EP3405600B1 - Procédé de fabrication d'un produit en acier doté d'un revêtement de zinc et d'une couche active tribilogiquement appliquée sur celui-ci ainsi que produit en acier obtenu de maniere correspondante - Google Patents

Procédé de fabrication d'un produit en acier doté d'un revêtement de zinc et d'une couche active tribilogiquement appliquée sur celui-ci ainsi que produit en acier obtenu de maniere correspondante Download PDF

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Publication number
EP3405600B1
EP3405600B1 EP16702489.2A EP16702489A EP3405600B1 EP 3405600 B1 EP3405600 B1 EP 3405600B1 EP 16702489 A EP16702489 A EP 16702489A EP 3405600 B1 EP3405600 B1 EP 3405600B1
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EP
European Patent Office
Prior art keywords
coating
steel product
aqueous solution
protective coating
zinc
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EP16702489.2A
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German (de)
English (en)
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EP3405600A1 (fr
Inventor
Thomas Lostak
Christian Timma
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ThyssenKrupp Steel Europe AG
ThyssenKrupp AG
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ThyssenKrupp Steel Europe AG
ThyssenKrupp AG
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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc 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
    • C23C2/26—After-treatment
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

Definitions

  • the invention relates to a process for producing a steel product which has a protective coating based on zinc and a tribologically active layer applied to the protective coating.
  • the invention relates to a provided with such a layer structure steel product, wherein this steel product is in particular a flat steel product.
  • flat steel products refers to rolled products that are available as strip, sheet metal or blanks and blanks derived therefrom.
  • thin sheet here refers to flat steel products with a sheet thickness of typically up to 3 mm.
  • galvanized steel flat products In order to optimize their surface properties, galvanized steel flat products usually undergo temper rolling after galvanizing, in which they are deformed with low degrees of deformation. By temper rolling the texture of the respective flat steel product is imprinted, which increases the roughness of the substrate and as a result improves the adhesion and the appearance of the subsequently applied organic coatings. In addition, it is known that the temper rolling process has positive effects on the mechanical properties of the flat steel product.
  • Hot-dip galvanized flat steel products are increasingly replacing electrolytically galvanized flat steel products in the field of automobile body construction.
  • the steel flat product to be formed in each case or an already preformed steel component for forming into a component is inserted into a forming machine and then shaped by the machine to the respective component.
  • the transformation can be carried out as cold forming, that is to say as forming at temperatures below the recrystallization temperature of the respective steel of the flat steel products, or as hot forming, ie as forming at working temperatures which are above the recrystallization temperature.
  • a typical example of such a forming process is deep-drawing, in which the flat steel product to be formed is pressed by means of a punch into a die.
  • the shape of the die and die here determine the shape that the flat steel product receives through the forming process.
  • This friction can be very different locally, especially during the forming of flat steel products, because the material of the flat steel product is deformed differently in sections as part of the forming and thus the material of the flat steel product flows locally as differently at the deformation. It is therefore precisely in the production of complex-shaped components by deep drawing or comparable cold forming processes, which are usually achieved in large degrees of deformation and complex shapes are displayed, dynamically changing frictional conditions in which static and sliding friction can occur alternately.
  • flat steel products in which a zinc-based protective coating protecting against corrosion or other environmental influences is applied to the actual flat steel product, prove to be particularly critical.
  • a phosphate layer is built up on the Zn coating.
  • Tri-cation phosphating takes place first a pickling attack on the Zn-coated base substrate, in which first metal cations go under hydrogen evolution in solution.
  • poorly soluble phosphates precipitate near the surface due to the pH change and form a firmly adhering conversion layer.
  • Modern phosphatizations belong to the so-called layer-forming phosphatizations.
  • the layer build-up is carried out by metal cations from the phosphating solution (e.g., zinc, manganese).
  • the phosphating solution e.g., zinc, manganese
  • cations from the base substrate can also be incorporated into the phosphate layer.
  • the good sliding properties of the phosphate layer are based z.T. on easy shearing of phosphate crystals.
  • phosphating improves the corrosion protection of the electrolytically galvanized sheet. For procedural reasons, a line phosphating of hot-dip galvanized flat steel products, however, is not economically feasible.
  • the phosphate coating applied in the typical automotive phosphating process does not belong to the classic dry lubricants (such as graphite, MoS 2 ).
  • the lubricating effect of the phosphate layer is due to the effect of interacting with the anticorrosive oils or pre-lubes with the phosphate layer and the underlying hot-dip galvanized substrate for added protection to the flat steel products.
  • coated thin sheets are applied with a corrosion protection oil or a pre-lube to guarantee sufficient corrosion protection during transport and subsequent storage. Furthermore, lubrication ensures additional pre-lubrication during the forming process.
  • the carbonate supplier is for example selected from ammonium hydrogencarbonate, ammonium carbonate etc. and a hydroxide supplier, selected from alkali metal hydroxides, alkali metal oxides etc.
  • This layer is applied according to invention by means of Chem Coater.
  • the layer weight of the dry substance is 25 to 200 mg / m 2 .
  • the pH of the aqueous solution according to the invention is preferably in the range of 9 ⁇ 0.5. Due to the basic environment, purposeful technical and personal protective measures (eg protective gloves, safety goggles) must be taken.
  • Example 7 of this publication illustrates the relationship between the water-insoluble and water-soluble portion of the zinc hydroxysulfate formed. From this example it can be seen that the improvement of the lubricating effect is provided by the water-insoluble part. In addition, it is shown that the proportion of the water-insoluble fraction increases with increasing coating time.
  • the emulsions consist of the following components: (A) water-soluble inorganic salt (eg borax, potassium tetraborate, sodium sulphate etc.), (B) solid lubricant (eg phyllosilicates, metal soaps etc.), (C) natural (eg mineral oil etc.) and synthetic oils, (D) surfactant and (E) water.
  • A water-soluble inorganic salt
  • B solid lubricant
  • C eg phyllosilicates, metal soaps etc.
  • C natural (eg mineral oil etc.) and synthetic oils
  • surfactant and E water.
  • the ratio between (B) and (A) is in the range of 0.05: 1 to 2: 1.
  • the ratio between (C) and (B) + (A) is between 0.05: 1 and 1: 1.
  • the dry layer weight of the coating described is given in a range between 1 and 50 g / m 2 .
  • the layer according to the invention unfolds its positive tribological properties on metals only by means of all stated components ((A) - (E)). Individual components of the layer according to the invention, such as potassium tetraborate, are classified as hazardous to health.
  • a solid lubricant based on a sulfate (calcium or barium sulfate), an already known lubricant from the group of graphite, graphite fluoride, molybdenum disulfide, etc. and an organic lubricant (eg fatty acids, metal soaps, etc.) described.
  • the sulfate-based solid lubricant exhibits its intended effect when the particle size is ⁇ 100 ⁇ m. This requires a more complex manufacturing process.
  • the dry layer weight of the coating is in the range of 5 to 15 g / m 2 .
  • an oxalate-containing coating which is intended to improve the tribological properties of the metallic substrate coated with it. In doing so, the improved tribological Properties of the coating attributed to the contained iron oxalate.
  • iron oxalate is hazardous to health.
  • WO-A-2015 197430 discloses a method of coating zinc coated steel substrates.
  • a solution containing alkali metal sulfate, and alkali metal carbonate having a pH of 9-12 is used.
  • the object has arisen of naming a method which, with simple products that are harmless with regard to environmental pollution, allows to produce a coating having the optimum tribological effect on a galvanized surface of a steel product.
  • a steel product should be specified which, in addition to optimized corrosion protection, has optimum suitability for forming into a component, in particular a body component.
  • the solution according to the invention is that a steel product has the features mentioned in claim 9.
  • the invention thus provides, in a no-rinse method (ie in a method in which rinsing after application of the aqueous solution consisting of ammonium sulfate and demineralized water is dispensed with the protective coating) on the Zn protective coating of each processed Steel product to apply an aqueous solution consisting of ammonium sulfate and demineralized water.
  • the concentration of ammonium sulfate in relation to the total volume is in the range of 0.01 to 5.7 mol / l.
  • a conventional chemical or coil coater can be used for the application of the present invention to be applied to the Zn coating solution.
  • chem- or coil coater are for example in the book " Coil Coating - Coil Coating: Processes, Products and Markets "by P. Meuthen, Almuth-Sigrun Jandel, Friedr. Vieweg & Sohn Verlag / GWV fraverlage GmbH, 1st edition 2005, ISBN: 3-528-03975-2 described.
  • the aqueous solution is applied to at least one side of the zinc alloy coating of the steel substrate.
  • aqueous solution by means of spraying, wherein the spraying is followed by squeezing to adjust the thickness of the film formed from the solution remaining on the respective substrate. This procedure is typically used in coating systems that are completed in continuous operation of the respective steel product.
  • the dry layer weight of the tribologically active layer produced according to the invention and accordingly present on a steel product according to the invention is typically 1-100 mg / m 2, based on the sulfur content, with dry layer weights of at most 20 mg / m 2 , in particular from 10 to 20, particularly with regard to weldability mg / m 2 , in each case based on the S-content of the coating have proven to be particularly favorable.
  • Practical dry film thicknesses are 10 to 15 mg / m 2, also based on the S content.
  • Another surface chemical characteristic of the tribologically active layer produced according to the invention is that the double sulfate (NH 4 ) 2 Zn (SO 4 ) 2 shows a high adhesion to the zinc alloy coating due to the Zn mixed crystal formed.
  • the tribologically active coating applied according to the invention simultaneously offers an exceptionally high lubricating effect, in particular Automotive typical cold forming processes and is thus optimally suitable for forming into a component in a forming tool. Examinations have proven that the tribologically active layer produced according to the invention does not adversely affect the subsequent processes typical for the production of automobile body parts, such as gluing, welding, phosphating or electrophoretic painting. Flat steel products coated according to the invention have significantly improved tribological properties compared to only oiled thin sheets. Furthermore, the coating produced and obtained according to the invention offers excellent sequence process compatibility in the automobility-typical production process (joining, phosphatability, KTL-capability, etc.).
  • inventively provided and generated, tribologically active layer is also easily removable, for example, with water, if any influence on the succession processes should be excluded by them safely. Due to their chemical composition, the inventively produced and provided on a steel product Ammoniumzinksulfat coating is extremely environmentally friendly and harmless to health.
  • the invention is based on the findings, in a general form already in the non-prepublished European patent application 14 18 44 15.9 ( EP-A-2 995 674 In addition, however, provides information on the parameters, such as in particular the reaction time between the applied, according to the invention ammonium sulfate aqueous solution and the respective steel substrate, which are crucial to the inventively recognized as favorable constitution of the tribologically active layer receive.
  • the content of the European patent application 14 18 44 15.9 is therefore included to explain the technical context in which the invention stands, and the possible practical implementation of the method according to the invention by reference in the present patent application.
  • the steel substrates to be provided for the process according to the invention and forming the basis of the steel products designed according to the invention are coated with a protective coating based on zinc in order to protect against corrosion.
  • the Zn-based coating may be applied conventionally as a pure zinc layer or as a zinc alloy layer and may have levels of Mg, Al, Fe or Si to improve or adjust its properties. Alloy prescriptions which characterize typical practice-proven compositions of such Zn-based anticorrosive coatings are disclosed in e.g. 0.5-5% by weight of aluminum and / or up to 5% by weight of magnesium and balance zinc and unavoidable impurities.
  • a flat steel product can be cooled to the respective bath inlet temperature by a conventional pretreatment and then immersed in an immersion time of 0.1-10 s with an iron saturated 420-520 ° C Zn Melt bath containing, in addition to the main component zinc and unavoidable impurities 0.05 to 5 wt .-% Al and / or up to 5 wt .-% Mg.
  • the Zn protective coating of the steel product provided according to the invention may have been applied electrolytically, for example. From a practical and economic point of view, however, it proves to be particularly advantageous if the Zn protective coating has been applied to the respective steel substrate of the flat steel product by application of methods which are likewise known per se by hot-dip coating.
  • the respective steel substrate of the flat steel product to be coated by the method according to the invention may have any composition known from the prior art as long as it permits a coating with a Zn-based protective coating and is suitable for the respective subsequent process.
  • Typical examples of steels which make up the steel substrate of flat steel products coated according to the invention are IF steels, microalloyed steels, bake hardening steels, TRIP steels, Dual-phase steels and deep-drawing steels such as, for example, the steels known under the designation DX51D to DX58D (material numbers 1.0226, 1.0350, 1.0355, 1.0306, 1.0309, 1.0322, 10.0853).
  • the aqueous solution applied according to the invention to the Zn-based protective coating contains, in addition to the main components “demineralized water” and "ammonium sulfate", no additional constituents. In particular, the presence of other organic components, especially those that might be environmentally hazardous, is excluded.
  • the concentration of the ammonium sulfate in the aqueous solution is based on the SO 4 2- ions in the range of 0.01 to 5.7 mol / l chosen so that the inventively provided, from the double sulfate (NH 4 ) 2 Zn ( SO 4 ) 2 forms existing coating securely on the Zn coating.
  • concentration of ammonium sulfate with respect to the SO 4 2- ions is 0.1-3 mol / l.
  • the concentration of ammonium sulfate in relation to the SO 4 2- ions is 0.4-0.7 mol / l
  • the optimum for the layer formation according to the invention is obtained without further addition of acids or bases pH value natively, without the need for additional aids to adjust the pH of the solution must be added.
  • this concentration range is optimal from an ecological and economic point of view, since only the amount of ammonium sulfate is used, which is necessary to form an inventive Ammoniumzinksulfat slaughter under the application conditions described on galvanized sheet.
  • the pH of the solution used is between 4 and 6, wherein the inventively provided, tribologically active (NH 4 ) 2 Zn (SO 4 ) 2 layer particularly reliable especially when the pH of the aqueous solution is 4.2 to 5.7.
  • Table 1 shows the relationship between the pH and the ammonium zinc sulfate layer formed according to the invention
  • the invention is effective regardless of the particular composition of the protective coating, as long as the base of the protective coating is zinc, so zinc is the predominant component of the protective coating.
  • a hot-dip galvanized sheet was used for the experiments reported here.
  • the pickling reaction i. the zinc dissolution due to the reaction between the solution applied according to the invention and the surface of the Zn protective layer wetted with the solution.
  • the invention here is based on the recognition that the pickling process is only effective at acidic pH's, i. at pH values less than 7 expires.
  • the adjusting pH of the solution is, as described above, dependent on the concentration of ammonium sulfate and must be within the range specified in the invention. If the ammonium sulfate concentration of the solution is too low, the pH of the solution is too high for the reaction desired according to the invention, the Zn of the coating does not dissolve and no ammonium zinc sulfate is formed.
  • the coating temperature plays no role in the application of the solution.
  • no-rinse method With the aqueous solution adjusted in accordance with the invention and applied without rinsing ("no-rinse method"), it is possible to ensure that the zinc dissolution process used for the formation of the (NH 4 ) 2 Zn (SO 4 ) 2 layer is required to reliably run off at the interface between the Zn protective coating and the aqueous solution.
  • the near-surface reaction time between the aqueous solution and the protective coating present on the steel substrate of the respective steel product is of particular importance according to the findings of the invention.
  • the reaction close to the surface after the application of the aqueous solution must take sufficiently long time to allow the formation of the double sulfate (NH 4 ) 2 Zn (SO 4 ) 2 on the Zn coating enable.
  • the reaction time must not last too long, otherwise there is the formation of undesirable, poorly soluble zinc sulfate.
  • the reaction time can be controlled over the period of time which elapses between the application of the respective solution to the Zn protective coating and the drying of the solution.
  • the available reaction time is defined by the line application process. If, for example, the length of the application zone in which the solution is applied to the respective steel product by spraying with subsequent squeezing is 2 to 3 m and this application zone is run through at a belt speed of 2-3 m / s, then the application time and concomitantly the reaction time is about 1s.
  • the steel product Directly behind the application zone, the steel product then enters a dryer, which dries the remaining wet film formed from the solution at a temperature of 70-90 ° C. Drying stops the reaction.
  • a steel substrate which has a Zn protective coating containing 1 wt .-% aluminum and the balance contained zinc and unavoidable impurities, hot-dip galvanized, in an ammonium sulfate solution with a concentration of ammonium sulfate based on the SO 4 2- ions of 0.1 mol / l and one with it associated pH of 5.1. This coating was carried out at room temperature.
  • the forming coating was measured continuously by means of confocal Raman spectroscopy.
  • the intensity of the v 1 -ZnSO 4 vibrational band at 962 wavenumbers served as a direct measure of the formation of the unwanted zinc sulphate.
  • X-ray diffractometry is a suitable analytical method for characterizing the ammonium zinc sulfate layer applied according to the invention.
  • Fig. 1 the X-ray diffractogram of a Ammoniumzinksulfat slaughter prepared according to the invention is shown on a hot-dip galvanized steel substrate.
  • the X-ray diffractogram shows typical reflections of a layer of ammonium zinc sulfate and was confirmed by reference spectra. No zinc sulfate was formed under the application parameters according to the invention.
  • confocal Raman spectroscopy is suitable as a vibrational spectroscopic method, especially for the characterization of thinnest coatings.
  • Fig. 2 the Raman spectrum of an ammonium zinc sulfate layer produced according to the invention is shown
  • the solids-free aqueous solution which is composed appropriately according to the invention, can be applied to at least one side of the galvanized steel sheet by means of a chemical or coil coater or any other suitable method.
  • a chemical reaction then takes place between the ammonium sulfate completely dissociated in the solution and the zinc surface.
  • the layer formation of the tribologically active substance consisting of ammonium zinc sulfate (4 Zn (NH 3 ) 4 2+ + 2 (NH 4 ) 2 SO 4 + 6H 2 O ⁇ (NH 4 ) 2 Zn (SO 4 2 x 6H 2 O + 6NH 3 + 2H + ).
  • ammonium zinc sulfate formed according to the invention is a specific double sulfate.
  • This double sulphate is decisive for the improved tribological properties as well as for the automotive-typical subsequent process compatibility. Investigations have shown that with the method according to the invention such a layer can be produced reliably and in a manner suitable for large-scale production.
  • the Ammoniumzinksulfat slaughter produced according to the invention is water-soluble and in this point has no special requirements for Cleaning processes, such as are typically performed in the manufacture of automobile bodies and the like typically after the shaping of the steel product and before its further processing.
  • the tribologically active layer formed according to the invention can thus be easily removed, for example, before a phosphating process and subsequent KTL application.
  • ammonium zinc sulfate layer according to the invention as a tribologically active layer can be easily checked by means of X-ray diffractometry and Raman spectroscopy.
  • Characteristic of the tribologically active layer produced according to the invention is that it consists entirely of the double sulfate ammonium zinc sulfate and that it is free from sparingly soluble zinc hydroxysulfate.
  • the aqueous solution After application of the aqueous solution, it can be dried in air at ambient temperatures. In industrial use, however, it can be expedient to accelerate the process sequence to force drying in an oven, in particular a continuous furnace.
  • the respective steel product can be kept at a temperature of 70-90 ° C over a period of 1 - 3 s in each oven.
  • the ammonium zinc sulfate layer of the present invention is formed.
  • the layer weight of dry matter related to the sulfur content per m 2 is 0.1 - 100 mg / m 2, preferably 10 - 50 mg / m 2, wherein based on the sulfur coating weights from 10 - to be particularly useful 20 mg / m 2 to have.
  • the "sulfur content per square meter" given in milligrams is also briefly referred to herein as "mgS / m 2 ".
  • the inventive method for producing the double sulfate on the surface of the hot-dip galvanized sheet requires no special safety measures, since ammonium sulfate is not a hazardous substance.
  • the application of the inventively provided tribologically active layer can be integrated easily into a conventional, the current state of the art fire-coating system.
  • the tribologically active layer can be analyzed by means of the likewise known glow discharge spectroscopy.
  • the metallic workpiece is switched as a cathode and removed with argon ions.
  • the ablated atoms are excited in the plasma and emit photons of characteristic wavelength.
  • the invention proves to be particularly advantageous when the steel product to be processed according to the invention is a flat steel product.
  • the work steps to be carried out according to the invention can be incorporated into a coating installation completed in the course, whereby a particularly economical large-scale implementation of the method according to the invention is possible. This applies in particular when the flat steel product according to the invention is a steel strip.
  • a corrosion protection oil or a pre-lube can be applied to the coated and dried steel product according to the invention in a manner known per se in order to avoid surface corrosion on the transport path to the respective forming plant and to further improve the forming behavior during the forming process.
  • the surface in question can be cleaned alkaline prior to application of the coating composition.
  • the process of the invention is carried out immediately after a zinc coating, can be dispensed with an alkaline cleaning. There, the coating is then applied directly after galvanizing.
  • test series which a) were carried out under laboratory conditions and b) on an industrial scale on a coating line.
  • a cold-rolled steel strip consisting of a typical DX51D automotive grade (material number 1.0226) was used, coated by conventional hot-dip galvanizing with a 7 ⁇ m zinc layer consisting of 1% by weight aluminum, balance Zn and technical grade unavoidable impurities existed.
  • an application solution consisting of ammonium sulfate dissolved in deionized water (Conductivity ⁇ 0.05 ⁇ S / cm).
  • the ammonium sulfate was completely in solution. No further substances were added.
  • the application solution was thus a completely aqueous, solids-free solution.
  • the substrate coated according to the invention is oiled with a pre-lube.
  • the tests used were, for example, those offered under the trade name Anticorit PL 3802-39S by FUCHS Europe Schmierstoffe GmbH (see catalog "Lubricants for Exterior and Car Body Parts in the Automotive Industry", bloesch-partner.de 07/2008 1.0) Pre-Lube.
  • the oil layer was 1.5 g / m 2 .
  • the sample geometry of the coated flat steel products was 700 x 50 mm 2 , while the tool area was 660 mm 2 .
  • the test speed was 60 mm / min.
  • the surface pressure increased linearly from 1 MPa to 100 MPa over the entire test area.
  • the measuring section was 500 mm.
  • the result of the investigation of the strip pulling test is shown as the dependence of the coefficient of friction ⁇ on the surface pressure [Mpa].
  • the experimental setup is schematic in Fig. 3 shown.
  • the fracture surface and the fracture pattern were then visually evaluated according to the specification of EN ISO 10365: 1995.
  • the break occurred either in the adhesive itself or in the joining part material. It was distinguished in fractures in the adhesive between a cohesive failure, in which the separation takes place in the adhesive, and an adhesion failure, in which the break occurs at the interface between the adherend and the adhesive. In addition, the material of the sample failed itself while the adhesive remained intact.
  • a distinction was made between a split part break and a break caused by delamination.
  • An aqueous coating solution was prepared. To this was dissolved 92.5 g of ammonium sulfate in one liter of demineralized water. No special measures were taken to adjust the pH of the coating solution, but the native pH of the solution was about 5. In particular, there was no addition of bases or acids to adjust the pH.
  • the hot dip galvanized steel flat product samples were alkaline cleaned prior to application of the coating.
  • the treatment solution was uniformly distributed on the hot-dip galvanized sheet by means of a conventional coil coater.
  • the applied wet film is dried in a continuous oven at a drying temperature of 50-90 ° C.
  • the applied amount of aqueous coating solution was adjusted so that the dry layer weight of the (NH 4 ) 2 Zn (SO 4 ) 2 layer obtained on the samples corresponded to the specifications according to the invention.
  • the measurement of the layer coverage in mgS / m 2 was carried out by means of mobile X-ray fluorescence analysis (RFA).
  • test samples were coated with the Pre-Lube (Anticorit PL 3802-39S).
  • the oil layer was 1.5 g / m 2 .
  • Table 3 summarizes the results of these experiments. It can be clearly seen that the forming capacity is significantly improved with increasing coating weight.
  • Table 3 Occurrence of the stick-slip effect as a function of (NH ⁇ sub> 4 ⁇ / sub>) ⁇ sub> 2 ⁇ / sub> Zn (SO ⁇ sub> 4 ⁇ / sub>) ⁇ sub> 2 ⁇ / sub> dry weight (laboratory application) Coating weight [mgS / m 2 ] Surface pressure up to which a stick-slip effect occurs [MPa] 0 2 10 35 20 > 100 30 > 100
  • a coating solution having a concentration of 51 g / L ammonium sulfate in demineralized water was prepared.
  • the unchanged native pH of the resulting aqueous solution was about 5.
  • the aqueous ammonium sulfate solution was applied by means of an application device arranged inline behind a conventional hot-dip galvanizing plant, in which the solution was sprayed onto the galvanized flat steel product and then squeezed off in a conventional manner to adjust the layer thickness.
  • the measurement of the layer coverage in mgS / m 2 was carried out by means of mobile X-ray fluorescence analysis (RFA).
  • the resulting flat steel product samples coated in the manner according to the invention were oiled with an oiling amount of about 1 g / m 2 with a thixotropic and barium-free corrosion protection oil sold under the trade name RP4107S by FUCHS Europe Schmierstoffe GmbH.
  • the friction-reducing effect of the ammonium zinc sulfate layer produced according to the invention was characterized by means of the strip-pulling experiment.
  • Table 4 shows the surface pressure achieved in MPa before the stick-slip effect occurred and the test had to be stopped. Again, there was a significant improvement in the tribological properties of ammonium zinc sulfate coated substrates.
  • Table 4 Occurrence of the stick-slip effect as a function of (NH ⁇ sub> 4 ⁇ / sub>) ⁇ sub> 2 ⁇ / sub> Zn (SO ⁇ sub> 4 ⁇ / sub>) ⁇ sub> 2 ⁇ / sub> layer weight (line application) Coating weight [mgS / m 2 ] Surface pressure up to which a stick-slip effect occurs [MPa] 0 7 20 65 25 > 100 36 > 100 70 > 100
  • Fig. 4 the tensile shear strength and the peel resistance of an uncoated reference (Z) and of an ammonium zinc sulfate layer according to the invention having a coating weight of 20 mg S / m 2 are shown.
  • the reduction in tensile shear strength and peel resistance compared to the uncoated reference is acceptable and, surprisingly, does not limit the use of this coating in the automotive body sector. Furthermore, the fracture pattern is close to the substrate cohesive.
  • a dry coating weight of, for example, 100 mgS / m 2 would severely adversely affect resistance spot welding and subsequent sticking.
  • the phosphating would not be a problem and continue to be unproblematic because shortly before the phosphating several rinsing and Purification cascades take place and the ammonium zinc sulfate layer according to the invention is thereby removed.
  • Table 5 Suitability of the thin plates coated according to the invention for various automobility-typical subsequent processes Coating weight [mg S / m 2 ]
  • Fitness to Resistance spot welding stick phosphating 10 Very well Very well Very well 20 Very well Very well Very well 30 medium medium Very well 40 Bad Bad Well 80 Very bad Very bad Well 100 Very bad Very bad Well
  • Variant 1 is a hot-dip galvanized steel sheet (99% zinc, 1% aluminum) coated with ammonium zinc sulphate with a dry film thickness of 20 mg S / m ⁇ sup> 2 ⁇ / sup>.
  • Variant 2 is a hot-dip galvanized steel sheet (99% zinc, 1% aluminum) coated with zinc sulphate with a dry-film coating of 20 mg S / m ⁇ sup> 2 ⁇ / sup> variant Delaminated area (visually assessed according to EN ISO 10365: 1995) 1 ⁇ 1% 2 > 80%

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Coating With Molten Metal (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (12)

  1. Procédé de fabrication d'un produit en acier, qui comprend un revêtement de protection à base de zinc et une couche tribologiquement active appliquée sur le revêtement de protection, comprenant les étapes de procédé suivantes:
    - la préparation d'un produit plat en acier muni du revêtement de protection,
    - l'application d'une solution aqueuse constituée par du sulfate d'ammonium et de l'eau entièrement dessalée sur le revêtement de protection du produit en acier,
    - la concentration du sulfate d'ammonium en termes d'ions SO4 2- étant de 0,01 à 5,7 mol/l,
    - le pH de la solution aqueuse étant de 4 à 6,
    et
    - le temps de réaction à proximité de la surface entre la solution aqueuse et le revêtement de protection étant supérieur à 0 seconde et d'au plus 5 secondes,
    - de telle sorte qu'après un séchage réalisé sans rinçage préalable, une couche tribologiquement active soit présente sur le revêtement de protection, qui est constituée par du sulfate d'ammonium et de zinc.
  2. Procédé selon la revendication 1, caractérisé en ce que la concentration du sulfate d'ammonium dans la solution aqueuse est de 0,1 à 3 mol/l.
  3. Procédé selon la revendication 2, caractérisé en ce que la concentration du sulfate d'ammonium dans la solution aqueuse est de 0,4 à 0,7 mol/l.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le pH de la solution aqueuse est de 4,2 à 5,7.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le produit en acier est un produit plat en acier.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse est appliquée au moyen d'un dispositif d'enduction chimique ou à bobine sur le revêtement de protection.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le produit en acier est séché à une température de 70 à 90 °C après l'application de la solution aqueuse.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la surface à revêtir du produit en acier est nettoyée par voie alcaline avant le revêtement.
  9. Produit en acier, qui comprend un substrat en acier et un revêtement protecteur à base de zinc porté par le substrat en acier, une couche tribologiquement active étant formée sur le revêtement de protection, qui est constituée par du sulfate d'ammonium et de zinc.
  10. Produit en acier selon la revendication 9, caractérisé en ce que le poids de couche à sec de la couche tribologiquement active est de 1 à 100 mg/m2, par rapport à la teneur en soufre.
  11. Produit en acier selon la revendication 10, caractérisé en ce que le poids de couche à sec de la couche tribologiquement active est de 10 à 50 mg/m2, par rapport à la teneur en soufre.
  12. Produit en acier selon la revendication 11, caractérisé en ce que le poids de couche à sec de la couche tribologiquement active est de 10 à 20 mg/m2, par rapport à la teneur en soufre.
EP16702489.2A 2016-01-19 2016-01-19 Procédé de fabrication d'un produit en acier doté d'un revêtement de zinc et d'une couche active tribilogiquement appliquée sur celui-ci ainsi que produit en acier obtenu de maniere correspondante Active EP3405600B1 (fr)

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CN108474118A (zh) 2018-08-31
US20190024240A1 (en) 2019-01-24
KR20180102163A (ko) 2018-09-14
JP2019503434A (ja) 2019-02-07
JP6629979B2 (ja) 2020-01-15
EP3405600A1 (fr) 2018-11-28
US11078573B2 (en) 2021-08-03
WO2017125131A1 (fr) 2017-07-27
CN108474118B (zh) 2020-05-08

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