WO2021185914A1 - Procédé pour la production de marquages sur une bande d'acier ou tôle d'acier galvanisée et bande d'acier ou tôle d'acier galvanisée ayant un marquage de cette sorte - Google Patents

Procédé pour la production de marquages sur une bande d'acier ou tôle d'acier galvanisée et bande d'acier ou tôle d'acier galvanisée ayant un marquage de cette sorte Download PDF

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Publication number
WO2021185914A1
WO2021185914A1 PCT/EP2021/056831 EP2021056831W WO2021185914A1 WO 2021185914 A1 WO2021185914 A1 WO 2021185914A1 EP 2021056831 W EP2021056831 W EP 2021056831W WO 2021185914 A1 WO2021185914 A1 WO 2021185914A1
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WIPO (PCT)
Prior art keywords
areas
steel
salt solution
zinc
layer
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PCT/EP2021/056831
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German (de)
English (en)
Inventor
Johann Gerdentisch
Thomas Steck
Ernst Commenda
Original Assignee
Voestalpine Stahl Gmbh
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Priority to EP21714105.0A priority Critical patent/EP4121579A1/fr
Publication of WO2021185914A1 publication Critical patent/WO2021185914A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1637—Composition of the substrate metallic substrate
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the invention relates to a method for producing identifications through areas with different visual appearances on galvanized steel strips or steel plates with the features of claim 1.
  • the invention further relates to galvanized steel strips or steel sheets produced by the above-mentioned method with areas with different visual appearances according to the preamble of claim 13.
  • a marking is defined below as a surface change that is visible to the human eye or measurable or detectable for a measuring device, which makes the changed area distinguishable relative to unchanged areas.
  • markings that are visible to the human eye without any aids.
  • a simple example is font of a first color on a background of a different color.
  • markings that are only visible to the human eye when they are illuminated with light of a certain wavelength (e.g. UV light).
  • the human eye is widely used for the detection of such markings. If a marking or change can be detected by the human eye, i.e. the relative differences between the changed area (the "marking") and a background can be detected, one speaks of a visible change or, in this case, marking. Such a marking calls you visible effect to the human eye.
  • a marking on a steel surface can be created by various methods. Markings are often achieved through mechanical and / or chemical processing.
  • depressions can be created by removing material, for example by laser embossing. Elevations are mostly created by applying structuring elements, e.g. by printing.
  • a change in topography changes the surface through elevations or depressions which either cause an optical effect (e.g. through a shadow cast) and are visible to the human eye or can be measured using a measuring device.
  • Screen printing is a printing process in which the material to be applied is applied with a squeegee through a fine-meshed fabric onto the surface to be printed.
  • the mesh openings of the fabric are made impermeable at those points of the fabric where no material is to be applied in accordance with the printed image.
  • Indirect gravure printing is a printing process in which the elements to be imaged are present as depressions in the printing matrix.
  • the entire printing matrix is dipped into the material to be applied before printing and the excess material is removed with a doctor blade so that the material to be applied is only located in the depressions.
  • the material transfer takes place through high contact pressure and adhesive forces between the surface to be printed and the material.
  • Ink-Jet is a matrix printing process in which the material to be applied is in liquid form and is applied by targeted shooting or deflection of small drops of material.
  • the drops of material are generated using a piezoelectric transducer and then electrostatically charged via a charging electrode. Then the Drops of material are accelerated and their trajectory is controlled by means of a deflection electrode. After it hits the surface to be printed, a print image is generated.
  • structuring elements are applied to the surface to be marked. These are mostly foreign substances that have a different chemical composition and therefore different physical properties than the coated surface. This can possibly make further surface treatment or processing of the workpiece more difficult.
  • a change in topography can also be produced by chemical means. It is known to produce depressions on the surface by etching with acids. For this purpose, the metal surface to be treated is brought into contact with, for example, hydrochloric or sulfuric acid. The depth of the marking is directly related to the treatment time.
  • the surface is treated with a basic solution, for example caustic soda, in order to prevent possible corrosion from remaining acid residues.
  • a basic solution for example caustic soda
  • An optical effect or a marking can also be created by means of a coating. It can be an organic or an inorganic coating.
  • An organic coating can be organic lacquers. Optical effects are often created using organic multilayer systems, such as the colofer®vario process. A steel surface is pretreated free of chromate. A chromate-free primer is then applied. The visual effect is defined by a basecoat and a texture layer on top. Finally, a top coat is applied. Several system runs are required for this. This increases the production costs. In addition, further processing of the workpiece coated in this way is made more difficult.
  • An inorganic coating can be a metallic coating, such as a zinc coating. A zinc coating is usually applied for corrosion protection purposes.
  • hot-dip galvanizing also known as hot-dip galvanizing
  • Steel is immersed continuously (e.g. strip or wire) or piece by piece (e.g. components) at temperatures of around 450 ° C to 600 ° C in a melt of liquid zinc (the melting point of zinc is 419.5 ° C).
  • the zinc melt conventionally has a zinc content of at least 98.0% by weight in accordance with DIN EN ISO 1461.
  • the zinc layer has a thickness of 5 ⁇ m to 40 ⁇ m.
  • the zinc layer can have a thickness of 50 ⁇ m to 150 ⁇ m.
  • the steel to be galvanized is introduced into the solution as a cathode and a dimensionally stable electrode is used as the anode. Electricity is passed through the electrolyte solution.
  • the zinc present in ionic form (oxidation level +11) is reduced to metallic zinc and deposited on the steel surface.
  • electrolytic galvanizing can apply thinner layers of zinc.
  • the zinc layer thickness is proportional to the strength and duration of the current flow, whereby - depending on the workpiece and anode geometry - a layer thickness distribution arises over the entire workpiece.
  • Careful surface pretreatment is required to ensure the adhesion and uniformity of the zinc layer. This can be, for example, degreasing, alkaline cleaning, pickling, rinsing and / or pickling. After galvanizing, one or more subsequent treatments can be carried out, such as phosphating, oiling, passivating, applying organic coatings (cathodic dip painting).
  • a marking and / or marking by means of laser of hot-dip galvanized metal components is known.
  • the markings are achieved by printing (e.g. ink printing) or embossing (e.g. laser technology).
  • the laser marking is carried out in such a way that the protective properties of the galvanized layer are retained in full.
  • the zinc layer is selectively removed in a specified area by means of a laser and then subjected to a chemical reaction with an ambient gas (reaction gas).
  • reaction gas ambient gas
  • the zinc layer can be completely removed in order to increase the legibility of the marking.
  • the subsequent oxidation of the base material increases the optical contrast.
  • DE 40 33 230 A1 describes a combined marking process in which a Me tallband is processed mechanically and chemically in order to create a surface structure. Initially, embossing engravings are made using a laser. The exposed areas are then etched by an acid to a specified depth, so that after the etching process, which can be repeated several times for the purpose of obtaining superimposed structures, a desired engraved profile is created.
  • a structuring process for electroplated thermoplastics is known from DE 103 20 237 A1.
  • the thermoplastic is removed by a burning laser beam in the area of the desired symbols or structural elements.
  • a galvanic layer is applied to the thermoplastic surface structured in this way. Since there is no thermoplastic layer in the structuring area, no electroplated layer can form there. As a result, the laser-generated structuring is also visible on the top electroplated layer.
  • a structuring method is known in which structuring elements are applied to the surface to be structured by means of ink printing. The elevations produced by the ink pressure are hardened through. The surface is then coated with an electroplating layer.
  • the object of the invention is to provide a method for generating markings on galvanized steel strips or steel sheets, which does not affect the zinc layer and can be controlled locally in a targeted manner.
  • a further object of the invention is to create a steel strip or sheet steel made according to the above-mentioned method with areas with a marking which is easily detectable and in particular visible and allows problem-free processing and further processing.
  • markings are created on galvanized steel strips which do not negatively affect further processing.
  • a marking is understood to mean everything that is suitable for visually representing information or a pattern or design, that is to say for example writing, barcodes, patterns, designs.
  • the identification according to the invention can appear on any surface, for example a partial surface of a tape (for example barcode) or over the entire surface (for example pattern, brand, company name).
  • This marking can be perceptible to the human eye, i.e. that there are areas of a first type which can be optically distinguished from areas of the second type by the human eye. Areas of the first type (first areas) thus have a visually different effect than areas of the second type (second areas) and thus together form the identification.
  • the identifiers can be detected by the human eye and thus also by measuring devices or sensors in that a light / dark contrast is generated, with first areas being brighter than second areas, for example. Or the areas of the first type have a different color than the areas of the second type, the color tone distance being so large that it is visible to the human eye or can be detected by a sensor.
  • the areas of the first type and the areas of the second type with different reflectivities.
  • the reflectivity is referred to, among other things, as gloss. Different gloss is visible to the human eye. In addition, gloss can also be measured. This is used, for example, when assessing paint surfaces, in particular on motor vehicles.
  • the performance of the human eye should not be underestimated here; the trained eye of specialists is often used in the assessment, whereby the human eye is very good at perceiving relative differences in gloss on a surface.
  • Machine or automated gloss measurements are particularly advantageous when absolute reflection values are to be determined by measuring different surfaces, for example in the course of a series of measurements, for example of manufactured goods. This is especially true when the products are processed inline and are therefore no longer available for a comparison measurement after the measurement. If there are first areas with a different gloss (higher or lower) than the second areas, this can be measured by a sensor as well as detected by the human eye.
  • Measuring devices such as sensors are used for fully automatic detection of machine-readable identification, for example barcodes.
  • Identifications that are an advertising message, a brand name, safety instructions or the like are aimed at people and can therefore be perceived with the human eye.
  • the markings according to the invention can be measured with measuring devices, the measurements being gloss measurements in accordance with ISO 2813: 2014 or color measurements in accordance with EN ISO 11664-3: 2013. Both measurement methods can be used.
  • the method according to the invention generates labels in which the relative gloss differences or the color differences are so far apart that the required differences for recognition with the eye are clearly, and in particular exceeded several times. In other words, the marks are easily perceptible to the human eye.
  • areas with different optical impressions in particular with areas with different optical properties (eg gloss) that cause the visual appearance, are produced on galvanized steel strip or galvanized steel plates without changing the topography of the zinc layer. That means that after subsequent Coating steps the marking is no longer visible, because the surface is just moderate.
  • optical properties eg gloss
  • the invention provides that a salt solution is applied locally in a targeted manner to a steel strip, in particular a continuously rolled cold wide strip (KBB).
  • KBB continuously rolled cold wide strip
  • the solution can be applied using any transfer method. This can be, for example, inkjet printing, stamping or indirect gravure printing.
  • the steel surface is then electrolytically galvanized.
  • metal salt solutions are suitable for this process, in particular metal salt solutions are well suited.
  • the metal salt solutions can contain, for example, metal ions of the 4th, 5th main group and / or 7th, 11th subgroup. It is advantageous if the following metals are included as cations: Mn, Sn, Pb, Bi, Cu, Au, Ag. It is particularly advantageous if the metal salt solution used comprises bismuth ions.
  • Organic, inorganic ions or complexing agents can be used as anions.
  • Inorganic anions can be monovalent, such as, for example, F ⁇ , CI, G, Br, divalent, such as, for example, O 2 ⁇ , S 2 ⁇ , or have a complex structure, such as, for example, NO3 2 , SO 2 , OH-. It is advantageous if chloride, nitrate, sulfate ions, hydroxide or oxide ions are present as inorganic anions. It is particularly advantageous if nitrate ions are used.
  • Anions derived from organic acids can be used as organic anions. It can be, for example, carbonates, alcoholates, organic sulfates, organic nitrates. It is advantageous if acetate, citrate and / or oxalate ions are present in the salt solution used.
  • the solution used can be selected from the group of Mn, Sn, Pb, Bi, Cu, Au, Ag and nitrate, chloride, hydroxide, oxide, sulfate, acetate, citrate, oxalate and mixtures and combinations thereof.
  • a so-called cementation reaction sets in, especially at low pH values.
  • a metallic intermediate layer is formed on the steel surface. The reaction can be exemplified by the following equation:
  • the metal ions are reduced from the salt solution and deposited on the steel surface.
  • the deposited intermediate layer can have a layer thickness which is in the nanometer range.
  • tin can be used without external power application
  • the cyanides shift the copper potential to negative values and thereby allow the deposition of tin on copper (an important reaction in printed circuit boards).
  • the saline solution is applied in-line. It is advantageous that the desired pattern is not impaired by the entire system cycle.
  • the steel strip or steel plate is electrolytically galvanized.
  • the steel plate and / or the steel strip is brought into contact with a zinc electrolyte solution.
  • the zinc ions present in the electrolyte solution are reduced by the current passed through and crystallize on the surface to be coated. This Process is called electrocrystallization.
  • the zinc layer produced can have a layer thickness that is in the micrometer range.
  • the layer thickness ratio of the metallic intermediate layer and the zinc layer can be defined as 1: 1000 to 1: 20000, for example.
  • the electrocrystallization of the zinc is influenced by the underlying metallic intermediate layer in such a way that the crystallization in this area (hereinafter also “area of the first type”) takes place in a different manner and in particular in a significantly more orderly manner.
  • area of the first type the crystallization in this area
  • the appearance of the zinc in the pretreated areas is changed in such a way that the pretreated areas in particular have a higher gloss.
  • the marked surface is fully compatible with the other typical subsequent processes, such as phosphating, passivating, oiling, cleaning, and applying organic coatings.
  • the invention thus relates to a method for producing markings on galvanized steel strips or steel sheets, a metal salt solution, in particular an inorganic metal salt solution, being applied to the steel surface in areas and the steel surface then being electrolytically galvanized.
  • a metal salt solution is used, its cations from the group of Mn, Sn, Pb, Bi, Cu, Au, Ag and its anions from the group of nitrate, chloride, Flydroxide, oxide, acetate, citrate, oxalate and mixtures thereof and combinations can be selected.
  • a metal salt solution is used, the solution containing bismuth ions.
  • a metal salt solution is used, the solution comprising bis mut (111) -n itrat- pen ta hydrate and dilute nitric acid.
  • the applied metal salt solution enters into a cementation reaction with the steel surface in such a way that the metals are electrochemically deposited from the metal salt solution without the effect of external current, so that a metallic intermediate layer is deposited on the steel surface.
  • the metallic intermediate layer has a layer thickness in the nanometer range.
  • the layer thickness ratio of the metallic intermediate layer and the zinc layer located above it is between 1: 1000 to 1: 20000.
  • the zinc electrocrystallization is influenced by the metallic intermediate layer, so that the crystallization of the zinc above the metallic intermediate layer takes place in a more orderly manner with an axially and radially higher alignment rate.
  • a continuously rolled cold wide strip in particular a ge annealed continuously rolled cold wide strip, is used as the substrate.
  • the zinc layer is deposited over the areas treated with the salt solution and untreated areas, both areas having a common, indistinguishable topography after galvanizing.
  • the zinc layer over the areas of the first type treated with the salt solution has a different gloss measured in accordance with ISO 2813 and / or a color difference measured in accordance with EN ISO 11664 due to the increased crystallization order compared to the areas of the second type.
  • the relative gloss difference exceeds 10% and / or the color difference exceeds 1 for dE *.
  • Another aspect of the invention relates to an electrolytically galvanized steel strip or sheet steel with a marking, in particular produced by an aforementioned method, the electrolytically galvanized steel strip or the steel plate having areas of the first type and areas of the second type, both areas having the same topography, in particular Zinc layer thickness, the areas of the first type having a thin metallic intermediate layer between the steel surface and the zinc layer and the identification being formed in that the areas of the first type are optically distinguishable from the areas of the second type for the human eye and / or a sensor.
  • the areas of the first type have a different optical effect than the areas of the second type and thus together form the identification.
  • the zinc layer over the areas of the first type treated with the salt solution has a different gloss measured in accordance with ISO 2813 and / or a color difference measured in accordance with EN ISO 11664 due to the increased crystallization order compared to the areas of the second type, which is a for the human Visual impression that can be detected by the eye and measuring sensors, the relative gloss difference exceeding 10% and / or the color difference exceeding 1 for dE *.
  • the metallic intermediate layer comprises a metal or metals which can be selected from the group of Mn, Sn, Pb, Bi, Cu, Au, Ag.
  • the metallic intermediate layer comprises bismuth.
  • the metallic intermediate layer has a layer thickness in the nanometer range.
  • the metallic intermediate layer and the zinc layer have layer thicknesses which are in a ratio of 1: 1000 to 1: 20000 to one another.
  • FIG. 2 a surface of a sheet metal treated according to the invention
  • FIG. 3 A table with the measured values of the degree of gloss measurement
  • FIG. 4 the CIEIab color space for color measurements
  • FIG. 5 a table showing the measurement results of the color measurement
  • FIG. 6 a table with the summarized values of the color measurement
  • FIG. 7 electron micrographs of the different areas, showing the order structure of the zinc surface
  • Figure 8 Light microscope and topographical image of a modified zinc layer.
  • a salt solution is applied to the steel surface.
  • a KBB continuously rolled cold wide strip
  • an annealed KBB continuously rolled cold wide strip
  • the steel strip provided with the salt solution is then electrolytically galvanized in-line in one pass through the plant.
  • the areas treated according to the invention with the salt solution are still visible after galvanizing.
  • Figure 1 one recognizes an identification pattern generated by the method according to the invention.
  • the generated identification pattern shows no topography change in terms of layer thickness or sheet thickness change. This can be seen in FIGS. 7 and 8.
  • the area shown in the dark is the area of the first type, which has a metallic intermediate layer.
  • the zinc atoms are deposited on this metallic intermediate layer in a more ordered crystal structure according to Figure 7, which creates the different visual appearance, in particular areas with different optical properties (e.g. gloss, color difference) that create an optical impression.
  • the brightly shown area was not treated with the salt solution and therefore only has an electrolytically deposited zinc layer.
  • the right-hand area shown at the top right in FIG. 8 is, as stated, the area with the metallic intermediate layer according to the invention. In this case, this area appears darker. This is also related to the lighting, in this case a ring light, which is hardly reflected by the relatively flat area (evenly arranged "zinc shingles"). In the disordered area on the left, however, there are several surfaces that reflect the light and therefore appear brighter. The gloss effect created depends on the lighting angle.
  • the image at the bottom right in FIG. 8 is a topographical image of the same sample. It can be seen that both areas have an identical topography. There are no elevations or depressions in the area of the marking.
  • the markings according to the invention can be measured with measuring devices, the measurements being gloss measurements in accordance with ISO 2813: 2014 or color measurements in accordance with EN ISO 11664-3: 2013. Both measuring methods are common and applicable.
  • the method according to the invention generates characteristics in which the relative gloss differences or the color differences are so far apart that the differences required for recognition with the eye are clearly, and in particular exceeded several times. In other words, the marks are easily perceptible to the human eye.
  • An inorganic aqueous metal salt solution is prepared by adding 50 mL FINO3 (IN) to a spatula tip of Bi (N03) 3'5Fl20. The solution is stirred at room temperature until the salt is completely dissolved. The stock solution prepared in this way is then diluted with deionized water in a ratio of 1: 9. The diluted salt solution is applied in-line to a KBB (continuously rolled cold wide strip) using ink-jet or indirect gravure printing. The steel strip pretreated in this way is then electrolytically galvanized. After the electrolytic galvanizing, a gloss measurement is carried out in accordance with the standard given above and a color measurement in accordance with the standard also given above.
  • FIG. 2 shows a sample sheet produced according to the above-mentioned sequence with an area of the first type on the left and an area of the second type on the right.
  • FIG. 5 shows a table with the recorded values and the resulting color deviations which are also summarized in the table according to FIG.
  • the color differences are summarized as dE * value.
  • the rule here is that a value of 1 or greater can be distinguished from the human eye.
  • FIG. 7 shows an electron microscope image in which an area is visible in the middle in which all order states occur.
  • a zinc coating is shown in the picture on the right.
  • the metallic intermediate layer is located under this zinc coating.
  • the salt solution is applied locally in a targeted manner.
  • the visual impression that occurs later or a marking can be defined locally in a targeted manner.
  • the marking produced according to the invention is no longer visible after a further coating, for example a cathodic dip coating.
  • the marking according to the invention can thus be used for markings of any kind. It can be used, for example, for material description and / or data backup, such as for batch number, coil number, Fiersteller information.
  • barcodes or 3D codes can be generated with the method according to the invention.
  • the brand name under which the material is sold possibly in combination with the name of the manufacturer or design or pattern on the strip or sheet metal.
  • the emissivities of such a sheet can also be changed in certain areas by the corresponding coating. This is an important factor when heating sheet metal, as it affects the heat absorption capacity.
  • the degree of heating can be adjusted via different emissivities, so that different degrees of austenitization and thus hardness / tensile strengths can also be set via the surface conditioning according to the invention are.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un procédé pour la production de marquages sur une bande d'acier ou tôle d'acier galvanisée, procédé dans lequel une solution de sel métallique, plus particulièrement une solution de sel métallique inorganique, est appliquée sur des régions de la surface de l'acier, et la surface de l'acier est ensuite galvanisée électrolytiquement. L'invention concerne également une bande d'acier ou tôle d'acier galvanisée ayant un marquage produit de cette manière.
PCT/EP2021/056831 2020-03-18 2021-03-17 Procédé pour la production de marquages sur une bande d'acier ou tôle d'acier galvanisée et bande d'acier ou tôle d'acier galvanisée ayant un marquage de cette sorte WO2021185914A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP21714105.0A EP4121579A1 (fr) 2020-03-18 2021-03-17 Procédé pour la production de marquages sur une bande d'acier ou tôle d'acier galvanisée et bande d'acier ou tôle d'acier galvanisée ayant un marquage de cette sorte

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20163979.6 2020-03-18
EP20163979.6A EP3882374A1 (fr) 2020-03-18 2020-03-18 Procédé de génération de zones à différentes propriétés optiques sur des bandes en acier galvanisées et bandes en acier galvanisées pourvues de zones à différentes propriétés optiques

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WO2021185914A1 true WO2021185914A1 (fr) 2021-09-23

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EP (2) EP3882374A1 (fr)
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2148324A (en) * 1983-04-26 1985-05-30 British Steel Corp Plated steel products
DE4033230A1 (de) 1990-10-19 1992-04-23 Hueck Fa E Oberflaechenstrukturierte, grossformatige metallene pressplatten und/oder endlosbaender und verfahren zu deren herstellung
US5494706A (en) * 1993-06-29 1996-02-27 Nkk Corporation Method for producing zinc coated steel sheet
KR20020053290A (ko) * 2000-12-27 2002-07-05 이구택 광택성이 우수한 전기아연 도금강판의 제조방법
DE10320237A1 (de) 2003-05-07 2004-12-02 Dirk Kieslich Verfahren zur Herstellung durchleuchtbarer, galvanisch veredelter Thermoplastteile und durchleuchtbare Thermoplastteile mit galvanisch veredelter Oberfläche
DE102007010932A1 (de) 2007-03-05 2008-09-11 Hünnebeck Group GmbH Verzinkte längenverstellbare Stahlrohrstütze mit Markierungen und Verfahren zur Herstellung derselben
DE102011051266A1 (de) 2011-06-22 2012-12-27 Guido Schulte Presskörper zur Herstellung eines Laminats sowie Verfahren zur Herstellung eines Presskörpers
WO2013117249A1 (fr) * 2012-02-06 2013-08-15 Nv Bekaert Sa Revêtement en alliage ternaire ou quaternaire pour vieillissement à la vapeur et élément allongé en acier à adhérence par durcissement à l'humidité comprenant un revêtement en alliage de laiton ternaire ou quaternaire et procédé correspondant
JP2018044190A (ja) * 2016-09-12 2018-03-22 東洋鋼鈑株式会社 亜鉛めっき鋼板の製造方法
DE102017106672A1 (de) 2017-01-17 2018-07-19 Fontaine Holdings Nv Verfahren zur Kennzeichnung und/oder Markierung verzinkter, insbesondere feuerverzinkter Bauteile
US20180230625A1 (en) * 2012-02-06 2018-08-16 Nv Bekaert Sa Process for manufacturing an elongated steel element to reinforce rubber products
US20190366687A1 (en) * 2016-12-26 2019-12-05 Posco Zinc alloy plated steel having excellent weldability and corrosion resistance

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2148324A (en) * 1983-04-26 1985-05-30 British Steel Corp Plated steel products
DE4033230A1 (de) 1990-10-19 1992-04-23 Hueck Fa E Oberflaechenstrukturierte, grossformatige metallene pressplatten und/oder endlosbaender und verfahren zu deren herstellung
US5494706A (en) * 1993-06-29 1996-02-27 Nkk Corporation Method for producing zinc coated steel sheet
KR20020053290A (ko) * 2000-12-27 2002-07-05 이구택 광택성이 우수한 전기아연 도금강판의 제조방법
DE10320237A1 (de) 2003-05-07 2004-12-02 Dirk Kieslich Verfahren zur Herstellung durchleuchtbarer, galvanisch veredelter Thermoplastteile und durchleuchtbare Thermoplastteile mit galvanisch veredelter Oberfläche
DE102007010932A1 (de) 2007-03-05 2008-09-11 Hünnebeck Group GmbH Verzinkte längenverstellbare Stahlrohrstütze mit Markierungen und Verfahren zur Herstellung derselben
DE102011051266A1 (de) 2011-06-22 2012-12-27 Guido Schulte Presskörper zur Herstellung eines Laminats sowie Verfahren zur Herstellung eines Presskörpers
WO2013117249A1 (fr) * 2012-02-06 2013-08-15 Nv Bekaert Sa Revêtement en alliage ternaire ou quaternaire pour vieillissement à la vapeur et élément allongé en acier à adhérence par durcissement à l'humidité comprenant un revêtement en alliage de laiton ternaire ou quaternaire et procédé correspondant
US20180230625A1 (en) * 2012-02-06 2018-08-16 Nv Bekaert Sa Process for manufacturing an elongated steel element to reinforce rubber products
JP2018044190A (ja) * 2016-09-12 2018-03-22 東洋鋼鈑株式会社 亜鉛めっき鋼板の製造方法
US20190366687A1 (en) * 2016-12-26 2019-12-05 Posco Zinc alloy plated steel having excellent weldability and corrosion resistance
DE102017106672A1 (de) 2017-01-17 2018-07-19 Fontaine Holdings Nv Verfahren zur Kennzeichnung und/oder Markierung verzinkter, insbesondere feuerverzinkter Bauteile

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PAUNOVIC, MSCHLESINGER, M: "Fundamentals of electrochemical deposition", 1998, WILEY, pages: 161 - 166

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EP4121579A1 (fr) 2023-01-25

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