EP1060290B1 - Solution aqueuse et procede pour phosphater des surfaces metalliques - Google Patents

Solution aqueuse et procede pour phosphater des surfaces metalliques Download PDF

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Publication number
EP1060290B1
EP1060290B1 EP99911702A EP99911702A EP1060290B1 EP 1060290 B1 EP1060290 B1 EP 1060290B1 EP 99911702 A EP99911702 A EP 99911702A EP 99911702 A EP99911702 A EP 99911702A EP 1060290 B1 EP1060290 B1 EP 1060290B1
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Prior art keywords
solution
aqueous
phosphate
nitroguanidine
aqueous solution
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EP99911702A
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German (de)
English (en)
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EP1060290A1 (fr
Inventor
Peter Schubach
Joachim Heitbaum
Thomas Kolberg
Margit Fleischhacker-Jeworrek
Peter Jörns
Michael Deemer
Ralf Stickler
Jürgen SPECHT
Michael Lenhard
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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
    • 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
    • C23C22/07—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
    • C23C22/12—Orthophosphates containing 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
    • C23C22/07—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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—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
    • C23C22/186—Orthophosphates containing manganese cations containing also copper 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
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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 invention relates to an aqueous, phosphate-containing solution for the production of phosphate layers on metallic Surfaces made of iron, steel, zinc, zinc alloys, aluminum or aluminum alloys.
  • the invention further relates to a Process for phosphating metallic surfaces under Use of an aqueous phosphating solution.
  • GB-A 510684 discloses a method for improving the corrosion resistance of metals, in particular iron and steel, by treatment in a zinc-containing solution which forms phosphate coatings, in which the solution contains an accelerating agent and in which hydroxylamine is used as an accelerating agent , Nitromethane, nitrobenzene, picric acid, a nitraniline, a nitrophenol, a nitrobenzoic acid, a nitroresorcinol, nitrourea, a nitrourethane or nitroguanidine is used.
  • the optimum concentration for the individual accelerators is different, but it is generally between 0.01 and 0.4% by weight in the phosphating solutions.
  • the optimal concentration for the accelerator nitroguanidine should be 0.2% by weight and for the accelerator hydroxylamine the optimal concentration should be 0.3% by weight.
  • GB-A 510684 makes no statements about the zinc content, the S value and the Zn-P 2 O 5 ratio of the phosphating solution, nor does it recommend the use of a mixture consisting of several accelerators.
  • WO-A95 / 07370 discloses a process for phosphating metal surfaces with aqueous, acidic phosphating solutions which contain zinc, manganese and phosphate ions and, as an accelerator, hydroxylamine or a hydroxylamine compound and / or m-nitrobenzenesulfonic acid or its water-soluble salts which the metal surface is brought into contact with a phosphating solution which is free from nickel, cobalt, copper, nitrite and oxo anions from halogens and which contains 0.3 to 2 g / l of Zn 2+ , 0.3 to 4 g / l of Mn Contains 2+ , 5 to 40 g / l phosphate ions, 0.1 to 5 g / l hydroxylamine in free or bound form and / or 0.2 to 2 g / l m-nitrobenzenesulfonate and at most 0.5 g / l nitrate ions, wherein the Mn content is at
  • the invention is based on the object of phosphate-containing solution and the process for phosphating, which in German patent application 196 34 685.1 have been proposed to improve the maximum Edge length of those present in the phosphate layers produced Crystallite is significantly ⁇ 15 ⁇ m that the generated Phosphate layers have a layer weight of 2 to 4 g / l and that the phosphate layers produced with regard to Layer weight and the edge length of the crystallites too during a longer operating time of the phosphating bath are constant or even.
  • the essence of the invention is therefore that the solution proposed in the cited German patent application contains not only the accelerator nitroguanidine but also the accelerator hydroxylamine in a low concentration, the nitroguanidine concentration of the solution according to the invention compared to the nitroguanidine concentration of that proposed in the German patent application Solution was significantly lowered.
  • the 0.1 to 1.5 g nitroguanidine / l and 0.1 to 0.4 g contains hydroxylamine / l.
  • EP-B 0 315 059 discloses a solution for phosphating iron surfaces, which has a zinc concentration of 0.2 to 2 g / l and which, as an accelerator, contains hydroxylamine, hydroxylamine salts or hydroxylamine complexes contains, which give the solution a hydroxylamine concentration of 0.5 to 50 g / l, preferably 1 to 10 g / l, and although on the other hand from the publication EP-B 0 633 950 a solution for producing copper-containing phosphate layers on metal surfaces steel, galvanized steel, alloy galvanized steel, aluminum and its alloys is known which has a zinc concentration of 0.2 to 2 g / l, a copper concentration of 0.5 to 25 mg / l, a P 2 O 5 -Concentration of 5 to 30 g / l, which contains hydroxylamine, hydroxylamine salts and hydroxylamine complexes as accelerators, which give the solution a hydroxylamine concentration of
  • the solution according to the invention is also not known to the person skilled in the art discloses the prior art cited above or suggested because compared to that in the German patent application 196 34 685.1 uses the proposed solution solution according to the invention only the lower nitroguanidine concentrations and additionally hydroxylamine and compared to Solutions resulting from the two Europeans cited Are known patents, uses the invention Solution hydroxylamine concentrations lower than that in The prior art cited disclosed hydroxylamine concentrations are, with the fact that in both European patents cited the use of Nitroguanidine as an accelerator is not disclosed and that both European patents cited the expert prompt to use high hydroxylamine concentrations, because according to EP-B 0 315 059 is a hydroxylamine concentration from 1 to 10 g / l as preferred and claimed in accordance with Example 1 of EP-B 0 633 950 a hydroxylamine sulfate concentration of 1.7 g / l worked, which corresponds to a hydroxylamine concentration of 0.68 g / l
  • the solution contains 0.3 to 3 g of Zn 2+ / l.
  • the solution is therefore particularly suitable for use in the context of low-zinc technology.
  • the solution additionally contains 0.5 to 20 g / NO 3 - / l, that the solution additionally contains 0.01 to 3 g Mn 2+ / l and / or 0.01 to 3 contains Ni 2+ / l and / or 1 to 100 mg Cu 2+ / l and / or 0.01 to 3 g Co 2+ / l.
  • the copper content of 1 to 100 mg Cu 2+ / l is responsible for the fact that high-quality phosphate layers are produced in the absence of nickel.
  • the solution contains 0.01 to 3 g F - / l and / or 0.05 to 3.5 g / l of at least one complex fluoride.
  • the solution contains as complex fluoride (SiF 6 ) 2- or (BF 4 ) - .
  • the nitrate content according to the invention advantageously favors maintaining a constant layer weight.
  • the nitrate is added to the phosphating solution in the form of alkali metal nitrates and / or by the cations present in the system, for example as zinc nitrate and / or as HNO 3 . Since the nitrate-free aqueous solution also gives good phosphating results, the acceleration effect of the nitrate, which is known per se, is in most cases of minor importance in the present case.
  • the metal ions Mn 2+ , Ni 2+ , Cu 2+ and Co 2+ added to the phosphating solution are built into the phosphate layer and improve paint adhesion and corrosion protection.
  • the free fluoride is added to the phosphating solution when metallic surfaces consisting of aluminum or aluminum alloys are phosphated.
  • the complex fluorides are added to the phosphating solution, in particular to improve the phosphating result on galvanized surfaces.
  • the object underlying the invention is further achieved by the creation of a process for phosphating metallic Surfaces solved where the metallic surfaces cleaned, then with the aqueous, phosphate-containing Phosphating solution for a period of 5 seconds to 10 Minutes at a temperature of 15 to 70 ° C and treated finally be rinsed with water.
  • This procedure can be carried out with simple technical means and works extremely reliably.
  • the one with the procedure generated phosphate layers have a consistently good Quality that lasts even longer Phosphating bath does not decrease.
  • the minimum phosphating time is lower in the method according to the invention than in known ones Low zinc process with the usual accelerators work.
  • the minimum phosphating time is the time in which the Surface is phosphated closed.
  • the treatment of the metallic surfaces with the phosphating solution is carried out by spraying, dipping, splash-dipping or rolling.
  • These working techniques open up a very broad and diverse range of applications for the method according to the invention.
  • the metallic surfaces after cleaning with a Activating agents are treated, which is a titanium-containing Contains phosphate. This will form a closed, crystalline phosphate layer supports. It is also provided according to the invention that the metallic surfaces after the one after the phosphating Rinsing process can be treated with a passivating agent.
  • the passivating agents used can contain Cr as well also be Cr-free.
  • Cleaning the metallic surfaces will be both mechanical impurities as well as adhering fats from the surface to be phosphated removed.
  • the cleaning of the metallic surfaces belong to the known state of the art and can be beneficial with an aqueous alkaline cleaner be performed. It is useful if the metallic Surfaces are rinsed with water after cleaning. The Rinsing the cleaned or the phosphated metallic Surfaces are made either with tap water or with desalinated water.
  • the nitroguanidine is introduced into the aqueous solution in the form of a stable, aqueous suspension.
  • the stable, aqueous suspension contains a layered silicate as stabilizer, the layered silicates [Mg 6 (Si 7 , 4 Al 0.6 ) O 20 (OH) 4 ] Na 0.6 x XH 2 O or [(Mg 5.4 Li 0.6 ) Si 8 O 20 (OH, F) 4 ] Na 0.6 x XH 2 O in an amount of 10 to 30 g / l nitroguanidine suspension, or it can be used take place that the stable, aqueous suspension contains a stabilizer consisting of a polymeric sugar and polyethylene glycol, the weight ratio of the polymeric sugar to polyethylene glycol being 1: 1 to 1: 3 and the stabilizer in an amount of 5 to 20 g / l Nitroguanidine suspension is used.
  • nitroguanidine With both stabilizers of the nitroguanidine suspension it is advantageously achieved that the suspension remains unchanged for several months and that the sludge separation in the phosphating bath is favored.
  • the introduction of the nitroguanidine into the phosphating solution in the form of a stabilized suspension avoids the disadvantages which result from the fact that nitroguanidine is present as a powder and can only be distributed evenly in the phosphating solution in this form with difficulty.
  • the suspensions produced according to the invention can be easily pumped and are stable over 12 months, which means that the nitroguanidine does not settle even after a long time.
  • the suspensions are prepared by suspending the layered silicate or the organic stabilizer in deionized water and then stirring in the nitroguanidine.
  • the phosphating according to Comparative Example 1 was carried out under Accelerators excluded. At the Comparative example 2 was only the accelerator Hydroxylamine present, while in Comparative Example 3 only the accelerator nitroguanidine was used. The embodiments 4 to 9 were in the presence of both Accelerator performed, the concentration of both Accelerator in the preferred according to the invention Area.
  • the table shows both the layer weights and the crystallite edge lengths which could be achieved when Examples 1 to 9 were carried out. These data show that in Comparative Example 1, which was carried out in the absence of the two accelerators according to the invention, a phosphate layer of insufficient quality resulted, since both the layer weight and the edge length of the crystallites of the phosphate layer are comparatively large. In comparative examples 2 and 3, tolerable layer weights and sufficiently small crystallite edge lengths were obtained, so that both phosphate layers can be regarded as quite useful.
  • the exemplary embodiments 4 to 9 show that, according to the invention, both optimum layer weights and extraordinarily fine-crystalline phosphate layers could be produced.
  • Exemplary embodiments 4 to 9 thus demonstrate that the invention can be used to produce very high quality phosphate layers, using very low concentrations of nitroguanidine and hydroxylamine in the phosphating bath.
  • the phosphate layers produced in accordance with Examples 1 to 9 were closed.
  • the edge lengths of the crystallites given in the table were determined on the basis of electron microscopic images of the individual phosphate layers.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)
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Claims (20)

  1. Solution aqueuse contenant des phosphates, permettant de former une couche de phosphates sur des surfaces métalliques en fer, en acier, en zinc, en alliage de zinc, en aluminium ou en alliage d'aluminium, qui contient de 0,3 à 5 g/l d'ions Zn2+, de 0,1 à 2 g/l de nitroguanidine et de 0,05 à 0,5 g/l d'hydroxylamine, et dans laquelle le rapport pondéral Zn2+/P2O5 vaut de 1/5 à 1/30 et l'indice d'acide vaut de 0,03 à 0,3, cet indice d'acide indiquant le rapport de la quantité d'acide libre, calculée en P2O5 libre, à la quantité totale de P2O5.
  2. Solution aqueuse conforme à la revendication 1, contenant de 0,1 à 1,5 g/l de nitroguanidine.
  3. Solution aqueuse conforme à l'une des revendications 1 à 2, contenant de 0,1 à 0,4 g/l d'hydroxylamine.
  4. Solution aqueuse conforme à l'une des revendications 1 à 3, contenant de 0,3 à 3 g/l d'ions Zn2+.
  5. Solution aqueuse conformé à l'une des revendications 1 à 4, contenant de 0,5 à 20 g/l d'ions NO3 -.
  6. Solution aqueuse conforme à l'une des revendications 1 à 5, contenant de 0,01 à 3 g/l d'ions Mn2+ et/ou de 0,01 à 3 g/l d'ions Ni2+ et/ou de 1 à 100 mg/l d'ions Cu2+ et/ou de 0,01 à 3 g/l d'ions Co2+.
  7. Solution aqueuse conforme à l'une des revendications 1 à 5, contenant de 0,01 à 3 g/l d'ions F- et/ou de 0,05 à 3,5 g/l d'au moins un fluorure complexe.
  8. Solution aqueuse conforme à l'une des revendications 1 à 7, contenant, en tant que fluorure complexe, des ions (SiF6)2- ou (BF4)-.
  9. Procédé de phosphatation de surfaces métalliques, dans lequel on nettoie une surface métallique, puis on la traite avec une solution aqueuse contenant des phosphates, conforme à l'une des revendications 1 à 8, pendant un laps de temps de 5 secondes à 10 minutes et à une température de 15 à 70 °C, et enfin, on la lave avec de l'eau.
  10. Procédé conforme à la revendication 9, dans lequel le traitement de la surface métallique avec la solution de phosphatation s'effectue par pulvérisation, immersion, pulvérisation-immersion, ou application au rouleau.
  11. Procédé conforme à l'une des revendications 9 à 10, dans lequel, dans la solution de phosphatation employée en pulvérisation, le rapport pondéral Zn2+/P2O5 vaut de 1/5 à 1/30, et la pulvérisation dure de 5 à 300 secondes.
  12. Procédé conforme à l'une des revendications 9 à 10, dans lequel, dans la solution de phosphatation employée en bain d'immersion, le rapport pondéral Zn2+/P2O5 vaut de 1/5 à 1/18, et l'immersion dure de 5 secondes à 10 minutes.
  13. Procédé conforme à l'une des revendications 9 à 12, dans lequel, après avoir nettoyé la surface métallique, on la traite avec un agent d'activation qui contient un phosphate comprenant du titane.
  14. Procédé conforme à l'une des revendications 9 à 13, dans lequel, après l'opération de lavage qui suit la phosphatation, on traite la surface métallique avec un agent de passivation.
  15. Procédé conforme à la revendication 9, dans lequel la nitroguanidine est incorporée dans la solution aqueuse sous forme d'une suspension aqueuse stable.
  16. Procédé conforme à la revendication 15, dans lequel la suspension aqueuse stable contient, en guise d'agent stabilisant, un silicate à structure en feuillets.
  17. Procédé conforme à la revendication 16, dans lequel on emploie, comme agent stabilisant, le silicate à structure en feuillets [Mg6(Si7,4Al0,6)O20(OH)4]Na0,6 . xH2O ou [(Mg5,4Li0,6)Si8O20(OH,F)4]Na0,6 . xH2O à raison de 10 à 30 grammes par litre de suspension de nitroguanidine.
  18. Procédé conforme à la revendication 15, dans lequel la suspension aqueuse stable contient un agent stabilisant constitué d'un polysaccharide et d'un polyéthylèneglycol, présents en un rapport pondéral de 1/1 à 1/3 du polysaccharide au polyéthylèneglycol, cet agent stabilisant étant employé à raison de 5 à 20 grammes par litre de suspension de nitroguanidine.
  19. Emploi d'une solution aqueuse contenant des phosphates, conforme à l'une des revendications 1 à 8, et d'un procédé de phosphatation conforme à l'une des revendications 9 à 18, pour le traitement de pièces ouvrées avant revêtement.
  20. Emploi conforme à la revendication 20, pour le traitement de pièces avant revêtement électrophorétique.
EP99911702A 1998-02-27 1999-02-24 Solution aqueuse et procede pour phosphater des surfaces metalliques Expired - Lifetime EP1060290B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19808440 1998-02-27
DE19808440A DE19808440C2 (de) 1998-02-27 1998-02-27 Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen sowie eine Verwendung der Lösung und des Verfahrens
PCT/EP1999/001186 WO1999043868A1 (fr) 1998-02-27 1999-02-24 Solution aqueuse et procede pour phosphater des surfaces metalliques

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EP1060290A1 EP1060290A1 (fr) 2000-12-20
EP1060290B1 true EP1060290B1 (fr) 2002-09-18

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EP (1) EP1060290B1 (fr)
JP (1) JP2002505378A (fr)
KR (1) KR20010041417A (fr)
CN (1) CN1292041A (fr)
AT (1) ATE224466T1 (fr)
AU (1) AU740987B2 (fr)
BR (1) BR9909236A (fr)
CA (1) CA2325012A1 (fr)
DE (2) DE19808440C2 (fr)
PL (1) PL342623A1 (fr)
SI (1) SI20378A (fr)
SK (1) SK12352000A3 (fr)
TR (1) TR200002495T2 (fr)
WO (1) WO1999043868A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10155666A1 (de) * 2001-11-13 2003-05-22 Henkel Kgaa Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren
AU2003250917A1 (en) * 2002-07-10 2004-02-02 Chemetall Gmbh Method for coating metallic surfaces
US20040118483A1 (en) * 2002-12-24 2004-06-24 Michael Deemer Process and solution for providing a thin corrosion inhibiting coating on a metallic surface
US6923153B2 (en) 2003-06-26 2005-08-02 Mahle Technology, Inc. Piston and connecting rod assembly having phosphatized bushingless connecting rod and profiled piston pin
US20040261752A1 (en) * 2003-06-26 2004-12-30 Wolfgang Rein Phosphatized and bushingless piston and connecting rod assembly having an internal gallery and profiled piston pin
US8613137B2 (en) 2004-11-16 2013-12-24 Mahle International Gmbh Connecting rod lubrication recess
US7516546B2 (en) * 2004-11-16 2009-04-14 Mahle Technology, Inc. Method of manufacturing a connecting rod assembly for an internal combustion engine
US7581315B2 (en) * 2004-11-16 2009-09-01 Mahle Technology, Inc. Connecting rod assembly for an internal combustion engine and method of manufacturing same
CN102953055B (zh) * 2012-11-07 2014-05-14 长沙沃尔金属表面技术有限公司 一种黑色磷化液及其使用方法
KR101968836B1 (ko) * 2017-09-26 2019-04-12 현대제철 주식회사 전기아연도금강판 및 이의 제조방법
WO2019158508A1 (fr) * 2018-02-19 2019-08-22 Chemetall Gmbh Procédé de phosphatation sélective d'une construction métallique composite

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BE432557A (fr) * 1938-02-04
DE977633C (de) * 1950-07-06 1967-11-02 Galvapol Ges Fuer Galvanotechn Verfahren zur Herstellung von Phosphatueberzuegen auf eisenhaltigen Metallgegenstaenden
US2768104A (en) * 1952-03-25 1956-10-23 Heintz Mfg Co Method for coating iron
GB2148950B (en) * 1983-10-26 1987-02-04 Pyrene Chemical Services Ltd Phosphating composition and processes
CA1257527A (fr) * 1984-12-20 1989-07-18 Thomas W. Tull Procede de deformation a froid avec enduction lubrifiante amelioree
DE3800835A1 (de) * 1988-01-14 1989-07-27 Henkel Kgaa Verfahren zur phosphatierung von metalloberflaechen
US5137589A (en) * 1990-02-09 1992-08-11 Texo Corporation Method and composition for depositing heavy iron phosphate coatings
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
DE4210513A1 (de) * 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
ATE162233T1 (de) * 1993-09-06 1998-01-15 Henkel Kgaa Nickelfreies phosphatierverfahren
DE4417965A1 (de) * 1994-05-21 1995-11-23 Henkel Kgaa Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren
DE19634685A1 (de) * 1996-08-28 1998-03-05 Metallgesellschaft Ag Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen

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KR20010041417A (ko) 2001-05-15
DE59902751D1 (de) 2002-10-24
DE19808440C2 (de) 2000-08-24
AU3029899A (en) 1999-09-15
AU740987B2 (en) 2001-11-22
DE19808440A1 (de) 1999-09-09
ATE224466T1 (de) 2002-10-15
SI20378A (sl) 2001-04-30
BR9909236A (pt) 2000-11-14
PL342623A1 (en) 2001-06-18
EP1060290A1 (fr) 2000-12-20
JP2002505378A (ja) 2002-02-19
SK12352000A3 (sk) 2001-05-10
TR200002495T2 (tr) 2000-12-21
CN1292041A (zh) 2001-04-18
CA2325012A1 (fr) 1999-09-02
WO1999043868A1 (fr) 1999-09-02
US6497771B1 (en) 2002-12-24

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