EP3856947B1 - Verfahren zur verbesserung der phosphatierbarkeit von metallischen oberflächen, welche mit einer temporären vor- bzw. nachbehandlung versehen werden - Google Patents

Verfahren zur verbesserung der phosphatierbarkeit von metallischen oberflächen, welche mit einer temporären vor- bzw. nachbehandlung versehen werden Download PDF

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Publication number
EP3856947B1
EP3856947B1 EP19778901.9A EP19778901A EP3856947B1 EP 3856947 B1 EP3856947 B1 EP 3856947B1 EP 19778901 A EP19778901 A EP 19778901A EP 3856947 B1 EP3856947 B1 EP 3856947B1
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EP
European Patent Office
Prior art keywords
coating
zinc
steel product
flat steel
activation particles
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EP19778901.9A
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German (de)
English (en)
French (fr)
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EP3856947A1 (de
Inventor
Fabian JUNGE
Christian Altgassen
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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
    • 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
    • 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
    • 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
    • C23C22/07—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 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • 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
    • C23C22/73—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 characterised by the process
    • 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
    • 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
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to a method for producing a formed component, comprising at least the steps (A) providing a flat steel product, (B) skin rolling the flat steel product from step (A), (C) applying a functional coating to the flat steel product from step (B), (D) forming the flat steel product from step (C) to obtain a formed component, (E) removing the functional coating from the formed component from step (D), (F) applying activation particles to the formed component from step (E), and (G) applying a phosphating to the formed component from step (F), wherein additional activation particles are applied to the flat steel product before and/or during step (B) and/or before and/or during step (C). Furthermore, the present invention relates to a corresponding flat steel product and its use in the automotive sector.
  • US 2015/0352825 A1 discloses a process in which a flat steel product having an anti-corrosive coating is first treated with an acidic solution so that a subsequently applied adhesive shows better adhesion.
  • WO 2017/125131 A1 discloses a method for producing a steel product having a zinc-based protective coating and a tribologically active layer applied to the protective coating.
  • the anti-corrosive coated steel flat products known from the state of the art often have the problem that during their production a temporary pre- or post-treatment, i.e. a functional coating such as an adhesion-promoting layer, a forming aid, a passivation or a combination thereof, is applied and then removed again. This removal is usually carried out by a cleaning step. It can happen that the cleaning step is not completed, i.e. that residues of the functional coating remain on at least some areas of the flat steel product.
  • a temporary pre- or post-treatment i.e. a functional coating such as an adhesion-promoting layer, a forming aid, a passivation or a combination thereof
  • a subsequent two-stage phosphating step which includes the application of activation particles and phosphating, the activation particles cannot fully reach the actual surface of the flat steel product due to the residues of the functional layer, so that the result is a phosphate layer that consists in areas of zinc phosphate crystals of different sizes that appear uneven when viewed macroscopically, which is undesirable.
  • the object of the present invention is therefore to provide a method for producing a phosphated flat steel product which, compared to the prior art, produces improved phosphated surfaces which, in particular, exhibit better adhesive adhesion.
  • the invention aims to provide a method which produces good phosphated surfaces, in particular with improved adhesive adhesion, even when functional coatings applied in the meantime have not been completely removed.
  • Step (A) of the method according to the invention comprises providing a flat steel product.
  • a flat steel product provided with a coating that protects against corrosion is provided.
  • the flat steel product used according to the invention can consist of any steel grade known to the person skilled in the art, for example CR3 or DX51.
  • This steel preferably used according to the invention contains, for example, max. 0.08 wt.% C, max. 0.45 wt.% Mn, max. 0.030 wt.% P, max. 0.030 wt.% S, max. 0.15 wt.% Cr, max. 0.20 wt.% Cu, max. 0.06 wt.% Mo, max. 0.008 wt.% Nb, max. 0.20 wt.% Ni, where the sum of Cu, Ni, Cr and Mo must not exceed 0.50 wt.% and the sum of Cr and Mo must not exceed 0.16 wt.%, the remainder being Fe and unavoidable impurities.
  • the flat steel product according to the invention is a hot strip or a cold strip. These can be obtained by methods known to those skilled in the art.
  • so-called blanks can also be used in step (A) of the method according to the invention, which are preferably obtained by cutting pieces from a hot or cold strip using suitable methods.
  • the flat steel product according to the invention is based on a steel sheet, preferably containing a coating that protects against corrosion.
  • the coating that protects against corrosion which is preferably present according to the invention, is preferably metallic.
  • the steel sheet can be coated in a known manner, for example in a hot-dip process (hot-dip galvanizing) or by electrolytic deposition. According to the invention, the coating is preferably carried out in a hot-dip process. Corresponding processes are known per se to those skilled in the art.
  • the coating that is preferably present on the flat steel product according to the invention is preferably based on zinc, a zinc alloy, aluminum or an aluminum alloy.
  • a non-coated, in particular non-galvanized, steel surface can also be used in step (A).
  • Suitable coatings therefore contain, for example, zinc or zinc and magnesium, zinc and aluminium or zinc which has been applied electrolytically.
  • the flat steel product in particular the steel strip, is preferably coated by first mechanically and/or chemically cleaning the strip surface in a first stage of the coating process.
  • the strip surface is then roughened, preferably in an acidic pickling solution, before the strip is passed through an electrolytic coating cell and coated, in particular galvanized, there.
  • the steel strip is dipped in a sulfuric acid zinc electrolyte and simultaneously switched as a cathode.
  • soluble electrodes these are also dipped in the electrolyte solution and switched as an anode.
  • the cations migrate from the anode through the electrolyte to the steel strip surface and are cathodically deposited there.
  • the metal for example zinc
  • the electrolyte is already dissolved in the electrolyte, whereby the anodes consist of correspondingly more noble materials.
  • the amount of metal deposited on the strip surface depends on the current density and the coating duration.
  • the steel strip In order to achieve a metal layer thickness of a few micrometers at a belt speed of, for example, 100 m/min, the steel strip must pass through several coating cells connected in series in an electrolytic cell because of the relatively short coating time and thus the correspondingly low deposition rate at such a belt speed.
  • the electrolytically coated steel strip is preferably passed through a multi-stage rinsing device.
  • the present coating particularly preferably consists of zinc or a zinc alloy, which has more preferably been applied by hot-dip coating.
  • Methods for hot-dip coating are known per se to those skilled in the art.
  • the coating in particular made of zinc or a zinc alloy, is preferably present with a coating weight of 1 to 600 g/m 2 , ie 0.5 to 300 g/m 2 per side, particularly preferably 20 to 300 g/m 2 , ie 10 to 150 g/m 2 per side.
  • Step (B) of the process according to the invention comprises the skin passing of the flat steel product from step (A).
  • Dressing is known to the expert and is described, for example, in Handbook of forming, Günter Spur, ISBN: 978-3-446-43004-4, page 155 .
  • the present invention preferably relates to the method according to the invention, wherein the skin-passing in step (B) is carried out using a skin-passing agent.
  • a skin-passing agent is therefore applied to the flat steel product before and/or during step (B).
  • Usable skin-passing agents are known per se to the person skilled in the art.
  • the at least one dressing agent contains organic compounds selected from the group consisting of saturated hydrocarbons, in particular hydrogenated naphtha, alkoxylated alcohols, in particular 2-(2-butoxyethoxy)ethanol, 2-(methoxymethyloxy)propane and/or branched poly(oxy-1,2-ethanediyl)-alpha-tridecyl-omega-alcohol, adducts of organic acids and amines, for example the adduct of 3,5,5-trimethylhexanoic acid and 2-aminoethanol, derivatives of fatty acids, for example oleoylsarcosine, amines, for example dodecylpropylenetriamine, glycols, for example hexylene glycol, and mixtures thereof.
  • saturated hydrocarbons in particular hydrogenated naphtha
  • alkoxylated alcohols in particular 2-(2-butoxyethoxy)ethanol, 2-(methoxymethyloxy)propane and/or branched poly(oxy-1
  • the at least one dressing agent is selected from the group consisting of compositions with the trade names Friocut LF 280, Gardolube L 8256, QWERL 4305 and mixtures thereof.
  • the present invention therefore preferably relates to the process according to the invention, wherein at least one skin-pass agent and additional activation particles are applied to the flat steel product before and/or during step (B).
  • a mixture containing at least one skin-pass agent and additional activation particles is applied to the flat steel product before and/or during step (B).
  • At least one skin-pass agent and additional activation particles are applied separately to the flat steel product before and/or during step (B).
  • the at least one skin-pass agent is generally applied to the flat steel product in an amount such that the subsequent skin-pass step can proceed advantageously.
  • the at least one skin-pass agent is applied in an amount of 1 to 50 g/L, particularly preferably 10 to 30 g/L.
  • the application of the at least one dressing agent and optionally the activation particles can generally be carried out by all methods known to the person skilled in the art, for example spraying, dipping or coating methods.
  • Step (C) of the process according to the invention comprises applying a functional coating to the flat steel product from step (B).
  • the steel product obtained after the skin passing in step (B) contains on the surface at least parts of the possibly applied skin passing agent and, if applicable, additional activation particles.
  • step (C) of the method according to the invention at least one functional coating is applied to this flat steel product.
  • Functional coatings are also known to the person skilled in the art under the term "pre- or post-treatments”.
  • Functional coatings that can be applied to the flat steel product in the method according to the invention are known to the person skilled in the art and are selected, for example, from the group consisting of adhesion-promoting layer, forming aid, passivation or a combination thereof.
  • Suitable adhesion-promoting coatings are known to the person skilled in the art and contain, for example, alcohols, for example methanol, silane components, for example Polysiloxanes, silicate components, ammonium or amino compounds, organic polymers and mixtures thereof.
  • the at least one adhesion promoter is selected from the group consisting of compositions with the trade names GBX 4537, Bonderite 1461 and mixtures thereof.
  • An adhesion-promoting layer can be applied to the flat steel product by any method known to the person skilled in the art, for example spraying, dipping or coating processes.
  • An adhesion-promoting coating is generally applied in an amount sufficient to exert the adhesion-promoting effect, for example 1 mg/m 2 to 10 mg/m 2 , preferably 2 mg/m 2 to 6 mg/m 2 , in each case per layer of the silicon conductive element.
  • Suitable coatings that can act as a forming aid are known per se to the person skilled in the art and contain, for example, acids, for example phosphoric acid, bases, for example potassium hydroxide or organic amines, cyclic organic compounds, for example benzotriazole, other organic compounds, for example fatty acids, sulfonates, for example methanesulfonate, or alcohols, for example aminoethanol, inorganic salts, for example sulfates, in particular zinc sulfate or potassium sulfate, or carbonates, for example sodium carbonate, preferably as aqueous solutions.
  • acids for example phosphoric acid
  • bases for example potassium hydroxide or organic amines
  • cyclic organic compounds for example benzotriazole
  • other organic compounds for example fatty acids, sulfonates, for example methanesulfonate, or alcohols, for example aminoethanol
  • inorganic salts for example sulfates, in particular zinc sulfate or potassium s
  • the at least one forming aid is selected from the group consisting of compositions with the trade names Lubitreat, NIT, L-FM50000, L-FM50100, L-FM50200 and mixtures thereof.
  • a coating acting as a forming aid can be applied to the flat steel product by any method known to the person skilled in the art, for example spraying, dipping or coating processes.
  • a coating acting as a forming aid is generally applied in an amount sufficient to produce the corresponding effect, for example 5 mg/m 2 to 40 mg/m 2 , preferably 10 mg/m 2 to 25 mg/m 2 , in each case based on the sulfur conductive element.
  • Suitable passivating coatings are known per se to the person skilled in the art and contain, for example, chromium salts, for example chromium orthophosphate, chromium nitrate, chromium trifluoride, organic acids, for example citric acid, inorganic acids, for example hydrofluoric acid, and mixtures thereof.
  • the at least one passivating agent is selected from the group consisting of compositions with the trade names Gardolene D 6804, Gardolene D 6811, Bonderite M-PA 6003 and mixtures thereof.
  • a passivating coating can be applied to the flat steel product by any method known to the person skilled in the art, for example spraying, dipping or coating processes.
  • a passivating coating is generally applied in an amount sufficient to exert the passivating effect, for example 5 mg/m 2 to 40 mg/m 2 , preferably 10 mg/m 2 to 25 mg/m 2 , in each case based on the conductive element chromium, in the case of chromium-containing passivations.
  • step (C) of the process according to the invention two or more of the coatings mentioned are applied in appropriate amounts. This can be done sequentially or simultaneously.
  • the present invention preferably relates to the process according to the invention, wherein at least one functional coating agent and additional activation particles are applied before and/or during step (C).
  • a mixture containing at least one functional coating agent and additional activation particles is applied to the flat steel product before and/or during step (C).
  • At least one functional coating agent and additional activation particles are applied separately to the flat steel product before and/or during step (C).
  • Step (D) of the method according to the invention comprises forming the flat steel product from step (C) in order to obtain a formed component.
  • blanks are preferably first cut from the hot strip or cold strip at the beginning of step (D). This can be done using methods known to those skilled in the art.
  • the forming of the flat steel product from step (C) can be carried out by all methods known to the person skilled in the art, for example according to DIN 8580 (2010) and in particular DIN 8584 (2010).
  • the transformation preferably takes place at room temperature.
  • Step (E) of the method according to the invention comprises removing the functional coating from the formed component from step (D).
  • Step (E) of the process according to the invention can generally be carried out by any method known to the person skilled in the art, for example described in EP 2 311 928 A2 , EP 2 851 452 A1 and EP 2 937 411 A1 .
  • step (E) of the method according to the invention is carried out in that the formed component from step (D) can be treated with at least one cleaning agent in order to remove the functional coating.
  • the functional coating is removed in step (E) of the method according to the invention by treating the surface of the formed component with a cleaning agent.
  • the cleaning agent can be acidic, neutral or alkaline.
  • an alkaline cleaning agent is used.
  • the cleaning agent is also preferably used as an aqueous solution.
  • the cleaning-active substance for example a surfactant, is preferably present in an amount that appears suitable to the person skilled in the art.
  • Further components of the cleaning agent which are preferably present according to the invention are, for example, selected from the group consisting of sodium hydroxide or potassium hydroxide and mixtures thereof.
  • Step (E) of the method according to the invention can also be carried out using mechanical energy, for example by brushing the surfaces to be cleaned or by applying water and/or cleaning agents to the surface under high pressure.
  • Step (E) of the method according to the invention is preferably carried out at a temperature of 30 to 70 °C.
  • the cleaning in step (E) of the method according to the invention is complete, since the best result is then achieved in the phosphating in step (G).
  • the cleaning in step (E) of the method according to the invention does not necessarily have to be complete in order to obtain a particularly advantageous result in the phosphating step.
  • by applying additional activation particles to the flat steel product before and/or during step (B) and/or before and/or during step (C) it is possible to obtain a very good phosphating result, even though the functional coating does not have to have been completely removed. This circumstance greatly simplifies the process and helps to obtain high-quality phosphated and formed components.
  • the method according to the invention therefore comprises the feature essential to the invention that additional activation particles are applied to the flat steel product before and/or during step (B) and/or before and/or during step (C).
  • the additional activation particles may differ from the activation particles used in step (F).
  • the additional activation particles and the activation particles used in step (F) of the process according to the invention are the same.
  • the additional activation particles are preferably selected from the group consisting of powder activations, in particular based on titanium phosphates, or liquid activations, in particular based on zinc phosphates and metal oxides.
  • water-dispersible compounds are used, for example oxalates of silver or copper compounds, disodium phosphate in combination with titanium compounds, in particular with water-soluble titanium compounds, for example titanium phosphate or sodium titanyl phosphates, zinc phosphates and mixtures of zinc phosphates and metal oxides, e.g. zinc or iron oxides and mixtures thereof.
  • the additional activation particles are preferably applied in powder form or as an aqueous composition.
  • the batch concentration of the activating agent is, for example, 0.1 to 20 g activating agent concentrate /I pre- or post-treatment , particularly preferably 1 to 6 g activating agent concentrate /I pre- or post-treatment .
  • Step (F) of the method according to the invention comprises the application of activation particles to the formed component from step (E).
  • activation particles are applied in step (F) and before and/or during step (B) and/or before and/or during step (C) in order to improve the nucleation process of the subsequent phosphating.
  • the additional application of crystallization nuclei increases the number of nucleation sites on the substrate, since the zinc phosphate precipitating from the phosphating solution preferentially crystallizes on the additional nuclei.
  • the number of phosphate crystals per unit area is increased, so that the crystals are increasingly hindered in their growth. This leads to a reduction in crystal size and weight per unit area, while the crystal formation rate increases and the degree of coverage increases.
  • the phosphate layer is formed more evenly and the consumption of chemicals can be reduced.
  • the crystals become mechanically more stable and the adhesion of the crystals to the substrate is improved.
  • the formation of smaller, evenly distributed phosphate crystals leads to an improvement in the adhesion of the paint film applied in the subsequent process.
  • the phosphating process can therefore be precisely adjusted and controlled.
  • the actual activation step is generally preceded by a separate cleaning step in which the surface is first freed of electrolyte, oils, fats, solid particles, oxides and other contaminants using an alkaline or acidic cleaner.
  • the pH range can be between 6 and 13.
  • the surface is then rinsed with fresh water and deionized water to prevent carryover into the subsequent activation bath.
  • the additional activation particles that are applied in step (F) of the process according to the invention are preferably selected from the group consisting of powder activations, in particular based on titanium phosphates, or liquid activations, in particular based on zinc phosphates and metal oxides.
  • water-dispersible compounds are used, for example oxalates of silver or copper compounds, disodium phosphate in combination with titanium compounds, in particular with water-soluble titanium compounds, for example titanium phosphate or sodium titanyl phosphates, zinc phosphates and mixtures of zinc phosphates and metal oxides, e.g. zinc or iron oxides and mixtures thereof.
  • the additional activation particles are preferably applied in powder form.
  • the present invention therefore preferably relates to the process according to the invention, wherein the additional activation particles which are applied to the flat steel product before and/or during step (B) and/or before and/or during step (C) are selected from the group consisting of powder activations, in particular based on titanium phosphates, or liquid activations, in particular based on zinc phosphates and metal oxides.
  • the concentration of the activating agent is, for example, 0.1 to 20 g activating agent concentrate /I pre- or post-treatment , particularly preferably 1 to 6 g activating agent concentrate /I pre- or post-treatment.
  • activation particles with a concentration (powder or liquid) are thus present on the formed component after step (F) of the process according to the invention.
  • Step (G) of the process according to the invention comprises applying a phosphating to the formed component from step (F).
  • an aqueous solution containing zinc phosphate, phosphoric acid, optionally nickel and/or manganese cations, and an accelerator is preferably used.
  • the accelerator used is, for example, nitrate, for example zinc nitrate, nitrite, for example sodium nitrite, or hydrogen peroxide.
  • Step (G) of the process according to the invention is preferably carried out by immersing the formed components from step (F) in an aqueous solution containing the above-mentioned components.
  • the contact time is, for example, 100 to 200 s.
  • the process steps are preferably carried out in the order (A), (B), (C), (D), (E) and (F).
  • the process according to the invention can optionally comprise further steps, for example oiling and/or bonding, which then take place between the steps mentioned.
  • steps (C), (F) and/or (G) are preferably carried out by a spraying, dipping or coating process.
  • the application of solutions in steps (B), (C), (F), (G) of the process according to the invention, in particular the application of the additional activation particles before and/or during step (B) and/or before and/or during step (C), is preferably carried out in a coating process.
  • Coating processes are known to the person skilled in the art.
  • the ratio is preferably the rotational speed of the application roller to the belt speed 70 to 130%.
  • the temperature of the solution, in particular the aqueous solution is preferably 15 to 30 °C.
  • a wet film with a thickness of 1 to 4 ⁇ m, corresponding to 1 to 4 ml/m 2 is preferably applied. After the wet film has been applied, the coated board is preferably dried.
  • the temperature of the dryer is set so that a suitable temperature is set in relation to the belt speed, for example 60 to 130 °C.
  • the belt speed is for example 30 to 180 m/min, preferably 80 to 120 m/min, for example 100 m/min.
  • the present invention also relates to a component manufactured by the method according to the invention.
  • the components manufactured according to the invention are characterized in that they have a particularly homogeneous phosphating layer on the surface.
  • the activation causes the zinc phosphate crystals to become particularly finely crystalline, i.e. this results in lower chemical consumption, the mechanical stability is higher, which means better paint adhesion and corrosion resistance. Furthermore, the process times are shorter because small crystals crystallize out more quickly than large ones.
  • the present invention also relates to the use of a component according to the invention in the automotive sector.
  • the component according to the invention is suitable for use in the automotive sector due to its advantageous properties.
  • the concentration of the adhesion promoter is 2 to 6 (silicon coating as a conductive element) g/L.
  • a wetting agent available under the trade name H7475, is also applied.
  • activation particles available under the trade name ZL 6, are also applied.
  • the aqueous solutions are applied at a temperature of 15 to 30 °C, the wet film thickness of the applied solution is 1 to 4 ⁇ m, corresponding to 1 to 4 ml/m 2 .
  • the coated tape is dried at a temperature of 60 to 130 °C. During the process, the tape speed is 100 m/min -1 .

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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)
  • Chemical Treatment Of Metals (AREA)
EP19778901.9A 2018-09-24 2019-09-20 Verfahren zur verbesserung der phosphatierbarkeit von metallischen oberflächen, welche mit einer temporären vor- bzw. nachbehandlung versehen werden Active EP3856947B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018216216.6A DE102018216216A1 (de) 2018-09-24 2018-09-24 Verfahren zur Verbesserung der Phosphatierbarkeit von metallischen Oberflächen, welche mit einer temporären Vor- bzw. Nachbehandlung versehen werden
PCT/EP2019/075340 WO2020064548A1 (de) 2018-09-24 2019-09-20 Verfahren zur verbesserung der phosphatierbarkeit von metallischen oberflächen, welche mit einer temporären vor- bzw. nachbehandlung versehen werden

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EP3856947A1 EP3856947A1 (de) 2021-08-04
EP3856947B1 true EP3856947B1 (de) 2024-09-04

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EP19778901.9A Active EP3856947B1 (de) 2018-09-24 2019-09-20 Verfahren zur verbesserung der phosphatierbarkeit von metallischen oberflächen, welche mit einer temporären vor- bzw. nachbehandlung versehen werden

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EP (1) EP3856947B1 (pl)
DE (1) DE102018216216A1 (pl)
PL (1) PL3856947T3 (pl)
WO (1) WO2020064548A1 (pl)

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CN117535653A (zh) * 2022-08-01 2024-02-09 宝山钢铁股份有限公司 一种用于高强钢可磷化性能改善的环保水基处理剂
DE102023110138A1 (de) * 2023-04-21 2024-10-24 Thyssenkrupp Steel Europe Ag Stahlblech mit doppelschichtigem temporärem Korrosionsschutz
DE102023110139A1 (de) 2023-04-21 2024-10-24 Thyssenkrupp Steel Europe Ag Stahlblech mit doppelschichtigem temporärem Korrosionsschutz für optimierte Lackierung

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4012795A1 (de) * 1990-04-21 1991-10-24 Metallgesellschaft Ag Aktivierungsmittel fuer die phosphatierung
JP3857866B2 (ja) * 2000-02-29 2006-12-13 日本ペイント株式会社 ノンクロメート金属表面処理剤、表面処理方法および処理された塗装鋼材
DE10110833B4 (de) * 2001-03-06 2005-03-24 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
EP1350865A3 (de) * 2002-04-05 2004-12-29 ThyssenKrupp Stahl AG Verzinktes und phosphatiertes Blech sowie Verfahren zur Herstellung eines solchen Blechs
DE10256639A1 (de) 2002-12-03 2004-06-24 Thyssenkrupp Stahl Ag Schmierstoffbeschichtetes Metallblech mit verbesserten Umformeigenschaften
US7947333B2 (en) * 2006-03-31 2011-05-24 Chemetall Gmbh Method for coating of metallic coil or sheets for producing hollow articles
DE102008004728A1 (de) * 2008-01-16 2009-07-23 Henkel Ag & Co. Kgaa Phosphatiertes Stahlblech sowie Verfahren zur Herstellung eines solchen Blechs
WO2013160568A1 (fr) 2012-04-25 2013-10-31 Arcelormittal Investigacion Y Desarrollo, S.L. Procédé de réalisation d'une tôle à revêtements ZnAlMg comprenant l'application d'une solution acide et tôle correspondante.
EP2824213A1 (de) 2013-07-12 2015-01-14 Voestalpine Stahl GmbH Verfahren zur Verbesserung der Haftfähigkeit auf einem schutzbeschichteten Stahlblech
ES2734456T3 (es) 2013-09-19 2019-12-10 Fuchs Petrolub Se Capa funcional inorgánica sobre acero galvanizado por inmersión en caliente como ayuda para la conformación
DE102014105226A1 (de) * 2014-04-11 2015-10-15 Thyssenkrupp Ag Verfahren zur Aktivierung von zu phosphatierenden Metalloberflächen, vorzugsweise verzinktem Stahlblech
EP2937411A1 (de) 2014-04-25 2015-10-28 Voestalpine Stahl GmbH Blech und Verfahren zur Verbesserung der Umformbarkeit eines Blechs
KR20180102163A (ko) * 2016-01-19 2018-09-14 티센크루프 스틸 유럽 악티엔게젤샤프트 아연 코팅 및 상기 코팅 상에 도포된 마찰공학적 활성 층을 갖는 강 제품의 제조 방법, 및 상응하게 제조된 강 제품

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WO2020064548A1 (de) 2020-04-02
PL3856947T3 (pl) 2024-11-25
EP3856947A1 (de) 2021-08-04

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