EP0656957B1 - Procede de phosphatation d'acier zingue d'un seul cote - Google Patents

Procede de phosphatation d'acier zingue d'un seul cote Download PDF

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Publication number
EP0656957B1
EP0656957B1 EP93919089A EP93919089A EP0656957B1 EP 0656957 B1 EP0656957 B1 EP 0656957B1 EP 93919089 A EP93919089 A EP 93919089A EP 93919089 A EP93919089 A EP 93919089A EP 0656957 B1 EP0656957 B1 EP 0656957B1
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EP
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Prior art keywords
phosphating
content
cations
galvanized
steel strip
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EP93919089A
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German (de)
English (en)
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EP0656957A1 (fr
Inventor
Jörg Riesop
Raschad Mady
Dieter Geruhn
Frank Panter
Franz Ricke
Hubertus Peters
Jürgen Verheien
Manfred Wessel
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Henkel AG and Co KGaA
Krupp Hoesch Stahl AG
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Henkel AG and Co KGaA
Krupp Hoesch Stahl AG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C22/07—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
    • C23C22/182—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
    • C23C22/188—Orthophosphates containing manganese cations containing also magnesium 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
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/77—Controlling or regulating of the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

Definitions

  • the present invention relates to a method for phosphating one-sided electrolytically galvanized steel strip with the formation of nickel-containing zinc phosphate layers on the galvanized surface. These zinc phosphate layers are applied by brief spraying or dipping treatment with aqueous, acidic phosphating solutions.
  • DE-A-32 45 411 discloses a process for the phosphating of electrolytically galvanized metal products, in particular electrolytically galvanized steel strips, by short-term treatment with acid phosphating solutions which, in addition to zinc and phosphate ions, can contain further metal cations and / or anions of oxygen-containing acids with accelerating action .
  • acid phosphating solutions which, in addition to zinc and phosphate ions, can contain further metal cations and / or anions of oxygen-containing acids with accelerating action .
  • zinc phosphate layers with a mass per unit area below 2 gm -2 are formed. It works with acid phosphating solutions, the content of Zn 2+ cations is about 1 to 2.5 g / l, while the free acid content in the range of 0.8 to 3 points and the total acid / free acid ratio in the range of 5 to be held to 10.
  • the duration of the treatment should not be significantly more than 5 seconds.
  • nitrate-containing phosphating baths are used, the weight ratio of Zn 2+ / NO 3 - in the range from 1: 1 to 1: 8 and the weight ratio of PO 4 3- / NO 3 - in the range from 1: 0.1 to 1 : 2.5 is held.
  • EP-A-0 219 779 describes a process for the phosphating of electrolytically galvanized metal products, preferably electrolytically galvanized steel products, in particular of electrolytically galvanized steel strips, by short-term treatment of acid phosphating solutions which are not significantly longer than 5 seconds and which, in addition to zinc, manganese and phosphate ions can contain further metal cations and / or anions of oxygen-containing acids with accelerating action.
  • phosphating solutions are used whose content of zinc cations (Zn 2+ ) is in the range of 0.1 to 0.8 g / l and their content of manganese cations ( Mn 2+ ) are in the range from 0.5 to 2.0 g / l, while the free acid content is in the range from 4 to 8 points and the acid ratio (total acid / free acid) is in the range from 2.5 to 5 becomes.
  • JP-A-62 020 879 a method for one-sided phosphating of galvanized steel strip is known.
  • the phosphating is carried out by spraying the phosphating solution on one side only onto the lower side of the steel strip, while compressed air is blown onto the upper side of the steel strip.
  • the object of the present invention was to maintain the treatment times of 2 to 20 s Manufacture corrosion protection values of zinc phosphate layers by spray or dip application on one side of electrolytically galvanized steel strip, in which the steel side still has a bright metallic surface even after phosphating.
  • the invention deliberately wants to achieve thin coating masses of the phosphate layers in the range from 0.5 to 3.0 gm -2 , in particular from 1.0 to 2.0 gm -2 , without, however, uniformly covering the one-sided galvanized steel strip with a to have to give up finely crystalline, firmly adhering, self-contained zinc phosphate layer.
  • electrolytically galvanized steel strip also includes, of course, generally known zinc alloys (for example ZNE electrolytically applied zinc alloy containing 10 to 13% Ni or ZFE electrolytically applied zinc alloy containing Fe).
  • the free acid score is accordingly defined as the number of ml 0.1 N NaOH required to titrate 10 ml bath solution against dimethyl yellow, methyl orange or bromophenol blue.
  • the total acid score is calculated as the number of ml of 0.1 N NaOH required to titrate 10 ml of bath solution using phenolphthalein as an indicator until the first pink color.
  • the acidic phosphating solutions quickly remove zinc from the galvanized strip.
  • a higher zinc content in the phosphating bath occurs during operation due to the usual entry of Zn 2+ cations due to the steel strip galvanized on one side.
  • a content of Zn 2+ cations in the range from 3.0 to 5.0 g / l is preferred.
  • the content of nickel cations is less than 0.5 g / l, the adhesion between the substrate and the coating after the cataphoresis becomes insufficient. On the other hand, if the nickel content is more than 5.0 g / l, no further improved effects can be achieved for the subsequent coating.
  • the content of nickel cations is therefore preferably adjusted so that a concentration of 1.0 to 3.0 g / l is maintained in the phosphating bath.
  • phosphate anions in the solution is less than 14 g / l, a defective zinc phosphate layer is formed.
  • the phosphate content is more than 25 g / l, no additional advantageous effects can be obtained.
  • the use of larger proportions of phosphate is therefore disadvantageous for economic reasons. It is therefore preferred to use a phosphating solution containing 19 to 23 g / l phosphate ions.
  • the phosphating solutions additionally contain at least one further divalent cation selected from manganese, cobalt, iron, calcium and magnesium.
  • these additional divalent cations are used in the following concentrations in the phosphating solutions: 0.2 to 3.0 g / l manganese, 0.5 to 4.0 g / l cobalt, 0.05 to 1.0 g / l Iron and 0.5 to 5.0 g / l calcium or magnesium.
  • Divalent manganese is preferably used as a further, additional cation.
  • An essential criterion of the present invention is the duration of the phosphating treatment. While times in the automotive industry are usually used for phosphating above 120 s, phosphating is one-sided galvanized steel strip definitely strives for a time well below 1 min. For the purposes of the present invention, the duration of the treatment will therefore be between 2 to 20 s. A duration of the treatment of 5 to 10 s is particularly preferred.
  • the main advantage of the present invention is that zinc phosphate coatings can be produced according to the invention on one-sided galvanized steel strip, which have a bright surface appearance of the galvanized surface with a simultaneously bright metallic surface of the non-galvanized surface.
  • a further preferred embodiment of the present invention is characterized in that the phosphating solutions have a fluoride anion content of 0.1 to 0.5 g / l, preferably 0.1 to 0.2 g / l.
  • the phosphating itself takes place at moderately elevated temperatures in the range from about 40 to 70 ° C.
  • the temperature range from 55 to 65 ° C. can be particularly suitable.
  • the phosphating solutions 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.
  • Suitable starting products for the preparation of the phosphating solutions are water-soluble salts of the cations mentioned, for example the nitrates or carbonates, or corresponding soluble oxides or hydroxides.
  • the cations mentioned are used in the form of their nitrates, but the nitrate content of the phosphating solutions has no influence on that Phosphating result comes.
  • the phosphate anions are usually introduced into the phosphating solutions in the form of phosphoric acid. Here, the total acid content is adjusted via the phosphate anions in the phosphating solutions.
  • the free acid content is optionally adjusted by increasing the pH, for example by adding sodium hydroxide or sodium carbonate.
  • the fluoride anions which may be used in the phosphating solutions are generally introduced in the form of sodium fluoride or complex fluorides, for example tetrafluoroborate or hexafluorosilicate.
  • the surface galvanized on one side must be completely water-wettable. This is usually the case in continuously operating conveyor systems. If the surface of the one-sided galvanized strip is oiled for storage and corrosion protection, this oil must be removed before phosphating using known suitable means and methods.
  • the water-wettable galvanized metal surface is then expediently subjected to an activating pretreatment known per se before the phosphating solution is applied. Suitable pretreatment processes are described in particular in DE-A-20 38 105 and DE-A-20 43 085.
  • the metal surfaces to be subsequently phosphated are treated with solutions which contain, as activating agents, essentially titanium salts and sodium phosphate, optionally together with organic components such as, for example, alkyl phosphonates or polycarboxylic acids.
  • Soluble compounds of titanium such as potassium titanium fluoride or titanyl sulfate, can preferably be used as the titanium component.
  • Disodium orthophosphate is generally used as the sodium phosphate.
  • the process according to the invention produces zinc phosphate coatings on the galvanized side with a weight per unit area of the zinc phosphate layers of preferably from 0.5 to 2 gm -2 , in particular from 1.0 to 2.0 gm -2 , which have a closed, finely crystalline structure and which on one side electrolytically galvanized steel strip give a desired, uniform, light gray appearance, with a bare metallic surface of the non-galvanized surface.
  • a steel strip phosphated in this way can also be processed without subsequent coating.
  • the thin phosphate layers produced by the process according to the invention behave favorably in many deformation processes. Subsequent organic coatings also show significantly improved adhesion compared to the prior art, both during and after the deformation processes.
  • a phosphate layer with a mass per unit area of 0.9 to 1.5 gm -2 was produced for steel galvanized on one side.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Laminated Bodies (AREA)
  • Coating With Molten Metal (AREA)

Claims (10)

  1. Procédé de phosphatation d'un ruban d'acier galvanisé d'un seul côté par électrolyse sur la surface galvanisée, par la formation de couches de phosphate de zinc contenant du nickel dont la masse par unité de surface se situe dans le domaine de 0,5 à 3,0 gm-2, à l'aide d'un traitement par pulvérisation ou par immersion de courte durée avec des solutions acides de phosphatation, dans lequel la durée du traitement s'élève de 2 à 20 s en fonction de la vitesse du ruban; on effectue la phosphatation à une température de 40 à 70°C et les solutions de phosphatation respectent les paramètres suivants:
    Teneur en cations Zn2+ : 1,0 à 6,0 g/l,
    Teneur en cations Ni2+ : 0,5 à 5,0 g/l,
    Teneur en anions PO4 3- : 14 à 25,0 g/l,
    Teneur en « acide libre » dans le domaine de 3,5 à 8,0 points,
    Teneur en « acide total » dans le domaine de 22 à 40 points.
  2. Procédé selon la revendication 1, caractérisé en ce que la durée du traitement s'élève de 5 à 10 s.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la teneur en cations Zn2+ s'élève de 3,0 à 5,0 g/l.
  4. Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce que la teneur en cations Ni2+ s'élève de 1,0 à 3,0 g/l.
  5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce que la solution de phosphatation contient de 19 à 23 g/l d'anions phosphate.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que les solutions de phosphatation présentent en outre une teneur d'au moins un autre cation bivalent supplémentaire choisi parmi le manganèse, le cobalt, le fer, le calcium et le magnésium, dans des concentrations des cations respectifs de 0,2 à 3,0 g/l de manganèse, de 0,5 à 4,0 g/l de cobalt, de 0,05 à 1,0 g/l de fer et de 0,5 à 5,0 g/l de calcium ou de magnésium.
  7. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que les solutions de phosphatation présentent une teneur en anions fluorure de 0,1 à 0,5 g/l.
  8. Procédé selon une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'on effectue la phosphatation dans le domaine de températures de 55 à 65°C.
  9. Procédé selon une ou plusieurs des revendications 1 à 8, caractérisé en ce que la masse par unité de surface des couches de phosphate de zinc s'éleve de 1,0 à 2,0 gm-2.
  10. Procédé selon une ou plusieurs des revendications 1 à 9, caractérisé en ce que le ruban d'acier galvanisé d'un seul côté par électrolyse est soumis au préalable à un prétraitement d'activation connu en soi.
EP93919089A 1992-08-27 1993-08-18 Procede de phosphatation d'acier zingue d'un seul cote Expired - Lifetime EP0656957B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4228470 1992-08-27
DE4228470A DE4228470A1 (de) 1992-08-27 1992-08-27 Verfahren zur Phospatierung von einseitig verzinktem Stahlband
PCT/EP1993/002205 WO1994005826A1 (fr) 1992-08-27 1993-08-18 Procede de phosphatation d'acier zingue d'un seul cote

Publications (2)

Publication Number Publication Date
EP0656957A1 EP0656957A1 (fr) 1995-06-14
EP0656957B1 true EP0656957B1 (fr) 1997-03-26

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EP93919089A Expired - Lifetime EP0656957B1 (fr) 1992-08-27 1993-08-18 Procede de phosphatation d'acier zingue d'un seul cote

Country Status (7)

Country Link
US (1) US5516372A (fr)
EP (1) EP0656957B1 (fr)
JP (1) JPH08501829A (fr)
KR (1) KR950703075A (fr)
AT (1) ATE150803T1 (fr)
DE (2) DE4228470A1 (fr)
WO (1) WO1994005826A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4326388A1 (de) * 1993-08-06 1995-02-09 Metallgesellschaft Ag Verfahren zur phosphatierenden Behandlung von einseitig verzinktem Stahlband
FR2713669B1 (fr) * 1993-12-14 1996-01-05 Lorraine Laminage Inhibiteur de la corrosion d'un matériau métallique, tel que l'acier.
US5888315A (en) * 1995-03-07 1999-03-30 Henkel Corporation Composition and process for forming an underpaint coating on metals
DE19639597C2 (de) * 1996-09-26 2000-01-20 Henkel Kgaa Verfahren zur Phosphatierung von laufenden Bändern aus kalt- oder warmgewalztem Stahl in schnellaufenden Bandanlagen
DE19639596A1 (de) * 1996-09-26 1998-04-02 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
DE19756735A1 (de) * 1997-12-19 1999-06-24 Henkel Kgaa Phosphatierung von einseitig verzinktem Stahlband
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EP0656957A1 (fr) 1995-06-14
US5516372A (en) 1996-05-14
DE59305978D1 (de) 1997-04-30
KR950703075A (ko) 1995-08-23
DE4228470A1 (de) 1994-03-03
WO1994005826A1 (fr) 1994-03-17
JPH08501829A (ja) 1996-02-27
ATE150803T1 (de) 1997-04-15

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