the protective coating the quotients of Al to (Mg + Al) should be in a range of 0.38 to 0.48. Disadvantageously, however, such compositional provisions cause a relatively high outlay, in particular when protective coatings are to be applied to a metal sheet with the aid of a hot-dip method - the reproducibility of the method is therefore difficult to ensure. In addition, such regulations usually lead only to a compromise between on the one hand improved corrosion behavior on the one hand and undesirable changes in mechanical, chemical and / or electrical properties on the other hand. The usability of the thus protective coated sheet can be significantly limited.
    The invention is therefore based on the object, starting from the above-described prior art, a method for surface treatment of a Zn-based protective coated sheet such that increases the corrosion resistance, reduces the fluctuation range and its production is accelerated. In addition, a high reproducibility of the method should be ensured and the method be applicable regardless of the composition of the protective coating based on Zn.
    The invention solves the stated object in that the protective-coated substrate with the, with the aid of an acid to a pH in the range of 4 to 6 and a 1.8 to 18.5 wt .-% chloride-containing solution to form a compared to the Hydrozinkitanteil increased Simonkolleitanteils in the anticorrosion layer reacts.
    If the protective-coated substrate reacts with the solution adjusted with the aid of an acid to a pH in the range from 4 to 6 and a solution containing from 1.8 to 18.5% by weight of chloride, a particularly advantageous anticorrosion layer can thus be obtained Protective coating can be achieved. This solution according to the invention, in particular also water-based, can in fact considerably promote the formation of silicon monolith on the treated or corroded surface of the protective coating and thus in particular influence the composition of the anticorrosive layer in a direction such that it always does so an increased proportion of Simonkolleit compared to hydrozincite. This can certainly be expected with a high corrosion resistance of the protective coated substrate. In addition, this directional treatment or corroding of the protective coating can be carried out independently of the composition of a Zn-based protective coating - that is, any compositions can be improved in corrosion resistance. A universally applicable and reproducible method can thus be made available, in which the influence of a hot dip method on corrosion resistance or its range of variation with respect to the layer thickness of their patency and composition can be significantly reduced. In particular, however, the aqueous solution according to the invention was able to excel in increasing the corrosion resistance of protective coatings based on Zn-Al-Mg. Their corrosion-susceptible and superficial intermetallic phases can be supplemented with Simonkolleit namely and corrosion-resistant. In addition, this formed a comparatively compact surface coating, which in turn can lead to increased mechanical strength of the protective coating. As a consequence, the improved bondability achieved by this for further layers, for example paints or the like, can be used on this protective coating. In addition, due to the increased chloride content of the solution, the production of the improved corrosion resistance in the protective coating is accelerated and thus the process can be carried out comparatively quickly.
    A solution which has 5 to 30% by weight of NaCl has proved particularly advantageous. This is not only inexpensive and easy to manufacture, it also has positive process engineering influence. In particular, 5 to 10% by weight of NaCl may be suitable for ensuring a sufficiently high chloride content in the solution for the process. 4/12 -4-
    If the pH of the solutions is adjusted with HCl, not only can the activation of the corrosion reaction in the direction of high training of Simonkolleit be accelerated, but also the composition of the solution can not be changed with regard to the number of components. This can have a positive effect on the reproducibility of the process.
    It can be particularly advantageous if the solution applied to the protective coating consists of water, NaCl and HCl. Of course, this solution may also have production-related unavoidable impurities. This solution, which was easy to prepare, proved particularly advantageous in the reaction with a Zn-Al-Mg protective coating, in which a proportion of Simonkolleit of more than 80% formed in the treated areas of the protective coating.
    A comparatively high proportion of Simonkolleit can be ensured by the solution reacting with the coating for a maximum of 20 minutes. Even with this relatively short reaction time, the method according to the invention can also ensure a particularly rapid process and, in turn, be suitable even for industrial purposes.
    The reaction time of the solution with the protective coating can be further reduced if the metallic substrate is anodically charged in the reaction with the solution.
    If the temperature of the solution is adjusted to a range of 30 to 60 degrees Celsius, the training of Simonkolleit can be fostered, thus further speeding up the process.
    The invention can be distinguished in particular with Zn-based protective coatings which are applied to the metal sheet by means of a hot-dip method. Known parameter fluctuations of the hot dip process, which can have an influence on the corrosion resistance of the protective coating formed therewith, can thus be compensated for. The method according to the invention can therefore ensure particularly highly reproducible corrosion protection on sheets.
    If the reaction of the solution with the protective coating forms a corrosion protection layer with a layer thickness in the range from 150 nm to 1.5 μm, a sufficiently compact reaction layer with simonollector can be obtained in order to reproducibly increase the corrosion resistance of the protective-coated substrate.
    The chemical resistance of the Zn-based protective coating can be further increased if the reaction of the solution with the protective coating forms a corrosion protection layer in a proportion of at least 80%, in particular of at least 90%, Simonkolleit.
    The method according to the invention can be distinguished in particular with a Zn-Al-Mg protective coating in which the quotient of Al / (Al + Mg) is in the range from 0.5 to 1.0, in particular when quotient of Al / (Al + Mg) is 0.5.
    In the following, the invention will be explained in more detail by way of example with reference to exemplary embodiments:
    In order to demonstrate the improved corrosion resistance achieved, two Zn-Al-Mg coated steel sheets were surface treated according to the invention with a solution consisting of NaCl, HCl and water together with unavoidable production-related impurities and compared with a Zn-Al-Mg coated steel sheet without inventive surface treatment. The quotient of Al / (Al + Mg) of the Zn-Al-Mg protective coating area is set to 0.5. 6/12 -6-
    The tested protective coated steel sheets are shown in Table 1.
    Composition of the solution Simonkolleit hydrozincite hydrotalcite 1 no treatment and efiniert / variable 2 5% NaCl with a pH of 4-5 90% 5% 5% 3 10% NaCl with a pH of 5 90% 5% 5%
    Table 1: Overview of the examined protective coated steel sheets 1,2, 3
    The protective coated sheets treated with the solution according to the invention each exhibited compact anticorrosive layers with layer thicknesses in the range from 150 nm to 1.5 pm.
    An increased corrosion resistance of the Zn ^ Al-Mg protective coating could be achieved in the protective coated steel sheet 2 already after 10 minutes and a temperature of the solution in the amount of 30 degrees Celsius, wherein in the reaction of the solution with the protective coating anodic load (20V, 50Am '2) was created.
    The same increased corrosion resistance of the Zn-Al-Mg protective coating could be achieved in the protective coated steel sheet 3 after 20 minutes and a solution temperature of 60 degrees Celsius. Anodic loading of the protective coating could be dispensed with here. 7/12
    权利要求:
    Claims (11)
    [1]
    Claims 1. A process for the surface treatment of a metallic substrate, in particular steel sheet, with a Zn-based protective coating, in particular with a Zn-Al-Mg protective coating, in which a chloride-containing solution is applied to this protective coating and thereby at least in some areas a corrosion protection layer comprising hydrozincite and Simonkolleit and in particular hydrotalcite is formed, characterized in that the protective-coated substrate with the, with the aid of an acid to a pH in the range of 4 to 6 and a 1.8 to 18, 5 wt .-% chloride-containing solution to form a relative to the Hydrozinkitanteil increased Simonkolleitanteils in the corrosion protection layer reacts.
    [2]
    2. The method according to claim 1, characterized in that the solution has 5 to 30 wt .-%, in particular 5 to 10 wt .-%, NaCl,
    [3]
    3. The method according to claim 1 or 2, characterized in that the pH of the solutions is adjusted with HCl.
    [4]
    4. The method according to claim 3, characterized in that, applied to the protective coating solution consists of water, NaCl and HCl.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that the solution reacts for a maximum of 20 minutes with the coating.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that the metallic substrate is charged anodically in the reaction with the solution. 8/12 2
    [7]
    7, Method according to one of claims 1 to 6, characterized in that the temperature of the solution is adjusted to a range of 30 to 60 degrees Celsius
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that the protective coating Zn-based is applied by means of a hot dip method on the sheet.
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that the reaction of the solution with the protective coating forms a KorröSionsschutzschicht with a layer thickness in the range of 150nm to 1.5 pm.
    [10]
    10. The method according to any one of claims 1 to 9, characterized in that the reaction of the solution with the protective coating forms a corrosion protection layer with a proportion of at least 80%, in particular of at least 90%, Simon-Kolleit.
    [11]
    11. The method according to any one of claims 1 to 10, characterized in that in the Zn-Al-Mg protective coating, the quotient of Al / (Al + Mg) in the range of 0.5 to 1.0, preferably 0.5 is. 12.9
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    引用文献:
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    法律状态:
    优先权:
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