EP0633950B1 - Procede de phosphatation exempte de nickel - Google Patents

Procede de phosphatation exempte de nickel Download PDF

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Publication number
EP0633950B1
EP0633950B1 EP92924684A EP92924684A EP0633950B1 EP 0633950 B1 EP0633950 B1 EP 0633950B1 EP 92924684 A EP92924684 A EP 92924684A EP 92924684 A EP92924684 A EP 92924684A EP 0633950 B1 EP0633950 B1 EP 0633950B1
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EP
European Patent Office
Prior art keywords
ions
phosphating solution
phosphating
hydroxylamine
phosphate
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EP92924684A
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German (de)
English (en)
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EP0633950A1 (fr
Inventor
Wolf-Achim Roland
Karl-Heinz Gottwald
Matthias Hamacher
Jan-Willem Brouwer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • 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
    • C23C22/18—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
    • C23C22/07—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
    • C23C22/22—Orthophosphates containing alkaline earth metal 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal

Definitions

  • the invention relates to a method for producing copper-containing, nickel-free phosphate layers on metal surfaces and to the use of the method as pretreatment of the metal surfaces before painting, in particular cataphoretic dip painting (KTL).
  • KTL cataphoretic dip painting
  • the quality of phosphate coatings before cataphoretic dip painting depends on a variety of parameters. These include physical quantities such as the shape and size of the crystals, their mechanical stability and in particular the free metal surface after phosphating, the so-called pore surface. With regard to the chemical parameters, the alkali stability during the cataphoretic coating, the binding strength of the crystal water of the zinc phosphate crystals when baking the paints and the rehydration ability are of particular interest.
  • the layer weight can be controlled, in particular reduced, by using activating agents prior to phosphating.
  • the polymeric titanium phosphates present in the activating agents form active centers on the metal surface from which crystal growth proceeds. The result is smaller and mechanically more stable crystals on the one hand, and on the other hand the pore area is reduced, making it more difficult to attack corrosive media if the paint is damaged.
  • the water hardness ions in particular deactivate the polymeric titanium phosphates.
  • Barium phosphate coatings do not contain zinc, but have a number of positive properties, such as high thermal stability. However, the achievable layer weights are not sufficient to achieve a high level of corrosion protection in combination with a cataphoretic dip coating.
  • the barium phosphate coatings thus occupy an intermediate position between the "thin” iron phosphate coatings (0.3-0.5 g / m) and the “thicker" zinc phosphate coatings (2.0-3.5 g / m).
  • Aluminum ions reduce the phosphate layer weights even more, so that so-called "passivation phenomena" already occur from a concentration of 5 ppm Al3 + ions in the phosphating bath, i. H. disturbances in the formation of zinc phosphate coatings.
  • the layer weight reduction by magnesium ions is so strong that other control parameters, which are usually also used to reduce the layer weight, such as very low zinc concentrations (0.6 g / l Zn+), high concentrations of accelerators such as sodium nitrite or meta-nitrobenzenesulfonate / Na salts do not have to be used to generate a mass per unit area in the range of 1.5 - 2.0 g / m.
  • control parameters which are usually also used to reduce the layer weight, such as very low zinc concentrations (0.6 g / l Zn+), high concentrations of accelerators such as sodium nitrite or meta-nitrobenzenesulfonate / Na salts do not have to be used to generate a mass per unit area in the range of 1.5 - 2.0 g / m.
  • EP-A-0 186 823 discloses strongly acidic phosphating solutions with a pH of 1.8-2.5 which contain 7.5-75 g / l zinc ions, Contain 0.1 - 10 g / l hydroxylamine and optionally up to 20 g / l manganese ions and 5 - 75 g / l nitrate ions.
  • the solutions tolerate an iron content of up to 25 g / l.
  • EP-A-0 315 059 discloses a process for zinc phosphating iron-containing surfaces.
  • the desired morphology of the zinc phosphate crystals is set by using hydroxylammonium salts, hydroxylamine complexes and / or hydroxylamine.
  • all of the examples contain nickel as another layer-forming cation.
  • the toxicological disadvantages of nickel are known.
  • the object was therefore to provide a process for the production of nickel-free phosphate layers which, in the absence of nickel on metal surfaces such as cold rolled steel, electrolytically galvanized steel and aluminum, ensures very good paint adhesion and excellent corrosion protection.
  • the above-mentioned object is achieved with the aid of a specially selected phosphating solution which contains hydroxylamine salts, hydroxylamine complexes and / or hydroxylamine in an amount of 500 to 5000 ppm of hydroxylamine, based on the phosphating solution, as an active ingredient for modifying the crystal morphology ("accelerator").
  • a specially selected phosphating solution which contains hydroxylamine salts, hydroxylamine complexes and / or hydroxylamine in an amount of 500 to 5000 ppm of hydroxylamine, based on the phosphating solution, as an active ingredient for modifying the crystal morphology.
  • the present invention relates, according to claim 1, to a method for producing copper-containing nickel-free phosphate layers with a copper content in the range from 0.1 to 5% by weight and an edge length of Phosphate crystals in the range of 0.5 to 10 ⁇ m on metal surfaces selected from steel, galvanized steel, alloy galvanized steel, aluminum and their alloys, by treating them in a spray, dip or spray / dip process with a phosphating solution which does the following Components contains: Zinc ions 0.2 to 2 g / l Copper ions 0.5 to 25 mg / l Phosphate ions 5 to 30 g / l (calculated as P2O5) and also hydroxylamine salts, hydroxylamine complexes and / or hydroxylamine in an amount of 500 to 5000 ppm hydroxylamine based on the phosphating solution.
  • the phosphating solution contains 5 to 20 ppm of copper ions when the metal surface is brought into contact with the phosphating solution by means of immersion processes.
  • the phosphating solutions contain 1 to 10 ppm copper ions in order to incorporate correspondingly high copper contents in the conversion coating.
  • the pH of the phosphating solution In order to ensure proper formation of the phosphate layer, it is known to adjust the pH of the phosphating solution to a value between 2.5 and 3.5. If necessary, further cations, for example alkali metal cations and / or alkaline earth metal cations with corresponding anions known in the prior art, are used to adjust the pH of the phosphating solution.
  • the pH value can be corrected during the phosphating, for example, with basic additives or acids.
  • the phosphating solution contains 0.1 to 5 g / l, in particular 0.5 to 1.5 g / l, of manganese (II) ions.
  • the quality of the copper-containing nickel-free phosphate layers produced with the aid of the method according to the invention is not impaired if the phosphating solution contains alkaline earth metal cations of up to 2.5 g / l, in particular magnesium and / or calcium ions.
  • the method according to the invention can be applied in particular to steel, steel galvanized on one or two sides, steel galvanized on one or both sides, aluminum and its alloys.
  • steel in the sense of the present invention includes, in addition to low-alloy steels, also soft, unalloyed steels and higher as well as high-strength steels.
  • the essential content of the invention is that the aqueous, acid phosphating solutions are free of nickel. However, this means that under technical conditions a small amount of nickel ions can be contained in the phosphating baths. However, in accordance with the prior art DE-A-40 13 483, this amount should be less than 0.0002 to 0.01 g / l, in particular less than 0.0001 g / l.
  • iron in the form of iron (II) ions dissolves.
  • iron (II) is converted into iron (III) and can thus be precipitated as iron phosphate sludge. Accordingly, it is typical in the sense of the present invention that the phosphating solution contains up to 50 ppm - briefly in the production process, but also up to 500 ppm - iron (II) ions.
  • a number of oxidizing agents are known in the prior art for limiting the iron (II) ion concentration.
  • the contact of the phosphating solution with oxygen for example atmospheric oxygen and / or the addition of suitable oxidizing agents, serves to limit the iron (II) ion concentration.
  • the phosphating solution contains oxidizing agents selected from peroxide compounds, chlorates, permanganates and organic nitro compounds.
  • the oxidizing agents of the phosphating solutions are preferably selected from peroxide compounds, in particular hydrogen peroxide, perborate, percarbonate and Perphosphate, and organic nitro compounds, especially nitrobenzenesulfonate.
  • peroxide compounds in particular hydrogen peroxide, perborate, percarbonate and Perphosphate
  • organic nitro compounds especially nitrobenzenesulfonate.
  • the amounts of oxidizing agent to be used are known from the prior art. For example: Peroxide compound calculated as hydrogen peroxide: 0.005 to 0.1 g / l, nitrobenzenesulfonate: 0.005 to 1 g / l.
  • the phosphating process is applied to galvanized steel, alloy galvanized steel, aluminum and its alloys, the presence of iron (II) ions is not harmful. Accordingly, the addition of oxidizing agents can be completely dispensed with when phosphating these materials when using the method according to the invention.
  • a preferred embodiment of the present invention consists in using phosphating solutions which are essentially free of nitrite ions.
  • a significant advantage of this process variant is that no toxic decomposition products of nitrites, for example nitrous gases which are hazardous to health, can arise.
  • modifying compounds from the group of surfactants hydroxycarboxylic acids, tartrate, citrate, hydrofluoric acid, alkali metal fluoride, boron trifluoride, silicon fluoride is known in principle from the prior art. While the addition of surfactants (for example 0.05 to 0.5 g / l) leads to an improvement in the phosphating of lightly greased metal surfaces, it is known that hydroxycarboxylic acids, in particular tartaric acid, citric acid and their salts, in a concentration range of 0.03 to 0.3 g / l contribute to a significant reduction in the weight of the phosphate layer.
  • Fluoride ions promote the phosphating of metals that are more difficult to attack, thereby shortening the phosphating time and also increasing the area coverage of the phosphate layer.
  • about 0.1 to 1 g / l of the fluorides are used.
  • the controlled addition of fluorides also enables the formation of crystalline phosphate layers on aluminum and its alloys. Salts of boron tetrafluoride and silicon hexafluoride increase the aggressiveness of the phosphating baths, which is particularly noticeable in the treatment of hot-dip galvanized surfaces, which is why these complex fluorides can be used, for example, in amounts of 0.4 to 3 g / l.
  • Phosphating processes are usually used at bath temperatures between 40 and 60 ° C. These temperature ranges are used in spraying as well as in spray-immersion and immersion applications.
  • the metal surfaces to be phosphated are cleaned, rinsed and, if necessary, treated with activating agents, in particular based on titanium phosphates, according to processes known per se in the prior art.
  • the phosphating baths for carrying out the process according to the invention are generally prepared in the customary manner which is known per se to the person skilled in the art.
  • the following compounds are suitable as starting products for the preparation of the phosphating bath: Zinc: in the form of zinc oxide, zinc carbonate or optionally zinc nitrate; Copper: in the form of acetate, sulfate or, where appropriate, nitrate; Manganese: in the form of carbonate, magnesium and calcium: in the form of carbonates; Phosphate: preferably in the form of phosphoric acid.
  • the fluoride ions which may be used in the bath are preferably used in the form of alkali metal or ammonium fluoride, in particular sodium fluoride or in the form of the complex compounds mentioned above.
  • the compounds mentioned above are dissolved in water in the concentration ranges essential for the invention; then, as has also been said above, the pH of the phosphating solutions is adjusted to the desired value.
  • hydroxylamine can originate from any source. Accordingly, any compound which provides hydroxylamine or a derivative thereof, for example a hydroxylamine salt or a hydroxylamine complex, which is often in the form of hydrate, can be used according to the invention. Examples which can be used include hydroxylamine phosphate, optionally hydroxylamine nitrate, hydroxylamine sulfate (also called hydroxylammonium sulfate [(NH2OH) 2.H2SO4]) or a mixture thereof. Hydroxylamine sulfate and hydroxylamine phosphate are particularly preferred as the hydroxylamine source.
  • test surfaces were phosphatized from electrolytically galvanized thin sheet at a temperature of 53 ° C. in the course of 1 min.
  • the test panels were then given a test coat of KTL and white top coat and subjected to the alternating climate test according to VDA 621-415. The results after a test period of 5 cycles are also shown in Table 2.
  • the corrosion protection effect of the phosphating according to the invention was determined in accordance with the standards of the German Association of the Automotive Industry (VDA 621-414 (outdoor weathering) and VDA 621-415 (alternating climate test)).
  • the testing of the corrosion protection of motor vehicle paints by exposure to the weather serves to determine the corrosion protection effect of motor vehicle paints under the influence of natural weathering in the overall structure, as in the example without light protection and additional stress by spraying with saline solution.
  • Test coats consisting of an automobile-typical structure made of KTL, filler, white top coat, each according to Ford specification, are provided with a straight scratch mark parallel to the long side, which runs through to the metal surface.
  • the test coats are stored on suitable racks. They are sprayed liberally once a week with a dilute sodium chloride solution.
  • the test time in the present case was 6 months.
  • the sample coats are rinsed with clear, flowing water, blown dry with compressed air if necessary and examined for visible changes.
  • the under rusting visible from both sides of the scoring is determined.
  • the width of the metal surface damaged by rust next to the scratch is generally easy to see on the paint surface.
  • the average total width is used for evaluation the rust zone in mm. For this purpose, the width is measured in several places and the arithmetic mean is formed.
  • Testing the corrosion protection of automotive paintwork in the case of cyclically changing stresses serves to assess the corrosion protection of automotive paintwork using a time-consuming laboratory process, which causes corrosion processes and corrosion patterns that are well comparable with those that occur during driving.
  • the short test simulates in particular the under rust caused by a paint injury, as well as the edge and edge rust in the case of special corrosion test sheets or components with known weak points in the paint and the surface rust.
  • test panels were provided with a straight scratch mark parallel to the long side, extending through to the metal surface.
  • test panels were set up in the tester at an angle of 60 ° to 75 ° to the horizontal.
  • the test time is 10 cycles corresponding to 70 days.
  • test plates are rinsed with clear, flowing water, blown dry with compressed air if necessary and examined for visible changes.
  • the width of the metal surface damaged by rust next to the scratch is easily recognizable as a trace of bubbles or rust on the paint surface.
  • an inclined knife blade e.g. B. with an eraser, carefully remove the rusted paint film to the still adherent zone.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
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Claims (10)

  1. Procédé pour la formation de couches phosphatées exemptes de nickel, contenant du cuivre, possédant une teneur en cuivre dans le domaine de 0,1 à 5,0% en poids et une longueur d'arête des cristaux de phosphate dans le domaine de 0,5 à 10 µm, sur des surfaces métalliques choisies parmi l'acier, l'acier galvanisé, l'acier allié galvanisé, l'aluminium et ses alliages, par traitement de ces dernières dans un procédé de pulvérisation, d'immersion ou encore de pulvérisation/immersion avec une solution de phosphatage qui contient les composants ci-après : ions zinc de 0,2 à 2 g/l ions cuivre de 0,5 à 25 mg/l ions phosphate de 5 à 30 g/l (calculé comme P₂O₅)
    ainsi que des sels d'hydroxylamine, des complexes d'hydroxylamine et/ou de l'hydroxylamine en une quantité de 500 à 5000 ppm d'hydroxylamine, rapportée à la solution de phosphatage.
  2. Procédé selon la revendication 1, caractérisé en ce que la solution de phosphatage contient jusqu'à 500 ppm d'ions fer(II), en particulier jusqu'à 50 ppm d'ions fer(II).
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la solution de phosphatage contient, lors de l'application du procédé d'immersion, de 5 à 20 ppm d'ions cuivre et, lors de l'application du procédé par pulvérisation, de 1 à 10 ppm d'ions cuivre.
  4. Procédé selon l'une ou plusieurs des revendications 1 à 3, caractérisé en ce que la solution de phosphatage contient, en outre, de 0,1 à 5 g/l, en particulier de 0,5 à 1,5 g/l d'ions manganèse(II).
  5. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce que la solution de phosphatage contient, en outre, des cations de métaux alcalino-terreux, en particulier des ions magnésium et/ou calcium en une quantité allant jusqu'à 2,5 g/l.
  6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce que le sel d'hydroxylamine est choisi parmi le phosphate d'hydroxylammonium, le nitrate d'hydroxylammonium, le sulfate d'hydroxylammonium ou leurs mélanges.
  7. Procédé selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que la solution de phosphatage contient, en outre, un agent d'oxydation choisi parmi des composés de peroxydes, des chlorates, des permanganates et des composés nitro organiques.
  8. Procédé selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'on met en oeuvre une solution de phosphatage qui est essentiellement exempte d'ions nitrite.
  9. Procédé selon l'une ou plusieurs des revendications 1 à 8, caractérisé en ce que l'on met en oeuvre une solution de phosphatage qui est essentiellement exempte d'ions nitrate.
  10. Utilisation du procédé selon l'une ou plusieurs des revendications 1 à 9, comme prétraitement des surfaces métalliques avant une peinture, en particulier une peinture cataphorique par immersion.
EP92924684A 1992-03-31 1992-12-07 Procede de phosphatation exempte de nickel Expired - Lifetime EP0633950B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4210513A DE4210513A1 (de) 1992-03-31 1992-03-31 Nickel-freie Phosphatierverfahren
DE4210513 1992-03-31
PCT/EP1992/002827 WO1993020259A1 (fr) 1992-03-31 1992-12-07 Procede de phosphatation exempte de nickel

Publications (2)

Publication Number Publication Date
EP0633950A1 EP0633950A1 (fr) 1995-01-18
EP0633950B1 true EP0633950B1 (fr) 1996-05-15

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EP92924684A Expired - Lifetime EP0633950B1 (fr) 1992-03-31 1992-12-07 Procede de phosphatation exempte de nickel

Country Status (8)

Country Link
US (1) US6197126B1 (fr)
EP (1) EP0633950B1 (fr)
JP (1) JPH07505445A (fr)
AT (1) ATE138112T1 (fr)
CA (1) CA2133455A1 (fr)
DE (2) DE4210513A1 (fr)
ES (1) ES2086782T3 (fr)
WO (1) WO1993020259A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675972A1 (fr) * 1992-12-22 1995-10-11 Henkel Corporation Composition et procede de revetement de conversion de phosphate pratiquement sans nickel
WO1998030732A1 (fr) * 1997-01-08 1998-07-16 Henkel Kommanditgesellschaft Auf Aktien Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre
WO1999043868A1 (fr) * 1998-02-27 1999-09-02 Metallgesellschaft Aktiengesellschaft Solution aqueuse et procede pour phosphater des surfaces metalliques

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE162233T1 (de) * 1993-09-06 1998-01-15 Henkel Kgaa Nickelfreies phosphatierverfahren
US5597465A (en) * 1994-08-05 1997-01-28 Novamax Itb S.R.L. Acid aqueous phosphatic solution and process using same for phosphating metal surfaces
IT1274594B (it) * 1994-08-05 1997-07-18 Itb Srl Soluzione fosfatica acquosa acida e processo di fosfatazione di superfici metalliche che la utilizza
DE19500927A1 (de) * 1995-01-16 1996-07-18 Henkel Kgaa Lithiumhaltige Zinkphosphatierlösung
DE19540085A1 (de) * 1995-10-27 1997-04-30 Henkel Kgaa Nitratarme, manganfreie Zinkphosphatierung
DE19606017A1 (de) * 1996-02-19 1997-08-21 Henkel Kgaa Zinkphosphatierung mit geringen Gehalten an Kupfer und Mangan
DE19716075A1 (de) * 1997-04-17 1998-10-22 Henkel Kgaa Mit Hydroxylamin und Chlorat beschleunigtes Phosphatierverfahren
EP1005578B1 (fr) 1997-08-06 2002-10-09 Henkel Kommanditgesellschaft auf Aktien Procede de phosphatation accelere par n-oxydes
US6720032B1 (en) 1997-09-10 2004-04-13 Henkel Kommanditgesellschaft Auf Aktien Pretreatment before painting of composite metal structures containing aluminum portions
JPH11264076A (ja) * 1998-01-14 1999-09-28 Nippon Paint Co Ltd 低鉛ｅｄ用の下地化成処理方法
US6723178B1 (en) 1999-08-16 2004-04-20 Henkel Corporation Process for forming a phosphate conversion coating on metal
DE10006338C2 (de) * 2000-02-12 2003-12-04 Chemetall Gmbh Verfahren zur Beschichtung von Metalloberflächen, wässeriges Konzentrat hierzu und Verwendung der beschichteten Metallteile
DE10110833B4 (de) * 2001-03-06 2005-03-24 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
DE10110834B4 (de) * 2001-03-06 2005-03-10 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen und Verwendung der derart beschichteten Substrate
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CA2467751A1 (fr) * 2001-12-13 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Utilisation d'hydroxylamines substituees pour les procedes de phosphatation de metal
WO2006108108A2 (fr) * 2005-04-06 2006-10-12 Rem Technologies, Inc. Superfinition de carbures de densite elevee
DE102010001686A1 (de) 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Zusammensetzung für die alkalische Passivierung von Zinkoberflächen
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WO1998030732A1 (fr) * 1997-01-08 1998-07-16 Henkel Kommanditgesellschaft Auf Aktien Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre
WO1999043868A1 (fr) * 1998-02-27 1999-09-02 Metallgesellschaft Aktiengesellschaft Solution aqueuse et procede pour phosphater des surfaces metalliques

Also Published As

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EP0633950A1 (fr) 1995-01-18
CA2133455A1 (fr) 1993-10-14
JPH07505445A (ja) 1995-06-15
DE59206327D1 (de) 1996-06-20
WO1993020259A1 (fr) 1993-10-14
US6197126B1 (en) 2001-03-06
ES2086782T3 (es) 1996-07-01
DE4210513A1 (de) 1993-10-07
ATE138112T1 (de) 1996-06-15

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