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EP3280831B1 - Procédé de phosphatation sans nickel de surfaces metalliques - Google Patents

Procédé de phosphatation sans nickel de surfaces metalliques Download PDF

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Publication number
EP3280831B1
EP3280831B1 EP16718613.9A EP16718613A EP3280831B1 EP 3280831 B1 EP3280831 B1 EP 3280831B1 EP 16718613 A EP16718613 A EP 16718613A EP 3280831 B1 EP3280831 B1 EP 3280831B1
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Prior art keywords
ions
phosphating
nickel
composition
approx
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German (de)
English (en)
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EP3280831A1 (fr
Inventor
Olaf Dahlenburg
Frank Hollmann
Lisa SCHMEIER
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Chemetall GmbH
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Chemetall GmbH
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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
    • 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
    • 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
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/362—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 fluorides or complex fluorides containing also phosphates containing also zinc 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
    • C23C22/05—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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 fluorides or complex fluorides containing also phosphates containing also manganese 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
    • C23C22/05—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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—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 fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and 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
    • C23C22/78—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
    • C23C22/82—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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • 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 the essentially nickel-free phosphating of a metallic surface, a corresponding phosphating composition and a corresponding phosphate-coated metallic surface.
  • Phosphate coatings on metallic surfaces are known from the state of the art. Such coatings serve to protect metallic surfaces from corrosion and also act as adhesion promoters for subsequent paint layers.
  • Such phosphate coatings are mainly used in the automotive industry and in general industry.
  • WO 95/33083 A1 discloses a process for coating phosphated metal substrates with organic coatings, wherein the substrates are treated with an aqueous solution after phosphating and before application of the first organic coating.
  • the subsequent paint layers are mainly cathodically deposited electrocoatings (CDPs), in addition to powder coatings and wet paints. Since a current must flow between the metallic surface and the treatment bath when CDPs are deposited, it is important to set a defined electrical conductivity of the phosphate coating in order to ensure efficient and homogeneous deposition.
  • CDPs cathodically deposited electrocoatings
  • Phosphate coatings are therefore usually applied using a nickel-containing phosphating solution.
  • the nickel deposited in elemental form or as an alloy component, e.g. Zn/Ni, ensures that the coating has suitable conductivity during the subsequent electrocoating.
  • nickel ions are no longer desirable as components of treatment solutions and should therefore be avoided if possible or at least their content reduced.
  • the coating may also be subject to non-optimal
  • the object of the present invention was therefore to provide a method with which metallic surfaces can be phosphated essentially nickel-free, wherein these are comparable or almost comparable in terms of their electrochemical properties to the metallic surfaces which have been treated with nickel-containing phosphating solutions, and in particular the aforementioned disadvantages of the prior art are avoided.
  • a metallic surface is first treated with an acidic aqueous phosphating composition which comprises zinc ions, manganese ions and phosphate ions, optionally rinsed and/or dried, and then treated with an aqueous rinsing composition which comprises at least one type of metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin, antimony, titanium, zirconium and hafnium and/or at least one polymer selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypropylenes and mixtures and copolymers thereof, wherein both the phosphating composition and the rinsing composition are essentially nickel-free.
  • an acidic aqueous phosphating composition which comprises zinc ions, manganese ions and phosphate ions, optionally rinsed and/or dried
  • an uncoated metallic surface but on the other hand, a metallic surface that has already been converted can also be treated with the method according to the invention. Whenever a "metallic surface” is mentioned below, this should therefore always include a metallic surface that has already been converted.
  • an "aqueous composition” refers to a composition which contains at least partly, preferably predominantly, water as a solvent. In addition to dissolved components, it can also comprise dispersed, i.e. emulsified and/or suspended components.
  • phosphate ions also include hydrogen phosphate, dihydrogen phosphate and phosphoric acid.
  • pyrophosphoric acid and polyphosphoric acid as well as all of their partially and fully deprotonated forms are also included.
  • metal ion means either a metal cation, a complex metal cation or a complex metal anion.
  • composition contains less than 0.3 g/l of nickel ions, it shall be considered “substantially nickel-free” for the purposes of the present invention.
  • the metallic surface is preferably steel, hot-dip galvanizing, electrolytic galvanizing, aluminum or their alloys such as Zn/Fe or Zn/Mg. Hot-dip galvanizing and electrolytic galvanizing are each particularly on steel. In particular, the metallic surface is at least partially galvanized.
  • the process according to the invention is particularly suitable for multi-metal applications.
  • a metallic surface is to be coated which is not a fresh hot-dip galvanized surface, it is advantageous to first clean, in particular degrease, the metallic surface in an aqueous cleaning composition before treatment with the phosphating composition.
  • an acidic, neutral, alkaline or strongly alkaline cleaning composition can be used, but if necessary also an acidic or neutral pickling composition.
  • An alkaline or strongly alkaline cleaning composition has proven particularly advantageous.
  • the aqueous cleaning composition may optionally also contain a cleaning framework and/or other additives such as complexing agents.
  • a cleaning framework and/or other additives such as complexing agents.
  • the use of an activating cleaner is also possible.
  • the metallic surface is then advantageously rinsed at least once with water, whereby an additive dissolved in water, such as a nitrite or surfactant, may also be added to the water.
  • an additive dissolved in water such as a nitrite or surfactant
  • the activation composition serves to deposit a large number of very fine phosphate particles as seed crystals on the metallic surface. In the subsequent process step, these help to form a particularly crystalline phosphate layer with the highest possible number of densely arranged fine phosphate crystals or a largely closed phosphate layer in contact with the phosphating composition - preferably without intermediate rinsing.
  • Acidic or alkaline compositions based on titanium phosphate or zinc phosphate are particularly suitable as activation compositions.
  • activating agents in particular titanium phosphate or zinc phosphate, to the cleaning composition, thus carrying out cleaning and activation in one step.
  • the acidic aqueous phosphating composition comprises zinc ions, manganese ions and phosphate ions.
  • the phosphating composition can be obtained from a concentrate by diluting with a suitable solvent, preferably with water, by a factor between 1 and 100, preferably between 5 and 50, and if necessary adding a pH-modifying substance.
  • the phosphating composition preferably comprises the following components in the following preferred and particularly preferred concentration ranges: Zn 0.3 to 3.0 g/l 0.5 to 2.0 g/l Mn 0.3 to 2.0 g/l 0.5 to 1.5 g/l Phosphate (calculated as P 2 O 5 ) 8 to 25 g/l 10 to 18 g/l free fluoride 30 to 250 mg/l 50 to 180 mg/l Complex fluoride (calculated e.g. as SiF 6 2- and/or BF 4 - ) 0 to 5 g/l 0.5 to 3 g/l
  • the complex fluoride is preferably tetrafluoroborate (BF 4 - ) and/or hexafluorosilicate (SiF 6 2- ).
  • a content of complex fluoride as well as simple fluoride, for example sodium fluoride, in the phosphating composition is advantageous.
  • Al 3+ is a bath poison in phosphating systems and can be removed from the system by complexing it with fluoride, e.g. as cryolite.
  • fluoride e.g. as cryolite.
  • Complex fluorides are added to the bath as a "fluoride buffer" because otherwise the fluoride content would quickly drop and no coating would take place. Fluoride thus supports the formation of the phosphate layer and thus indirectly leads to an improvement in paint adhesion and corrosion protection. Complex fluoride also helps to avoid defects such as specks on galvanized material.
  • the phosphating composition has a content of Fe(III).
  • An Fe(III) content in the range from 0.001 to 0.2 g/l is preferred, particularly preferably from 0.005 to 0.1 g/l and very particularly preferably from 0.01 to 0.05 g/l is preferred.
  • the phosphating composition preferably contains at least one Accelerator selected from the group consisting of the following compounds in the following preferred and particularly preferred concentration ranges: nitroguanidine 0.2 to 3.0 g/l 0.2 to 1.55 g/l H 2 O 2 10 to 100 mg/l 15 to 50 mg/l Nitroguanidine / H 2 O 2 0.2 to 2.0 g/l / 10 to 50 mg/l 0.2 to 1.5 g/l / 15 to 30 mg/l nitrite 30 to 300 mg/l 90 to 150 mg/l hydroxylamine 0.1 to 5 g/l 0.4 to 3 g/l
  • nitroguanidine a concentration in the range of 0.1 to 3.0 g/l and with regard to H 2 O 2 , a concentration in the range of 5 to 200 mg/l has already proven to be advantageous.
  • the at least one accelerator is H 2 O 2 .
  • the phosphating composition contains less than 0.5 g/l, preferably less than 0.1 g/l and more preferably less than 0.01 g/l nitrate.
  • the nitrate in the phosphating composition causes an additional acceleration of the layer formation reaction, which leads to lower layer weights but above all reduces the incorporation of manganese into the crystal.
  • the manganese content of the phosphate coating is too low, this is to the detriment of its alkali resistance.
  • Alkali resistance plays a crucial role in subsequent cathodic electrocoating. This involves electrolytic splitting of water on the substrate surface: Hydroxide ions are formed. This leads to an increase in the pH value at the substrate interface. This is what allows the electrocoating to agglomerate and be deposited. However, the increased pH value can also damage the crystalline phosphate layer.
  • the phosphating composition preferably has a temperature in the range of 30 to 55 °C.
  • the phosphating composition can be characterized by the following preferred and particularly preferred parameter ranges: FS 0.3 to 2.0 0.7 to 1.6 FS (concealed) 0.5 to 8 1 to 6 GSF 12 to 28 22 to 26 GS 12 to 45 18 to 35 S-value 0.01 to 0.2 0.03 to 0.15 temperature °C 30 to 50 °C 35 to 45 °C
  • FS stands for free acid
  • FS (diluted) for free acid (diluted)
  • GSF for total acid according to Fischer
  • GS for total acid
  • S-value for acid value
  • a suitable container for example a 300 ml Erlenmeyer flask. If the phosphating composition contains complex fluorides, 2-3 g of potassium chloride are added to the sample. Then, using a pH meter and an electrode, titrate with 0.1 M NaOH to a pH value of 3.6. The amount of 0.1 M NaOH used in ml per 10 ml of the phosphating composition gives the value of the free acid (FS) in points.
  • FS free acid
  • a suitable container for example a 300 ml Erlenmeyer flask. Then 150 ml of deionized water are added added. Using a pH meter and an electrode, titrate with 0.1 M NaOH to a pH value of 4.7. The amount of 0.1 M NaOH used in ml per 10 ml of the diluted phosphating composition gives the value of the free acid (diluted) (FS (dil.)) in points.
  • the content of complex fluoride can be determined from the difference to the free acid (FS). If this difference is multiplied by the factor 0.36, the content of complex fluoride is obtained as SiF 6 2- in g/l.
  • the diluted phosphating composition is titrated to a pH value of 8.9 after adding potassium oxalate solution using a pH meter and an electrode with 0.1 M NaOH.
  • the consumption of 0.1 M NaOH in ml per 10 ml of the diluted phosphating composition gives the total acid according to Fischer (GSF) in points. If this value is multiplied by 0.71, the total content of phosphate ions is calculated as P 2 O 5 ( See W. Rausch: "The Phosphating of Metals”. Eugen G. Leuze-Verlag 2005, 3rd edition, pp. 332 ff ).
  • the total acidity (TA) is the sum of the divalent cations contained as well as free and bound phosphoric acids (the latter are phosphates). It is determined by the consumption of 0.1 M NaOH using a pH meter and an electrode. To do this, 10 ml of the phosphating composition is pipetted into a suitable container, for example a 300 ml Erlenmeyer flask, and diluted with 25 ml of deionized water. Then titrate with 0.1 M NaOH to a pH of 9. The consumption in ml per 10 ml of the diluted phosphating composition corresponds to the total acidity (TA) score.
  • TA total acidity
  • S-value stands for the ratio FS : GSF and is obtained by dividing the value of the free acid (FS) by the value of the total acid according to Fischer (GSF).
  • the phosphating composition is essentially nickel-free. Preferably, it contains less than 0.1 g/l and more preferably less than 0.01 g/l of nickel ions.
  • the treatment of the metallic surface with the phosphating composition is preferably carried out for 30 to 480, particularly preferably for 60 to 300 and most particularly preferably for 90 to 240 seconds, preferably by dipping or spraying.
  • the following preferred and particularly preferred zinc phosphate layer weights are achieved on the metallic surface, depending on the treated surface (determined by X-ray fluorescence analysis (XRF)): Treated surface zinc phosphate coating weight (g/m 2 ) Steel 0.5 to 6 1 to 5 hot-dip galvanizing 1.0 to 6 1.5 to 5 electrolytic galvanizing 1.0 to 6 1.5 to 5 aluminum 0.5 to 6 1 to 5
  • the metallic surface is rinsed after treatment with the phosphating composition, more preferably rinsed with demineralized water or town water. If necessary, the metallic surface is dried before treatment with the post-rinse composition.
  • the already The metallic surface treated with the phosphating composition i.e. phosphate-coated, is further treated with an aqueous rinsing composition as defined in claim 1.
  • the rinse composition can be obtained from a concentrate by diluting with a suitable solvent, preferably with water, by a factor between 1 and 1000, preferably between 5 and 500, and if necessary adding a pH-modifying substance.
  • the rinse composition contains at least one type of metal ion selected from the group consisting of the ions of the following metals in the following preferred, particularly preferred and most particularly preferred concentration ranges (all calculated as the corresponding metal): Mo 10 to 500 mg/l 20 to 225 mg/l Cu 1 to 1000 mg/l 100 to 500 mg/l 150 to 225 mg/l Ag 1 to 500 mg/l 5 to 300 mg/l 20 to 150 mg/l Au 1 to 500 mg/l 10 to 300 mg/l 20 to 200 mg/l Pd 1 to 200 mg/l 5 to 100 mg/l 15 to 60 mg/l Sn 1 to 500 mg/l 2 to 200 mg/l 3 to 100 mg/l Sb 1 to 500 mg/l 2 to 200 mg/l 3 to 100 mg/l Ti 20 to 500 mg/l 50 to 300 mg/l 50 to 150 mg/l Zr 20 to 500 mg/l 50 to 300 mg/l 50 to 150 mg/l Hf 20 to 500 mg/l 50 to 300 mg/l 50 to 150 mg/l
  • the metal ions contained in the rinsing solution are deposited either in the form of a salt which contains the corresponding metal cation (e.g. molybdenum or tin) preferably in at least two oxidation states - in particular in the form of an oxide-hydroxide, a hydroxide, a spinel or a defect spinel - or in elemental form on the surface to be treated (e.g. copper, silver, gold or palladium).
  • a salt which contains the corresponding metal cation (e.g. molybdenum or tin) preferably in at least two oxidation states - in particular in the form of an oxide-hydroxide, a hydroxide, a spinel or a defect spinel - or in elemental form on the surface to be treated (e.g. copper, silver, gold or palladium).
  • Molybdenum ions are necessarily present as metal ions in the rinsing solution. These are deposited as molybdate, preferably as
  • Ammonium heptamolybdate and particularly preferably as ammonium heptamolybdate x 7 H 2 O is added to the rinse composition.
  • the molybdenum ions can also be added as sodium molybdate.
  • molybdenum ions can also be added to the rinse composition in the form of at least one salt containing molybdenum cations, such as molybdenum chloride, and then oxidized to molybdate by a suitable oxidizing agent, for example by the accelerators described above.
  • a suitable oxidizing agent for example by the accelerators described above.
  • the rinse composition itself contains a corresponding oxidizing agent.
  • the rinsing composition contains molybdenum ions in combination with copper ions, tin ions or zirconium ions, with zirconium ions being mandatory.
  • the rinsing solution contains molybdenum ions in combination with zirconium ions and optionally a polymer or copolymer, in particular selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypropylenes as well as their mixtures and copolymers and polyacrylic acid, wherein the content of molybdenum ions is mandatory and the content of zirconium ions is preferably in the range of 10 to 500 mg/l (calculated as metal).
  • the content of molybdenum ions is preferably in the range from 20 to 225 mg/l, particularly preferably from 50 to 225 mg/l and very particularly preferably from 100 to 225 mg/l and the content of zirconium ions is in the range from 50 to 300 mg/l, particularly preferably from 50 to 150 mg/l.
  • the metal ions are copper ions.
  • the rinsing solution preferably contains these in a concentration of 100 to 500 mg/l, more preferably 150 to 225 mg/l.
  • the rinse composition according to the invention contains at least one polymer selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypropylenes as well as mixtures and copolymers thereof.
  • the at least one polymer is preferably present in a concentration in the range from 0.1 to 5 g/l, more preferably from 0.1 to 3 g/l, more preferably from 0.3 to 2 g/l and particularly preferably in the range from 0.5 to 1.5 g/l (calculated as pure polymer).
  • the polymers used are preferably cationic polymers, in particular polyamines, polyethyleneamines, polyimines and/or polyethyleneimines.
  • a polyamine and/or polyimine is particularly preferably used, and a polyamine is most preferably used.
  • the rinse composition disclosed herein contains at least one type of metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin, antimony, titanium, zirconium and hafnium and at least one polymer selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypropylenes and mixtures and copolymers thereof, each in the following preferred, particularly preferred and very particularly preferred concentration ranges (polymer calculated as pure polymer and metal ions calculated as corresponding metal).
  • metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin, antimony, titanium, zirconium and hafnium
  • polymer selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and poly
  • the at least one polymer is a cationic polymer, in particular a polyamine and/or polyimine, and the metal ions are copper ions, molybdenum ions and/or zirconium ions, each in the following preferred, particularly preferred and very particularly preferred concentration ranges (polymer calculated as pure polymer and metal ions calculated as corresponding metal).
  • Mo 1 to 1000 mg/l 10 to 500 mg/l 20 to 225 mg/l Cu 1 to 1000 mg/l 100 to 500 mg/l 150 to 225 mg/l Zr 20 to 500 mg/l 50 to 300 mg/l 50 to 150 mg/l kat.
  • the rinsing composition preferably additionally comprises - particularly when the metallic surface is aluminum or an aluminum alloy - 20 to 500 mg/l, more preferably 50 to 300 mg/l and particularly preferably 50 to 150 mg/l of Ti, Zr and/or Hf in complexed form (calculated as metal). These are preferably fluorocomplexes.
  • the rinsing composition preferably comprises 10 to 500 mg/l, more preferably 15 to 100 mg/l and particularly preferably 15 to 50 mg/l of free fluoride.
  • the rinsing composition contains Zr in complexed form (calculated as metal) and at least one type of metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin and antimony, wherein the presence of ions of molybdenum is mandatory.
  • a rinsing composition comprising Ti, Zr and/or Hf in complexed form preferably additionally contains at least one organosilane and/or at least one hydrolysis product thereof, i.e. an organosilanol, and/or at least one condensation product thereof, i.e. an organosiloxane/polyorganosiloxane, in a concentration range of 5 to 200 mg/l, more preferably from 10 to 100 mg/l and particularly preferably from 20 to 80 mg/l (calculated as Si).
  • the at least one organosilane preferably has at least one amino group Particularly preferably, it is one which can be hydrolyzed to an aminopropylsilanol and/or to 2-aminoethyl-3-aminopropylsilanol and/or a bis(trimethoxysilylpropyl)amine.
  • the pH of the rinse composition is preferably in the acidic range, more preferably in the range of 3 to 5, particularly preferably in the range of 3.5 to 5.
  • the pH is therefore preferably 3.5 to 4.5 and particularly preferably 3.5 to 4.0.
  • the rinse composition is substantially nickel-free. Preferably, it contains less than 0.1 g/l and more preferably less than 0.01 g/l of nickel ions.
  • the rinsing composition preferably has a temperature in the range of 15 to 40 °C.
  • the treatment of the metallic surface with the rinsing composition is preferably carried out for 10 to 180, particularly preferably for 20 to 150 and most particularly preferably for 30 to 120 seconds, preferably by dipping or spraying.
  • the invention further relates to a phosphate-coated metallic surface which is obtainable by the method according to the invention.
  • the method according to the invention allows the electrical conductivity of the phosphate-coated metal surface to be specifically adjusted by creating defined pores in the phosphate layer.
  • the conductivity can be either greater, equal to or less than that of a corresponding metal surface provided with a nickel-containing phosphate coating.
  • the electrical conductivity of the phosphate-coated metal surface adjusted using the method according to the invention can be influenced by varying the concentration of a given metal ion or polymer in the rinsing solution.
  • An electrocoating paint can then be cathodically deposited and a paint system applied to the phosphate-coated metallic surface treated with the rinsing composition.
  • the metallic surface is first rinsed after treatment with the rinsing composition, preferably with demineralized water, and dried if necessary.
  • a test plate made of electrolytically galvanized steel (ZE) was coated with a phosphating solution at 53 °C containing 1.3 g/l Zn, 1 g/l Mn, 13 g/l PO 4 3- (calculated as P 2 O 5 ), 3 g/l NO 3 - and 1 g/l nickel. No rinsing was carried out.
  • the current density i in A/cm 2 was then measured across the voltage E in V applied to a silver/silver chloride (Ag/AgCI) electrode (see Fig. 1 : ZE_Variation11_2: Curve 3).
  • the measurement was carried out using so-called linear sweep voltammetry (potential range: -1.1 to -0.2 V ref ; scan rate: 1 mV/s).
  • the measured current density i depends on the electrical conductivity of the conversion coating. The following applies: the higher the measured current density i, the higher the electrical conductivity of the conversion coating. A direct measurement of the electrical conductivity in ⁇ S/cm, as is possible in liquid media, cannot be carried out with conversion coatings.
  • the current density i measured for a nickel-containing conversion coating always serves as a reference point for statements about the electrical conductivity of a given conversion coating.
  • a test plate according to Comparative Example 1 was coated using a nickel-free phosphating solution at 53 °C containing 1.3 g/l Zn, 1 g/l Mn, 16 g/l PO 4 3- (calculated as P 2 O 5 ) and 2 g/l NO 3 - without rinsing and then the current density i was measured against the voltage E according to Comparative Example 1 (see Fig. 1 .
  • a test plate according to Comparative Example 1 was coated using a nickel-free phosphating solution according to Comparative Example 2.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) with a pH value of approx. 4.
  • the current density i over the voltage E was measured according to Comparative Example 1 (see Fig. 2 .
  • a test plate according to Comparative Example 1 was coated using a nickel-free phosphating solution according to Comparative Example 2. The test plate coated in this way was then treated with a rinsing solution containing approx. 220 mg/l copper ions and having a pH value of approx. 4. The current density i over the voltage E was measured according to Comparative Example 1 (see Fig. 3 . ZE_Variation2_1: Curve 1; ZE_Variation2_2: Curve 2). Comparison is again made with comparison example 1 ( Fig. 3 : ZE_Variation11_2: Curve 3).
  • the resting potential of the nickel-free system when using a rinsing solution containing copper ions corresponds to that of the nickel-containing system (Comparative Example 1).
  • the conductivity of this nickel-free system is slightly higher than that of the nickel-containing system.
  • a test plate according to Comparative Example 1 was coated using a nickel-free phosphating solution according to Comparative Example 2.
  • the test plate thus coated was then treated with a rinsing solution containing approx. 1 g/l (calculated on the pure polymer) electrically conductive polyamine (Lupamin ® 9030, manufacturer BASF) with a pH value of approx. 4.
  • the current density i over the voltage E was measured according to comparative example 1 (see Fig. 4 .
  • ZE_Variation3_1 Curve 1; ZE_Variation3_2: Curve 2).
  • Comparison is made with comparative example 1 ( Fig. 4 : ZE_Variation11_2: Curve 3).
  • the resting potential of the nickel-free system when using a rinsing solution containing an electrically conductive polymer corresponds to that of the nickel-containing system (Comparative Example 1).
  • the electrical conductivity of the nickel-free system is slightly reduced compared to the nickel-containing system.
  • a test plate made of hot-dip galvanized steel (EA) was coated using a phosphating solution containing 1 g/l nickel according to Comparative Example 1.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) with a pH value of approx. 4 and then the current density i in A/cm 2 was measured across the voltage E in V applied to a silver/silver chloride (Ag/AgCI) electrode (see Fig. 5 : EA 173: Curve 1).
  • the measurement was carried out using so-called linear sweep voltammetry.
  • a test plate according to Comparative Example 4 was coated using a nickel- and nitrate-free phosphating solution containing 1.2 g/l Zn, 1 g/l Mn and 16 g/l PO 4 3- (calculated as P 2 O 5 ) at 35 °C without rinsing and then the current density i was measured against the voltage E according to Comparative Example 3 (see Fig. 5 .
  • a test plate according to Comparative Example 4 was coated using a nickel-free phosphating solution according to Comparative Example 2.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions with a pH value of approx. 4.
  • the current density i over the voltage E was measured according to Comparative Example 1 (see Fig. 6 .
  • Comparison is made with comparative example 3 ( Fig. 6 : EA 173: curve 1).
  • Test panels according to comparative examples 1 to 3 (VB1 to VB3) and examples 1 and 2 (B1 and B2) were coated with a cathodic electrocoat and a standard automotive paint system (filler, base coat, clear coat) after phosphating and then subjected to a cross-cut test according to DIN EN ISO 2409. Three panels were tested before and after exposure to condensation water for 240 hours (DIN EN ISO 6270-2 CH). The corresponding results can be found in Table 1. A cross-cut result of 0 is the best value and one of 5 is the worst value. Values of 0 and 1 are comparably good values.
  • Table 1 shows the poor results of VB2 and especially VB3 after each load, while B1 (copper ions) and B2 (electrically conductive polyamine) provide good results - at least comparable to VB1 (nickel-containing phosphate).
  • a test plate made of hot-dip galvanized steel (EA) was coated with a nitrite-accelerated phosphating solution (approx. 90 mg/l nitrite) at 53 °C containing 1.1 g/l Zn, 1 g/l Mn, 13.5 g/l PO 4 3- (calculated as P 2 O 5 ), 3 g/l NO 3 - and 1 g/l nickel.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and a pH value of approx. 4.
  • a test plate according to comparative example 6 was coated with a nickel-free phosphating solution at 35 °C containing 1.1 g/l Zn, 1 g/l Mn, 17 g/l PO 4 3- (calculated as P 2 O 5 ) and 0.5 g/l NO 3 - and accelerated with nitrite (approx. 90 mg/l nitrite).
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • a test plate according to Comparative Example 6 was coated with a nickel- and nitrate-free coating containing 1.1 g/l Zn, 1 g/l Mn and 17 g/l PO 4 3- (calculated as P 2 O 5 ).
  • the test plate was coated with a nitrite-accelerated phosphating solution at 35 °C (approx. 90 mg/l nitrite).
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions with a pH value of approx. 4.
  • test plate according to comparative example 6 was coated using a nickel-free, 35 °C warm phosphating solution containing 1.1 g/l Zn, 1 g/l Mn, 17 g/l PO 4 3- (calculated as P 2 O 5 ) and 0.5 g/l NO 3 - with peroxide acceleration (approx. 80 mg/l H 2 O 2 ).
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • test plate according to comparative example 6 was coated using a nickel- and nitrate-free phosphating solution containing 1.1 g/l Zn, 1 g/l Mn and 17 g/l PO 4 3- (calculated as P 2 O 5 ) at 35 °C and peroxide-accelerated (approx. 80 mg/l H 2 O 2 ).
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • Test panels according to comparative examples 6 to 8 (VB6 to VB8) and examples 4 and 5 (B4 and B5) were coated with a cathodic electrocoat and a standard automotive paint system (filler, base coat, clear coat) after phosphating and then subjected to a cross-cut test according to DIN EN ISO 2409. Three panels were tested before and after exposure to condensation water for 240 hours (DIN EN ISO 6270-2 CH). The corresponding results can be found in Tab. 2.
  • Table 2 shows the poor results of VB7 (nitrite accelerated) and VB8 (peroxide accelerated) in comparison to VB6, while B4 (nitrite accelerated) and B5 (peroxide accelerated) provide good results comparable to VB6 (nickel-containing phosphating).
  • a test plate made of hot-dip galvanized steel (EA) was coated with a nitrite-accelerated phosphating solution (approx. 90 mg/l nitrite) at 53 °C containing 1.1 g/l Zn, 1 g/l Mn, 13.5 g/l PO 4 3- (calculated as P 2 O 5 ), 3 g/l NO 3 - and 1 g/l nickel.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and a pH value of approx. 4.
  • a test plate according to comparative example 9 was coated using a nickel- and nitrate-free phosphating solution containing 1.1 g/l Zn, 1 g/l Mn and 17 g/l PO 4 3- (calculated as P 2 O 5 ) at 35 °C with peroxide acceleration (approx. 80 mg/l H 2 O 2 ).
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • test plate made of bare steel was treated with a 53 °C solution containing 1.1 g/l Zn, 1 g/l Mn, 13.5 g/l PO 4 3- (calculated as P 2 O 5 ), 3 g/l NO 3 - and 1 g/l nickel. warm phosphating solution with nitrite acceleration (approx. 90 mg/l nitrite).
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) with a pH value of approx. 4.
  • a test plate according to comparative example 10 was coated using a nickel- and nitrate-free phosphating solution containing 1.1 g/l Zn, 1 g/l Mn and 17 g/l PO 4 3- (calculated as P 2 O 5 ) at 35 °C with peroxide acceleration (approx. 80 mg/l H 2 O 2 ).
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • a test plate made of electrolytically galvanized steel (ZE) was coated with a nitrite-accelerated phosphating solution (approx. 90 mg/l nitrite) at 53 °C containing 1.1 g/l Zn, 1 g/l Mn, 13.5 g/l PO 4 3- (calculated as P 2 O 5 ), 3 g/l NO 3 - and 1 g/l nickel.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and having a pH value of approx. 4.
  • a test plate according to comparative example 11 was coated using a nickel- and nitrate-free phosphating solution containing 1.1 g/l Zn, 1 g/l Mn and 17 g/l PO 4 3- (calculated as P 2 O 5 ) at 35 °C with peroxide acceleration (approx. 80 mg/l H 2 O 2 ).
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • Test panels according to comparative examples 9 to 11 (VB9 to VB11) and examples 6 to 8 (B6 to B8) were coated with a cathodic electrocoat and a standard automotive paint system (filler, base coat, clear coat) after phosphating and subjected to the cross-cut test described above for VB6 to VB8, B4 and B5.
  • the results are summarized in Table 3.
  • test panels were subjected to a VDA test (VDA 621-415), in which the paint infiltration (U) in mm was determined and the paint detachment after stone impact (DIN EN ISO 20567-1, Verf. C) was determined.
  • VDA 621-415 the paint infiltration (U) in mm was determined and the paint detachment after stone impact (DIN EN ISO 20567-1, Verf. C) was determined.
  • a result of 0 is the best value and a result of 5 the worst value after stone impact.
  • a value of up to 1.5 is considered a good value.
  • Table 3 The results are also summarized in Table 3 .
  • Table 3 shows the good results that can be achieved with the nickel-free process according to the invention on hot-dip galvanized steel (B6), as well as on bright steel (B7) and on electrolytically galvanized steel (B8). These are comparable to the nickel-containing process (cf. B6 with VB9, B7 with VB10 and B8 with VB11).
  • a test plate made of hot-dip galvanized steel (EA) was coated with a nitrite-accelerated phosphating solution (approx. 90 mg/l nitrite) at 53 °C containing 1.1 g/l Zn, 1 g/l Mn, 13.5 g/l PO 4 3- (calculated as P 2 O 5 ), 3 g/l NO 3 - and 1 g/l nickel.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and a pH value of approx. 4.
  • a test plate according to Comparative Example 12 was coated with nickel and nitrate-free, peroxide-accelerated (approx. 80 mg/l H 2 O 2 ) phosphating solution containing 1.1 g/l Zn, 1 g/l Mn and 17 g/l PO 4 3- (calculated as P 2 O 5 ) at 35 °C.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions with a pH value of approx. 4.
  • a test plate according to comparative example 12 was coated using a nickel- and nitrate-free phosphating solution containing 1.2 g/l Zn, 1 g/l Mn and 13 g/l PO 4 3- (calculated as P 2 O 5 ) and peroxide-accelerated (approx. 50 mg/l H 2 O 2 ) at 45 °C.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • test plate made of bare steel was coated with a nitrite-accelerated phosphating solution (approx. 90 mg/l nitrite) according to Comparative Example 12.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and having a pH value of approx. 4.
  • a test plate according to Comparative Example 13 was coated using a phosphating solution according to Example 9 with a peroxide acceleration (approx. 80 mg/l H 2 O 2 ). The test plate thus coated was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • a test plate according to Comparative Example 13 was coated using a phosphating solution according to Example 10 with peroxide acceleration (approx. 50 mg/l H 2 O 2 ). The test plate thus coated was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • a test plate made of AA6014 S was coated with a nitrite-accelerated phosphating solution (approx. 90 mg/l nitrite) according to Comparative Example 12.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) with a pH value of approx. 4.
  • a test plate according to Comparative Example 14 was coated using a phosphating solution according to Example 9 with peroxide acceleration (approx. 80 mg/l H 2 O 2 ). The test plate thus coated was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • a test plate according to Comparative Example 14 was coated using a phosphating solution according to Example 10 with peroxide acceleration (approx. 50 mg/l H 2 O 2 ). The test plate thus coated was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions and having a pH value of approx. 4.
  • Test panels according to comparative examples 12 to 14 (VB12 to VB14) and examples 9 to 14 (B9 to B14) were coated with a cathodic electrocoat and a standard automotive paint system (filler, basecoat, clearcoat) after phosphating.
  • test panels of comparative examples 12 and 13 (VB12 and VB13) and examples 9 to 12 (B9 to B12) were subjected to the VDA test described above.
  • the results are summarized in Table 4 .
  • test panels of comparative example 14 (VB14) and examples 13 and 14 (B13 and B14) were subjected to a 240-hour CASS test according to DIN EN ISO 9227.
  • the results are summarized in Table 5 .
  • a test plate made of hot-dip galvanized steel (EA) was coated using a nickel- and nitrate-free phosphating solution containing 1.1 g/l Zn, 1 g/l Mn and 17 g/l PO 4 3- (calculated as P 2 O 5 ) at 35 °C and accelerated with peroxide (approx. 80 mg/l H 2 O 2 ).
  • the acid value of the phosphating solution was set to 0.07.
  • the test plate coated in this way was then treated with a rinsing solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr) and 220 mg/l molybdenum ions with a pH value of approx. 4.
  • a test plate made of hot-dip galvanized steel (EA) was coated using a nickel- and nitrate-free phosphating solution containing 1.1 g/l Zn, 1 g/l Mn and 17 g/l PO 4 3- (calculated as P 2 O 5 ) at 35 °C and peroxide-accelerated (approx. 80 mg/l H 2 O 2 ).
  • the acid value of the phosphating solution was set to 0.05.
  • the test plate coated in this way was then coated with a phosphating solution containing approx. 120 mg/l ZrF 6 2- (calculated as Zr). and 220 mg/l molybdenum ions containing rinsing solution with a pH value of approx. 4.
  • Test panels according to examples 15 and 16 were coated with a cathodic electrocoat and a standard automotive paint system (filler, base coat, clear coat) after phosphating and then subjected to a cross-cut test before and after exposure to condensation water for 240 hours as described above.
  • the results are summarized in Table 6 .
  • Example cross-hatch before exercise (0-5) after exercise (0-5) B15 0 / 0 / 1 3 / 2 / 1 B16 0 / 1 / 0 1 / 1 / 1 / 1
  • Table 6 shows that the cross-cut results after exposure to condensation water can be significantly improved by lowering the acid value (B16).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Detergent Compositions (AREA)
  • Chemically Coating (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (13)

  1. Procédé de phosphatation sensiblement exempte de nickel d'une surface métallique, caractérisé en ce qu'une surface métallique est d'abord traitée, le cas échéant après nettoyage et/ou activation, par une composition aqueuse acide de phosphatation, qui comprend des ions de zinc, de manganèse et de phosphate, elle est le cas échéant rincée et/ou séchée et ensuite traitée par une composition aqueuse de postrinçage, qui comprend 10 à 500 mg/l (calculés sous forme métallique) d'ions de molybdène sous forme de molybdate et d'ions de zirconium et qui présente un pH dans la plage de 3 à 5, la composition de phosphatation et la composition de postrinçage contenant toutes les deux moins de 0,3 g/l d'ions de nickel et la composition de phosphatation contenant moins de 0,5 g/l de nitrate.
  2. Procédé selon la revendication 1, caractérisé en ce que la surface métallique est au moins partiellement galvanisée.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition de phosphatation comprend 0,5 à 3 g/l de fluorure complexe et en ce qu'il s'agit, pour le fluorure complexe, de tétrafluoroborate (BF4 -) et/ou d'hexafluorosilicate (SiF6 2-).
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition de phosphatation contient du H2O2 comme accélérateur.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition de phosphatation présente un acide libre dans la plage de 0,3 à 2,0, un acide libre (dilué) dans la plage de 0,5 à 8, un acide total selon Fischer dans la plage de 12 à 28, un acide total dans la plage de 12 à 45 et une valeur d'acide dans la plage de 0,01 à 0,2.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition de phosphatation présente une valeur d'acide dans la plage de 0,03 à 0,065.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition de phosphatation présente une température dans la plage de 30 à 50°C, de préférence dans la plage entre 35 et 45°C.
  8. Procédé selon la revendication 1, caractérisé en ce que la composition de postrinçage comprend 20 à 225 mg/l d'ions de molybdène et 50 à 300 mg/l d'ions de zirconium.
  9. Procédé selon l'une des revendications 1 ou 8, caractérisé en ce que le pH de la composition de postrinçage est de 3,5 à 4,5, de préférence de 3,5 à 4,0.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition de postrinçage comprend des ions de cuivre.
  11. Procédé selon la revendication 10, caractérisé en ce que la composition de postrinçage comprend 100 à 500 mg/l d'ions de cuivre.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition de postrinçage comprend une polyamine et/ou une polyimine.
  13. Surface métallique revêtue de phosphate, caractérisée en ce qu'elle peut être obtenue par un procédé selon l'une des revendications 1 à 12.
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