Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • 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 process for essentially nickel-free phosphating of a metallic surface, a corresponding phosphating composition and a correspondingly phosphate-coated metallic surface.
• phosphate coatings on metallic surfaces are known. Such coatings serve to protect the corrosion of the metallic surfaces and also as adhesion promoters for subsequent paint layers. Such phosphate coatings are mainly used in the automotive industry and the general industry.
• KTL cathodically deposited electrodeposition paints
• phosphate coatings are usually applied by means of a nickel-containing phosphating solution.
• the elementary or as alloying constituent, e.g. Zn / Ni, deposited nickel ensures a suitable conductivity of the coating in the subsequent electrodeposition coating.
• nickel ions are no longer desirable as part of treatment solutions because of their high toxicity and environmental toxicity, and should therefore be avoided or at least reduced in content as much as possible.
• the use of nickel-free or low-nickel Phosphatierlositch is known in principle. However, this is limited to certain substrates such as steel.
• the object of the present invention was therefore to provide a process with which metallic surfaces can be phosphated essentially nickel-free, with respect to their electrochemical properties, comparable or nearly comparable to the metallic surfaces which have been treated with nickel-containing phosphating solutions, and in particular the abovementioned Disadvantages of the prior art can be avoided.
• a metallic surface In the method according to the invention for substantially nickel-free phosphating of a metallic surface, a metallic surface, optionally after purification and / or activation, is first treated with an acidic aqueous phosphating composition comprising zinc ions, manganese ions and phosphate ions, optionally rinsed and / or dried, and thereafter treated with an aqueous post-rinse composition comprising 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 classes of polymers comprising polyamines, polyethyleneamines, polyanilines, polyimines, polyethylenimines, polythiophenes and polypryrenes and mixtures and copolymers thereof, wherein both the phosphating composition and the post-rinse composition are substantially nickel free.
• aqueous composition refers to a composition which comprises at least some, preferably predominantly water, as the solvent, and may comprise, in addition to dissolved constituents, also dispersed, ie emulsified and / or suspended constituents.
• phosphate ions are also to be understood as meaning hydrogenphosphate, dihydrogenphosphate and phosphoric acid, and pyrophosphoric acid and polyphosphoric acid as well as all their partially and completely deprotonated forms are to be included in the term "metal ion" in the context of the present invention either a metal cation or a complex cation Metal cation or a complex metal anion understood.
• composition contains less than 0.3 g / l of nickel ions, it should be considered as "essentially 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.
• the hot-dip galvanizing and the electrolytic galvanizing in each case are in particular such on steel.
• the metallic surface is at least partially galvanized.
• the inventive method is particularly suitable for multi-metal applications.
• a metallic surface is to be coated, which is not a fresh hot-dip galvanizing, it is advantageous to clean the metallic surface before the treatment with the phosphating only in an aqueous cleaning composition, in particular to degrease.
• an acidic, neutral, alkaline or strongly alkaline cleaning composition it is possible in particular to use an acidic, neutral, alkaline or strongly alkaline cleaning composition, but optionally also an acidic or neutral pickling composition.
• the aqueous cleaning composition may optionally contain, in addition to at least one surfactant, a scaffold and / or other additives such as complexing agents.
• the use of an activating cleaner is also possible.
• After cleaning / pickling then takes place advantageously at least rinsing of the metallic surface with water, wherein the water optionally also dissolved in water additive such.
• a nitrite or surfactant may be added.
• the activation composition serves to deposit a plurality of ultrafine phosphate particles as seed crystals on the metallic surface. These help in the subsequent process step, in contact with the phosphating - preferably without interim rinsing - form a particular crystalline phosphate layer with the highest possible number of densely arranged fine phosphate crystals or a substantially closed phosphate layer.
• acidic or alkaline compositions based on titanium phosphate or zinc phosphate may be considered as activating compositions.
• activating agents in particular titanium phosphate or zinc phosphate, in the cleaning composition, ie to carry out purification and activation in one step.
• the acidic aqueous phosphating composition includes zinc ions, manganese ions, and phosphate ions.
• the phosphating composition may be obtained from a concentrate by dilution with a suitable solvent, preferably with water, by a factor of between 1 and 100, preferably between 5 and 50, and if necessary adding a pH modifying substance.
• a suitable solvent preferably with water
• the phosphating composition preferably comprises the following components in the following preferred and particularly preferred concentration ranges:
• a concentration in the range from 0.3 to 2.5 g / l has already been found to be advantageous with regard to the free fluoride, a concentration in the range from 10 to 250 mg / l.
• the complex fluoride is preferably tetrafluoroborate (BF " ) and / or hexafluorosilicate (SiF 6 2 ⁇ ).
• a content of complex fluoride and single fluoride, for example sodium fluoride, in the phosphating composition advantageous.
• Al 3+ is a bad poison in phosphating systems and can be removed from the system by complexation with fluoride, eg as cryolite.
• Complex fluorides are added to the bath as a "fluoride buffer", as otherwise the fluoride content quickly falls off and coating no longer takes place.Fluoride thus promotes the formation of the phosphate layer and thus indirectly also improves paint adhesion and corrosion protection.Complex fluoride also helps on galvanized material, errors In particular, in the treatment of aluminum, it is furthermore advantageous if the phosphating composition has a content of Fe (III), in which case a Fe (III) content in the range from 0.001 to 0.2 g / l, particularly preferably from 0.005 to 0.1 g / l and most preferably from 0.01 to 0.05 g / l.
• 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:
• a concentration in the range of 0.1 to 3.0 g / l has already been found to be advantageous with respect to the H2O2, a concentration in the range from 5 to 200 mg / l.
• the at least one accelerator is H2O2.
• the phosphating composition preferably contains less than 1 g / l, more preferably less than 0.5 g / l, more preferably less than 0.1 g / l and most preferably less than 0.01 g / l of nitrate.
• the nitrate in the phosphating composition causes an additional acceleration of the layer formation reaction, which leads to lower coating weights but, above all, reduces the incorporation of manganese into the crystal.
• the manganese content of the phosphate coating is too low, this is at the expense of its alkali resistance.
• Alkali resistance in turn plays a crucial role in subsequent cathodic electrodeposition.
• an electrolytic splitting of water occurs at the substrate surface: Hydroxide ions are formed. This causes the pH at the interface of the substrate to increase. It is true that only then can the electrocoating be agglomerated and separated. However, the increased pH 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 stands for free acid
• FS (verd.) For free acid (diluted)
• GSF for total acid according to Fischer
• GS for total acid
• S value for acid value
• a suitable vessel 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, it is titrated with 0.1 M NaOH to a pH of 3.6. The amount of 0.1 M NaOH consumed in ml per 10 ml of the phosphating composition gives the value of the free acid (FS) in points. Free acid (diluted) (FS (dil.)):
• the dilute phosphating composition is titrated to pH 8.9 after addition of potassium oxalate solution using a pH meter and electrode with 0.1 M NaOH.
• the consumption of 0.1 M NaOH in ml per 10 ml of the diluted phosphating composition hereby gives the total Fischer acid (GSF) in points. If this value is multiplied by 0.71, the total content of phosphate ions is calculated as P2O 5 (see W. Rausch: "The Phosphatization of Metals.” Eugen G. Leuze-Verlag 2005, 3rd edition, pp. 332 ff) ,
• the total acid (GS) is the sum of the divalent cations present as well as free and bound phosphoric acids (the latter being phosphates). It is determined by the consumption of 0.1 M NaOH using a pH meter and an electrode. For this purpose, 10 ml of the phosphating composition are pipetted into a suitable vessel, for example a 300 ml Erlenmeyer flask and diluted with 25 ml of deionized water. It is then titrated 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 acid score (GS).
• 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).
• a temperature of the phosphating of less than 45 ° C, preferably in the range between 35 and 45 ° C leads to further improved corrosion and paint adhesion values.
• the phosphating composition is essentially nickel free. It preferably 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 very particularly preferably for 90 to 240 seconds, preferably by means of dipping or spraying.
• the following preferred and particularly preferred zinc phosphate layer weights are obtained on the metallic surface (determined by X-ray fluorescence analysis (RFA)):
• the metallic surface is rinsed after treatment with the phosphating composition, more preferably rinsed with demineralized water or city water.
• the metallic surface is dried prior to treatment with the post-rinse composition.
• the post-rinse composition can be obtained from a concentrate by dilution with a suitable solvent, preferably with water, by a factor of between 1 and 1000, preferably between 5 and 500, and if necessary adding a pH-modifying substance.
• the post-rinse composition contains at least one kind of metal ion selected from the group consisting of the ions of the following metals in the following preferred, most preferred and most preferred concentration ranges (all calculated as corresponding metal):
• the metal ions contained in the rinsing solution separate either in the form of a salt which preferably contains the corresponding metal cation (eg molybdenum or tin) in at least two oxidation states - in particular in the form of an oxide hydroxide, a hydroxide, a spinel or a defect spinel - or elementally on the surface to be treated (eg copper, silver, gold or palladium).
• a salt which preferably contains the corresponding metal cation (eg molybdenum or tin) in at least two oxidation states - in particular in the form of an oxide hydroxide, a hydroxide, a spinel or a defect spinel - or elementally on the surface to be treated (eg copper, silver, gold or palladium).
• the metal ions are molybdenum ions. These are preferred as molybdate, more preferably as Ammonium heptamolybdate and more preferably added as ammonium heptamolybdate x 7 H 2 O the Nach Hugheszusammen experience.
• the molybdenum ions can also be added as Nathummolybdat.
• molybdenum ions may also be added to the post-rinse composition in the form of at least one molybdenum cation-containing salt, 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 post-rinse composition itself contains a corresponding oxidizing agent. More preferably, the post-rinse composition contains molybdenum ions in combination with copper ions, tin ions or zirconium ions.
• a polymer or copolymer in particular selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypryrenes and mixtures and copolymers thereof and polyacrylic acid, wherein the content molybdenum ions and zirconium ions are each 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 in the range from 50 to 300 mg / l. l, more preferably from 50 to 150 mg / l.
• the metal ions are copper ions.
• the rinsing solution then contains these in a concentration of 100 to 500 mg / l, more preferably from 150 to 225 mg / l.
• the rinse-off composition according to the invention comprises at least one polymer selected from the group consisting of the polymer classes of the polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypryrenes and also their mixtures and copolymers.
• the at least one polymer is preferably in a concentration in the range of 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. Particular preference is given to using a polyamine and / or polyimine, very particularly preferably a polyamine.
• the rinse-off composition according to the invention comprises at least one kind 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 the polyamines, polyethyleneamines, polyanilines, polyimines, polyethylenimines, polythiophenes and polypryrenes and their mixtures and copolymers, in each case in the following preferred, particularly preferred and very particularly preferred concentration ranges (polymer calculated as pure polymer and metal ions calculated as the 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 the polyamines, polyethyleneamines, polyanilines, polyimines, polye
• 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, in each case in the following preferred, particularly preferred and very particular preferred concentration ranges (polymer calculated as pure polymer and metal ions calculated as the corresponding metal).
• the post-rinse composition comprises, in particular, when the metallic surface is aluminum or an aluminum alloy, preferably additionally 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 fluoro complexes.
• the post-rinse composition preferably comprises 10 to 500 mg / l, more preferably 15 to 100 mg / l, and most preferably 15 to 50 mg / l of free fluoride.
• the post-rinse composition contains Zr in complexed form (calculated as metal) and at least one kind of metal ions selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin and antimony, preferably molybdenum.
• a post-rinse 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, ie an organosilanol, and / or at least one condensation product thereof, ie an organosiloxane / polyorganosiloxane, within 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 on. Particularly preferably it is one which can be hydrolyzed to an aminopropylsilanol and / or to 2-aminoethyl-3-amino-propyl-silanol and / or a bis (trimethoxysilylpropyl) amine.
• the pH of the post-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 preferably 3.5 to 4.5, and more preferably 3.5 to 4.0.
• the post-rinse composition is essentially nickel free. It preferably contains less than 0.1 g / l and more preferably less than 0.01 g / l of nickel ions.
• the post-rinse composition preferably has a temperature in the range of 15 to 40 ° C.
• the treatment of the metallic surface with the post-rinse composition is preferably carried out for 10 to 180, particularly preferably for 20 to 150 and very particularly preferably for 30 to 120 seconds, preferably by means of dipping or spraying.
• the invention further relates to a phosphate-coated metallic surface, which is obtainable by the method according to the invention.
• the electrical conductivity of the phosphate-coated metal surface can be adjusted in a targeted manner by producing defined pores in the phosphate layer.
• the conductivity may be either greater than, equal to, or smaller than that of a corresponding metal surface provided with a nickel-containing phosphate coating.
• the adjusted by the inventive method electrical conductivity of the phosphate-coated metal surface can be influenced by the variation of the concentration of a given metal ion or polymer in the rinse.
• On the phosphate-coated - as well as the Nachêtzusammen GmbH treated - metallic surface can then cathodically deposited an electrodeposition paint and a paint system can be applied.
• the metallic surface is first rinsed after the treatment with the Nach Whyzusammen GmbH, preferably with deionized water, and optionally dried.
• a test plate of electrolytically galvanized steel (ZE) was prepared by means of a 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 also 1 g / l nickel containing, 53 ° C hot Phosphatierlosung coated. No rinsing was done. Subsequently, the current density i in A / cm 2 was compared with the vs. a voltage applied to silver / silver chloride (Ag / AgCl) electrode E is measured in V (see FIG. 1: ZE_Variation1 1_2: curve 3).
• the measurement was carried out by means of so-called linear sweep voltammetry (potential range: -1, 1 to -0.2 V ref ; scan rate: 1 mV / s).
• the measured current density i is dependent on the electrical conductivity of the conversion coating. 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, can not be carried out in conversion coatings.
• the current density i measured in the case of 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 obtained by means of a nickel-free, 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 " , Coated 53 ° C warm Phosphatierlosung without rinsing and then the current density i over the voltage E according to Comparative Example 1 measured (see Fig. 1. ZE_Variation1_1: curve 1, ZE_Variation1_3: curve 2).
• a test plate according to Comparative Example 1 was coated by means of a nickel-free phosphating solution according to Comparative Example 2. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4. The current density i across the voltage E was measured according to Comparative Example 1 (see FIG. 2. ZE_Variation6_1: curve 1; ZE_Variation6_2: curve 2). Comparing with Comparative Example 1 (FIG. 2: ZE_Variation1 1_2: curve 3). As can be seen from FIG.
• a test plate according to Comparative Example 1 was coated by means of a nickel-free phosphating solution according to Comparative Example 2. Subsequently, the test plate coated in this way was treated with a rinsing solution containing about 220 mg / l copper ions and having a pH of about 4. The current density i across the voltage E was measured according to Comparative Example 1 (see FIG. 3. ZE_Variation2_1: curve 1; ZE_Variation2_2: curve 2). Compared again with Comparative Example 1 (FIG. 3: ZE_Variation1 1_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 increased over that of the nickel-containing system.
• a test plate according to Comparative Example 1 was coated by means of a nickel-free phosphating solution according to Comparative Example 2. Subsequently, the thus coated test plate was treated with a rinsing solution, which was about 1 g / l (calculated on the pure polymer) electrically conductive polyamine (Lupamin® 9030, manufacturer BASF) contained a pH of about 4 had.
• the current density i across 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_Variation1 1_2: curve 3).
• the quiescent potential of the nickel-free system when using an after-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 somewhat reduced compared to the nickel-containing system.
• a test plate of hot-dip galvanized steel (EA) was coated by means of a 1 g / l nickel-containing phosphating solution according to Comparative Example 1. Subsequently, the thus-coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4, and then the current density i in A / cm 2 was compared with the voltage. a voltage applied to silver / silver chloride (Ag / AgCl) electrode E was measured in V (see FIG. 5: EA 173: curve 1). The measurement was carried out by means of so-called linear sweep voltammetry. Comparative Example 5
• a test plate according to Comparative Example 4 was coated by means of a nickel-free and nitrate-free, 1, 2 g / l Zn, 1 g / l Mn and 16 g / l PO 3 " (calculated as P2O 5 ) containing 35 ° C warm phosphating without rinsing and then the current density i is measured via the voltage E according to Comparative Example 3 (see Fig. 5.
• EA 167 2 curve 2).
• a test plate according to Comparative Example 4 was coated by means of a nickel-free phosphating solution according to Comparative Example 2. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4. The current density i over the voltage E was measured according to Comparative Example 1 (see Fig. 6. EA 178: curve 3, EA 178 2: curve 2). Comparison is made with Comparative Example 3 (FIG. 6: EA 173: curve 1).
• FIG. 6 corresponds to the rest potential of the nickel-free system in the use of a ZrF 6 2 ⁇ and molybdenum ion-containing rinsing solution (Example 3) that of the nickel-containing system (Comparative Example 4).
• Test plates according to Comparative Examples 1 to 3 (VB1 to VB3) and Examples 1 and 2 (B1 and B2) were coated after phosphating with a cathodic electrodeposition paint and a standard autobillack construction (filler, basecoat, clearcoat) and then a cross-cut test according to DIN EN ISO 2409 subjected. In each case, 3 panels were tested before and after exposure to condensation for 240 hours (DIN EN ISO 6270-2 CH). The corresponding results can be found in Table 1. A grating cut result of 0 is the best, and one of 5 the worst value. Values of 0 and 1 are comparable good values.
• Tab. 1 reveals the poor results of VB2 and in particular VB3 in each case after loading, while B1 (copper ions) and B2 (electrically conductive polyamine) give good - VB1 (nickel-containing phosphating) at least comparable results.
• a test plate of hot-dip galvanized steel (EA) was prepared by means of a 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 also 1 g / l nickel-containing, 53 ° C warm Phosphatierlosung nitritbeuggt (about 90 mg / l nitrite) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4.
• a test panel according to Comparative Example 6 was prepared by means of a nickel-free, 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 " containing 35 ° C warm Phosphatierlosung nitrite accelerated (about 90 mg / l nitrite) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4.
• a test plate according to Comparative Example 6 was obtained by means of a nickel- and nitrate-free, 1, 1 g / l Zn, 1 g / l Mn and 17 g / l PO 4 3 " (calculated as P2O 5 ), 35 ° C warm Phosphatierates nitrite-accelerated (about 90 mg / l nitrite) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4. Comparative Example 8
• a test panel according to Comparative Example 6 was prepared by means of a nickel-free, 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 " containing 35 ° C warm phosphating accelerated peroxide (about 80 mg / l H2O2) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4.
• a test plate according to Comparative Example 6 was peroxide-accelerated by means of a nickel-free and nitrate-free, 1.3 g / l Zn, 1 g / l Mn and 17 g / l PO 4 3 (calculated as P2O 5 ) containing 35 ° C phosphating solution ( 80 mg / l H2O2), followed by the test plate coated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4 treated.
• Test plates according to Comparative Examples 6 to 8 (VB6 to VB8) and Examples 4 and 5 (B4 and B5) were coated after phosphating with a cathodic electrodeposition paint and a standard autobillack construction (filler, basecoat, clearcoat) and then a cross-cut test according to DIN EN ISO 2409 subjected. In each case, 3 panels were tested before and after exposure to condensation for 240 hours (DIN EN ISO 6270-2 CH). The corresponding results can be found in Tab. 2.
• Table 2 Table 2
• Table 2 shows the poor results of VB7 (nitrite accelerated) and VB8 (peroxide accelerated) compared to VB6, while B4 (nitrite accelerated) and B5 (peroxide accelerated) give good - VB6 (nickel phosphating) comparable results.
• a test plate of hot-dip galvanized steel (EA) was prepared by means of a 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 also 1 g / l nickel-containing, 53 ° C warm Phosphatierlosung nitritbeuggt (about 90 mg / l nitrite) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4.
• a test plate according to Comparative Example 9 was peroxide-accelerated by means of a nickel-free and nitrate-free, 1 g / l Zn, 1 g / l Mn and 17 g / l PO 4 3 (calculated as P2O 5 ), 35 ° C phosphating solution ( 80 mg / l H2O2), followed by the test plate coated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4 treated.
• a test plate of bare steel was prepared by means of a 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, 53 ° C hot Phosphatierlosung nitritbeuggt (about 90 mg / l nitrite) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4.
• a test plate according to Comparative Example 10 was peroxide-accelerated by means of a nickel-free and nitrate-free, 1 g / l Zn, 1 g / l Mn and 17 g / l PO 4 3 (calculated as P2O 5 ), 35 ° C phosphating solution ( 80 mg / l H2O2), followed by the test plate coated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4 treated.
• a test plate of electrolytically galvanized steel (ZE) was prepared by means of a 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 also 1 g / l nickel, 53 ° C warm Phosphatierlosung nitritbeuggt (about 90 mg / l nitrite) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4.
• a test plate according to Comparative Example 1 1 was peroxide-accelerated by means of a nickel- and nitrate-free, 1, 1 g / l Zn, 1 g / l Mn and 17 g / l PO 4 3 " (calculated as P2O 5 ) containing 35 ° C warm Phosphatierlosung 80 mg / l H2O2) and the test plate thus coated was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of ca. 4 treated.
• Test plates according to Comparative Examples 9 to 1 1 (VB9 to VB1 1) and Examples 6 to 8 (B6 to B8) were coated after phosphating with a cathodic electrodeposition paint and a standard autobillack construction (filler, basecoat, clearcoat) and that at VB6 to VB8 , B4 and B5 previously described cross-hatch test.
• the results are summarized in Tab. 3.
• said test plates were subjected to a VDA test (VDA 621-415), wherein the paint infiltration (U) was determined in mm and the paint peeling after rockfall (DIN EN ISO 20567-1, Verf. C) was determined.
• a result of 0 is the best, one of 5 is the worst value after the fall of the stone.
• a value up to 1, 5 is to be regarded as a good value.
• the results are also summarized in Tab. 3.
• Table 3 shows the good results which can be achieved with the nickel-free process according to the invention both on hot-dip galvanized steel (B6) and on bare steel (B7) and on electrolytically galvanized steel (B8). These are comparable to the nickel-containing process (compare B6 with VB9, B7 with VB10 and B8 with VB1 1).
• a test plate of hot-dip galvanized steel (EA) was prepared by means of a 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 also 1 g / l nickel-containing, 53 ° C warm Phosphatierlosung nitritbeuggt (about 90 mg / l nitrite) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4.
• a test plate according to Comparative Example 12 was by means of a nickel and nitrate-free, 1 g / l Zn, 1 g / l Mn and 17 g / l PO 4 3 " (calculated as P2O 5 ), 35 ° C warm phosphating peroxidized accelerated (about 80 mg / l H2O2) the so-coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4.
• test plate according to Comparative Example 12 was peroxide-accelerated by means of a nickel- and nitrate-free, 1, 2 g / l Zn, 1 g / l Mn and 13 g / l PO 3 " (calculated as P2O 5 ) containing 45 ° C phosphating (approx Subsequently, the test plate thus coated was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4 ,
• test plate made of bare steel was nitrite-accelerated by means of a phosphating solution according to Comparative Example 12 (about 90 mg / l nitrite). Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4.
• test plate according to Comparative Example 13 was peroxide-accelerated by means of a phosphating solution according to Example 9 (about 80 mg / l H2O2) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4.
• test plate according to Comparative Example 13 was peroxide-accelerated by means of a phosphating solution according to Example 10 (about 50 mg / l H2O2) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4. Comparative Example 14
• test plate of AA6014 S was coated with nitrite (about 90 mg / l nitrite) by means of a phosphating solution according to comparative example 12. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4.
• test plate according to Comparative Example 14 was peroxide-accelerated by means of a phosphating solution according to Example 9 (about 80 mg / l H2O2) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4.
• test plate according to Comparative Example 14 was peroxide-accelerated by means of a phosphating solution according to Example 10 (about 50 mg / l H2O2) coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4.
• Test plates according to Comparative Examples 12 to 14 (VB12 to VB14) and Examples 9 to 14 (B9 to B14) were coated after phosphating with a cathodic electrodeposition paint and a standard auto paint finish (filler, basecoat, clearcoat).
• a hot dip galvanized steel (EA) test panel was heated to 35 ° C. using a nickel and nitrate-free, 1.1 g / l Zn, 1 g / l Mn and 17 g / l PO 4 3 (calculated as P2O 5 ) 80 mg / l H2O2), the acid value of the phosphatizing solution was adjusted to 0.07, and the test plate thus coated was treated with about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 Mg / l rinsing solution containing molybdenum ions with a pH of about 4 treated.
• EA hot dip galvanized steel
• a test plate of hot-dip galvanized steel was by means of a 35 ° C phosphatizing solution containing nickel and nitrate, 1, 1 g / l Zn, 1 g / l Mn and 17 g / l PO 3 " (calculated as P2O 5 ) 80 mg / l H2O2), the acid value of the phosphating solution was adjusted to 0.05, and the test plate thus coated was then treated with about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr). and rinsing solution containing 220 mg / 1 molybdenum ions having a pH of about 4 treated.
• Test panels according to Examples 15 and 16 were coated after phosphating with a cathodic electrodeposition paint and a standard autobillack construction (filler, basecoat, clearcoat) and then - as described above - a cross-cut test before and after loading for 240 hours with condensed water subjected.
• the results are summarized in Tab. 6.
• Tab. 6 shows that the grating cut results can be significantly improved after loading with condensed water by lowering the acid value (B16).

Applications Claiming Priority (2)

Publications (1)

Family

ID=55802343

Family Applications (3)

Family Applications After (2)

Country Status (12)

Families Citing this family (14)

Family Cites Families (27)

• 2016
  • 2016-04-07 JP JP2017553108A patent/JP6810704B2/ja active Active
  • 2016-04-07 BR BR112017021409-1A patent/BR112017021409B1/pt active IP Right Grant
  • 2016-04-07 EP EP16718613.9A patent/EP3280831A1/de active Pending
  • 2016-04-07 RU RU2017138446A patent/RU2721971C2/ru active
  • 2016-04-07 MX MX2017012919A patent/MX2017012919A/es unknown
  • 2016-04-07 ES ES16717585T patent/ES2873381T3/es active Active
  • 2016-04-07 US US15/562,970 patent/US10738383B2/en active Active
  • 2016-04-07 KR KR1020177031821A patent/KR20170133480A/ko active IP Right Grant
  • 2016-04-07 WO PCT/EP2016/057620 patent/WO2016162422A1/de active Application Filing
  • 2016-04-07 JP JP2017553120A patent/JP6804464B2/ja active Active
  • 2016-04-07 CN CN201680032979.8A patent/CN107735511B/zh active Active
  • 2016-04-07 RU RU2017138445A patent/RU2746373C2/ru active
  • 2016-04-07 WO PCT/EP2016/057622 patent/WO2016162423A1/de active Application Filing
  • 2016-04-07 KR KR1020177031822A patent/KR20170134613A/ko not_active Application Discontinuation
  • 2016-04-07 BR BR112017021307-9A patent/BR112017021307B1/pt active IP Right Grant
  • 2016-04-07 US US15/562,653 patent/US11492707B2/en active Active
  • 2016-04-07 DE DE102016205814.2A patent/DE102016205814A1/de not_active Withdrawn
  • 2016-04-07 EP EP16717585.0A patent/EP3280830B1/de active Active
  • 2016-04-07 MX MX2017012917A patent/MX2017012917A/es unknown
  • 2016-04-07 DE DE102016205815.0A patent/DE102016205815A1/de not_active Withdrawn
  • 2016-04-07 CN CN201680032966.0A patent/CN107683348A/zh active Pending
• 2017
  • 2017-01-18 CN CN201780034820.4A patent/CN109312466B/zh active Active
  • 2017-01-18 EP EP17703041.8A patent/EP3440235A1/de active Pending
  • 2017-01-18 JP JP2018553121A patent/JP6986028B2/ja active Active
  • 2017-01-18 KR KR1020187031749A patent/KR20190002504A/ko unknown
  • 2017-01-18 RU RU2018138295A patent/RU2748349C2/ru active
  • 2017-01-18 MX MX2018012228A patent/MX2018012228A/es unknown
  • 2017-01-18 WO PCT/EP2017/050993 patent/WO2017174222A1/de active Application Filing
  • 2017-10-31 ZA ZA2017/07384A patent/ZA201707384B/en unknown
  • 2017-11-01 ZA ZA2017/07420A patent/ZA201707420B/en unknown

Also Published As

Similar Documents

Legal Events