EP0228151B1 - Solutions aqueuses acides de phosphatation pour leur utilisation dans un procédé de phosphatation de surfaces métalliques - Google Patents

Solutions aqueuses acides de phosphatation pour leur utilisation dans un procédé de phosphatation de surfaces métalliques Download PDF

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Publication number
EP0228151B1
EP0228151B1 EP86306622A EP86306622A EP0228151B1 EP 0228151 B1 EP0228151 B1 EP 0228151B1 EP 86306622 A EP86306622 A EP 86306622A EP 86306622 A EP86306622 A EP 86306622A EP 0228151 B1 EP0228151 B1 EP 0228151B1
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EP
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Prior art keywords
ion
phosphate
solution according
zinc
solution
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Revoked
Application number
EP86306622A
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German (de)
English (en)
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EP0228151A1 (fr
Inventor
Satoshi Miyamoto
Masamichi Nagatani
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Henkel Corp
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Nippon Paint Co Ltd
Henkel Corp
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Application filed by Nippon Paint Co Ltd, Henkel Corp filed Critical Nippon Paint Co Ltd
Priority to AT86306622T priority Critical patent/ATE99002T1/de
Priority to EP93200125A priority patent/EP0544650B1/fr
Publication of EP0228151A1 publication Critical patent/EP0228151A1/fr
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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
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations

Definitions

  • the present invention relates to an acidic, aqueous phosphate-coating solution for use in a process for phosphating metal surfaces. More particularly, it relates to a solution for forming a phosphate film especially suitable for cationic electrocoating, and is particularly applicable to metal surfaces which include both an iron-based surface and a zinc-based surface such as an automobile body.
  • Japanese Patent Publication (unexamined) No. 107784/1980 discloses a process for treating a metal surface by dip treatment, followed by spray treatment, with an acidic aqueous phosphate solution containing from 0.5 to 1.5 g/l of zinc ion, from 5 to 30 g/l of phosphate ion, and from 0.01 to 0.2 g/l of nitrite ion and/or from 0.05 to 2 g/l of m-nitrobenzenesulfonate ion.
  • Said process is reported to be capable of providing a phosphate film which is effective for forming a coating by cationic-resistance on complicated articles having many pocket portions like car bodies.
  • Japanese Patent Publication (unexamined) No. 145180/1980 discloses a process for treating a metal surface by spray treatment with an acidic aqueous phosphate solution containing from 0.4 to 1.0 g/l of zinc ion, from 5 to 40 g/l of phosphate ion, from 2.0 to 5.0 g/l of chlorate ion, and from 0.01 to 0.2 g/l of nitrite ion.
  • Japanese Patent Publication (unexamined) No. 1512183/1980 discloses an acidic aqueous phosphate solution containing from 0.08 to 0.20 wt.
  • a protective coating can be formed on steel or other metal surfaces at low temperatures, for instance below 40°C, by contact with a solution that is generally free of chlorate and chloride and that contains 0.5 to 1.5 parts silicofluoride or borofluoride, 0.8 to 2.5 parts zinc, 10 to 25 parts phosphate, 1.5 to 10 parts nitrate, 0.1 to 1.2 parts nickel and 0.25 to 2 parts sodium nitrobenzene sulfonate.
  • the composition may also contain 0 to 0.7 parts manganese.
  • each spot having a diameter of from 1 mm to 2 mm.
  • These white spots will cause craters in subsequent treatment, thereby resulting in inferior coatings.
  • the mechanism by which white spots are formed is believed to be as follows: In a first stage, there appear many pits, at the edge portions of which the galvanized layer is gradually dissolved in the form of concentric circles through an excessive etching reaction. As the growth of each pit continues, zinc phosphate is precipitated in the centre portion thereof. However, at the peripheral portions, the ion surface is exposed, which forms a galvanic cell with the zinc metal, thereby continuing the dissolution of the zinc.
  • phosphating compositions which are chlorate-free or at least substantially chlorate-free and which have a chloride ion level below 0.5 g/l provide excellent phosphate-coatings on iron, zinc, and aluminium-based surfaces, without the formation of deleterious white spots. It is important to the beneficial results of the present invention that the chloride ion level be consistently maintained below 0.5 g/l, which means that not only the chloride ion itself, but also the chlorate ion should not be added to the phosphating compositions, since the chlorate ion will be reduced to the chloride ion as the phosphating composition is used.
  • an acidic aqueous phosphate solution for use in a process for phosphating a metal surface, said solution containing at most 0.2 g/l and preferably no chlorate ion as well as the smallest practical concentration never exceeding 0.5 g/l of chloride ion, said solution otherwise containing:
  • the metal surfaces treated in accordance with the present invention include iron-based surfaces, zinc-based surfaces, aluminum-based surfaces, and their respective alloy-based surfaces. These metal surfaces can be treated either separately or in combination.
  • the advantage of the present invention is most prominently exhibited when the treatment is carried out on metal surfaces which include both an iron-based surface and a zinc-based surface, as for example in a car body.
  • zinc-based surfaces include galvanized steel plate, galvanealed steel plate, electrogalvanized steel plate, electro zinc-alloy plated steel plate, complex electrogalvanized steel plate, electro zinc-alloy plated steel plate, complex electrogalvanized steel plate, etc.
  • the manganese content in the phosphate film formed on zinc-based surfaces becomes smaller - and indeed it may be noted that at less than 0.2 g/l the adhesion between the substrate and the coating after the cationic electrocoating becomes insufficient.
  • the manganese ion is present in an amount of more than 4 g/l, no further beneficial effects are obtained for the coating, and the solution forms excessive precipitates, making it impossible to obtain a stable solution.
  • the manganese content in the phosphate film formed on the metal substrates should be in the range of from about 1 to about 20% by weight, based on the weight of the film, in order to have a phosphate film which exhibits the performance requirements for cationic electrocoating.
  • the manganese content can be calculated from the formula (W M /W C ) x 100 % .
  • the amount of fluoride ion in the phosphating solution is less than 0.05 g/l, micronization of the phosphate film, improvement of corrosion-resistance after coating, and phosphating treatment at a reduced temperature cannot be attained.
  • the fluoride ion can be present in an amount above 3 g/l, but use thereof in such quantities will not provide any greater effects than are obtainable in the range of 0.05 - 3 g/l.
  • the fluoride ion is contained in the form of a complex fluoride ion, e.g. the fluoroborate ion or the fluorosilicate ion, although the F ⁇ ion itself can also be used.
  • the weight ratio of zinc ion to phosphate be 1: (10 to 30). In this ratio an even phosphate film is obtained which exhibits all of the performance requirements needed for cationic electrocoating.
  • the weight ratio of zinc ion to manganese ion is preferably 1 : (0.5 to 2). In this ratio it is possible to obtain in an economic manner a phosphate film which contains the required amount of manganese and which displays all of the beneficial effects provided by the present invention.
  • the solutions of the invention it is desirable for the solutions to have a total acidity of 10 to 50 points, a free acidity of 0.3 to 2.0 points, and an acid ratio of 10 to 50.
  • the total acidity in the above range the phosphate film can be obtained economically, and with the free acidity in the above range the phosphate film can be obtained evenly without excessive etching of the metal surface.
  • Adjustments in the solution to obtain and maintain the above points and ratio can be achieved by use of an alkali metal hydroxide or ammonium hydroxide as required.
  • Sources of the ingredients of the phosphating solutions of the invention include the following: as to the zinc ion, one can use zinc oxide, zinc carbonate, zinc nitrate, etc.; as to the phosphate ion, one can use phosphoric acid, zinc phosphate, zinc monohydrogen phosphate, zinc dihydrogen phosphate, manganese phosphate, manganese monohydrogen phosphate, manganese dihydrogen phosphate, etc.; as to the manganese ion, one can use manganese carbonate, manganese nitrate, the above-mentioned mentioned manganese phosphate compounds, etc.; as to the fluoride ion, one can use hydrofluoric acid, fluoroboric acid, fluorosilicic acid, fluorotitanic acid, and their metal salts (e.g.
  • the sodium salt is excluded as it does not produce the desired effect
  • the phosphating accelerator one can use sodium nitrite, ammonium nitrite, sodium m-nitrobenzenesulfonate, sodium m-nitrobenzoate, aqueous hydrogen peroxide, nitric acid, zinc nitrate, manganese nitrate, nickel nitrate, etc..
  • the phosphating solutions of the invention can further contain, as an optional ingredient, nickel ion.
  • the content of the nickel ion should be from 0.1 to 4 g/l, preferably from 0.3 to 2 g/l.
  • performance of the resulting phosphate film is further improved, i.e. the adhesion and corrosion-resistance of the coating obtained after cationic electrocoating are further improved.
  • the weight ratio of zinc ion to the sum of the manganese ion and the nickel ion is desirably 1 : (0.5 to 5.0), preferably 1 : (0.8 to 2.5).
  • the supply source of nickel ion can be for example nickel carbonate, nickel nitrate, nickel phosphate, etc..
  • the phosphate film formed by the solutions of the present invention is a zinc phosphate-type film.
  • Such films formed on iron based metal surfaces contain from about 25 to about 40 wt. % of zinc, from about 3 to about 11 wt. % of iron, from about 1 to about 20 wt. % of manganese, and from 0 to about 4 wt. % of nickel.
  • the phosphating solutions of the invention can be used to phosphate metal surfaces by spray treatment, dip treatment, or by a combination of such treatments.
  • Spray treatment can usually be effected by spraying for 5 or more seconds in order to form an adequate phosphate film which exhibits the desired performance characteristics.
  • Spray treatment can be conveniently carried out using a cycle comprising first a spray treatment for about 5 to about 30 seconds, followed by discontinuing the treatment for about 5 to 30 seconds, and then spray treating again for at least 5 seconds, with a total spray treatment time of at least 40 seconds. This cycle can be carried out once, twice or three times.
  • Dip treatment is usually more to be preferred than spray treatment in the process of the present invention.
  • the dip treatment is usually effected for at least 15 seconds, preferably for about 30 to about 120 seconds.
  • treatment can be carried out by first dip treating for at least 15 seconds and then spray treating for at least 2 seconds.
  • the treatment can be effected by first spray treating for at least 5 seconds, and then dip treating for at least 15 seconds.
  • the former combination of first dip treating and then spray treating is especially advantageous for articles having complicated shapes like a car body. For such articles, it is preferable to first carry out a dip treatment for from 30 to 90 seconds, and then carry out the spray treatment for from 5 to 45 seconds. In this process, it is advantageous to effect the spray treatment for as long a time as possible within the limitations of the automotive production line, in order to remove the sludge which adheres to the article during the dip treatment stage.
  • the treating temperature can be from 30 to 70°C, preferably from 35 to 60°C. This temperature range is approximately 10 to 15°C lower than that which is used in the prior art processes. Treating temperatures below 30°C should not be used due to an unacceptable increase in the time required to produce an acceptable coating. Conversely, when the treating temperature is too high, the phosphating accelerator is decomposed and excess precipitate is formed causing the components in the solution to become unbalanced and making it difficult to obtain satisfactory phosphate films.
  • a convenient spray pressure is from 0.6 to 2 Kg/cm2G.
  • a preferred mode of treatment in using the solutions of the present invention is a dip treatment or a combined treatment using a dip treatment first and then a spray treatment.
  • An advantageous procedure for treating metal surfaces using a series of pre-coating treatment procedures followed by phosphating with the solutions of the present invention is as follows: A metal surface is first subjected to a spray treatment and/or a dip treatment with an alkaline degreasing agent at a temperature of 50 to 60°C for 2 minutes; followed by washing with tap water; spray treatment and/or dip treatment with a surface conditioner at room temperature for 10 to 30 seconds; dip treatment with the solution of the present invention at a temperature of about 30 to about 70°C for at least 15 seconds; and washing with tap water and then with deionized water, in that order. Thereafter, it is desirable to after-treat with an acidulated rinse common to the industry such as a dilute chromate solution.
  • This after-treatment is preferably adopted even when phosphating is carried out by spray treatment or by a combined treatment comprising a spray treatment, followed by a dip treatment.
  • a phosphate film which gives greater corrosion-resistance to a siccative coating can be obtained.
  • an acidic aqueous phosphate solution of the present invention comprising:
  • Concentrated aqueous compositions are employed for formulating the acidic aqueous phosphate solutions of the present invention.
  • the acidic aqueous treating solutions are conveniently prepared by diluting an aqueous concentrate which contains a number of the solution ingredients in proper weight ratios, and then adding other ingredients as needed to prepare the treating solutions of the invention.
  • the concentrates are advantageously formulated to contain zinc ion, phosphate ion, manganese ion, fluoride ion, and optionally nickel ion, in a weight proportion of 0.1 to 2 : 5 to 50 : 0.8 to 4 : at least 0.05 : 0.1 to 4.
  • the concentrates preferably contain a weight proportion of the above ingredients of 0.5 to 1.5 : 10 to 30 : 0.8 to 3 : 0.1 to 3 : 0.3 to 2.
  • the concentrates are preferably formulated to contain at least about 25 g/l, more preferably from about 50 g/l to 130 g/l of zinc ion.
  • care must be taken in forming the concentrates. For example, when manganese ion and complex fluoride ion are present together in a concentrate with sodium ion, a precipitate is formed. Also, it is not advisable to add any phosphating accelerator to the concentrate, since the accelerators tend to decompose and cause other problems.
  • a concentrated composition comprising 3.0 wt. % of zinc oxide, 1.8 wt. % of nickel carbonate (II), 48.2 wt. % of 75 % phosphoric acid, 10.0 wt. % of manganese nitrate (II) hydrate (20 wt. % manganese content), 7.9 wt. % of 40 % fluorosilicic acid, and 29.1 wt. % of water.
  • This concentrate is then diluted with water to 2.5 vol. %, followed by the addition of an aqueous solution of 20 % sodium nitrite to give an acidic phosphating solution of the invention.
  • Example 1 contained a small quantity of chlorate ion (0.2 g/l) which did not deleteriously affect the results obtained using the fresh bath, it is not recommended that the composition of Example 1 be employed commercially since maintaining even this low chlorate level in the bath as the bath continues to be used will eventually result in the reduction of sufficient chlorate ion to elevate the chloride ion above 0.5 g/l.
  • the present solution contains not more than about 0.2 g/l of chlorate ion. It is especially preferred that the solution contains no chlorate.
  • the present invention is advantageous in avoiding white spots, especially on galvanized steel, particularly when the phosphating treatment comprises dipping.
  • the present solution contains at least about 1.05 g/l, especially at least about 1.1 g/l of zinc ion, for instance from about 1.05 to about 1.5 g/l of zinc ion, especially when the phosphating treatment comprises dipping.
  • the solution contains at least about 15 g/l of phosphate ion, for instance from about 15 to about 50 g/l, especially from about 15 to about 30 g/l, of phosphate ion.
  • the solution contains more than about 4.0 g/l, especially more than about 5 g/l, of nitrate ion.
  • the solution may contain from about 5 to about 15 g/l, especially from about 5 to about 10 g/l, on nitrate ion.
  • the solution contains from about 0.3 g/l, especially more than about 0.4 g/l, of nickel ion.
  • the solution may contain from about 0.4 to about 4 g/l, especially from about 0.4 to about 2 g/l, of nickel ion.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
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  • Laminated Bodies (AREA)
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Claims (22)

  1. Solution aqueuse acide pour la phosphatation d'une surface métallique, ladite solution contenant au plus 0,2 g/l et de préférence aucun ion chlorate ainsi que la plus petite concentration pratique d'ion chlorure n'excédant jamais 0,5 g/l, cette solution comprenant de plus :
    a) de 0,1 à 1,5 g/l d'ion zinc,
    b) de 5 à 50 g/l d'ion phosphate,
    c) d'au moins 0,8 à 4 g/l d'ion manganèse,
    d) au moins 0,05 g/l d'un ion fluorure, et
    e) au moins l'un des accélérateurs de phosphatage suivant dans les concentrations suivantes :
    i) de 0,01 à 0,2 g/l d'ion nitrite,
    ii) de 1 à 15 g/l d'ion nitrate,
    iii)de 0,5 à 5 g/l de peroxyde d'hydrogène (basé sur 100 % d'H₂O₂),
    iv) de 0,05 à 2 g/l d'ion m-nitro-benzènesulfonate,
    v) de 0,05 à 2 g/l d'ion m-nitro-benzoate, et
    vi) de 0,05 à 2 g/l de p-nitrophénol.
  2. Solution selon la revendication 1, qui comprend de 0,5 à 1,4 g/l d'ion zinc.
  3. Solution selon la revendication 2, qui comprend de 0,7 à 1,2 g/l d'ion zinc.
  4. Solution selon l'une quelconque des revendications 1 à 3, qui comprend de 5 à 30 g/l d'ion phosphate.
  5. Solution selon la revendication 4, qui comprend au moins 10 g/l d'ion phosphate.
  6. Solution selon la revendication 5, qui comprend de 10 à 20 g/l d'ion phosphate.
  7. Solution selon l'une quelconque des revendications 1 à 3, qui comprend de 15 à 50 g/l d'ion phosphate.
  8. Solution selon l'une quelconque des revendications précédentes, qui comprend de 0,8 à 3 g/l d'ion manganèse.
  9. Solution selon la revendication 8, qui comprend 0,8 à 2 g/l d'ion manganèse.
  10. Solution selon l'une quelconque des revendications précédentes, dans laquelle la solution comprend de 0,1 à 3 g/l d'ion fluorure.
  11. Solution selon la revendication 10, qui comprend de 0,1 à 2 g/l d'ion fluorure.
  12. Solution selon l'une quelconque des revendications précédentes, qui comprend de 1 à 10 g/l d'ion nitrate.
  13. Solution selon l'une quelconque des revendications précédentes, qui comprend un ou plusieurs des accélérateurs suivants dans les quantités suivantes :
    i) de 0,04 à 0,15 g/l d'ion nitrite,
    ii) de 2 à 8 g/l d'ion nitrate,
    iii) de 1 à 1,5 g/l de peroxyde d'hydrogène (basé sur 100 % d'H₂O₂),
    iv) de 0,1 à 1,5 g/l d'ion m-nitro-benzènesulfonate,
    v) de 0,1 à 1,5 g/l d'ion m-nitrobenzoate, et
    vi) de 0,1 à 1,5 g/l de p-nitrophénol.
  14. Solution selon l'une quelconque des revendications précédentes, qui comprend :
    a) de 0,7 à 1,2 g/l d'ion zinc,
    b) de 10 à 20 g/l d'ion phosphate,
    c) de 0,8 à 2 g/l d'ion manganèse, et
    d) de 0,1 à 2 g/l d'un ion fluorure.
  15. Solution selon l'une quelconque des revendications précédentes, qui comprend de 0,4 à 4 g/l d'ion nickel.
  16. Solution selon l'une quelconque des revendications précédentes, qui comprend de 5 à 15 g/l d'ion nitrate.
  17. Solution selon l'une quelconque des revendications 1 à 15, qui comprend de 1 à 10 g/l d'ion nitrate.
  18. Solution selon l'une quelconque des revendications précédentes, qui comprend de 1,05 à 1,5 g/l d'ion zinc.
  19. Solution selon l'une quelconque des revendications précédentes, qui comprend de 15 à 50 g/l d'ion phosphate.
  20. Solution selon l'une quelconque des revendications précédentes, spécialement adaptée pour le traitement par immersion des surfaces métalliques, qui comprend :
    a) de 0,5 à 1,4 g/l d'ion zinc,
    b) de 5 à 30 g/l d'ion phosphate,
    c) d'au moins 0,8 à 3 g/l d'ion manganèse,
    d) d'au moins 0,05 g/l d'un ion fluorure, et
    e) au moins l'un des accélérateurs de phosphatage suivants dans les concentrations suivantes :
    i) de 0,01 à 0,2 g/l d'ion nitrite,
    ii) de 1 à 10 g/l d'ion nitrate,
    iii) de 0,5 à 5 g/l de peroxyde d'hydrogène (basé sur 100 % d'H₂O₂),
    iv) de 0,05 à 2 g/l d'ion m-nitro-benzènesulfonate,
    v) de 0,05 à 2 g/l d'ion m-nitro-benzoate, et
    vi) de 0,05 à 2 g/l de p-nitrophénol.
  21. Solution selon l'une quelconque des revendications précédentes, qui comprend :
    a) de 0,7 à 1,2 g/l d'ion zinc,
    b) de 10 à 20 g/l d'ion phosphate,
    c) de 0,8 à 2 g/l d'ion manganèse, et
    d) de 0,1 à 2 g/l d'un ion fluorure.
  22. Solution selon l'une quelconque des revendications précédentes, qui comprend de 0,4 à 4 g/l d'ion nickel.
EP86306622A 1985-08-27 1986-08-27 Solutions aqueuses acides de phosphatation pour leur utilisation dans un procédé de phosphatation de surfaces métalliques Revoked EP0228151B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AT86306622T ATE99002T1 (de) 1985-08-27 1986-08-27 Saure, waessrige phosphatueberzugsloesungen fuer ein verfahren zum phosphatbeschichten metallischer oberflaeche.
EP93200125A EP0544650B1 (fr) 1985-08-27 1986-08-27 Procédé de phosphatation de surfaces métalliques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US77003185A 1985-08-27 1985-08-27
US770031 1985-08-27

Related Child Applications (1)

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EP93200125.8 Division-Into 1986-08-27

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EP0228151A1 EP0228151A1 (fr) 1987-07-08
EP0228151B1 true EP0228151B1 (fr) 1993-12-22

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EP86306622A Revoked EP0228151B1 (fr) 1985-08-27 1986-08-27 Solutions aqueuses acides de phosphatation pour leur utilisation dans un procédé de phosphatation de surfaces métalliques
EP93200125A Revoked EP0544650B1 (fr) 1985-08-27 1986-08-27 Procédé de phosphatation de surfaces métalliques

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EP93200125A Revoked EP0544650B1 (fr) 1985-08-27 1986-08-27 Procédé de phosphatation de surfaces métalliques

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EP (2) EP0228151B1 (fr)
AT (2) ATE99002T1 (fr)
DE (2) DE3689442T2 (fr)
HK (2) HK1007771A1 (fr)
SG (1) SG52645A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE3630246A1 (de) * 1986-09-05 1988-03-10 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung
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DE3650659T2 (de) 1998-07-02
HK1007771A1 (en) 1999-04-23
ATE160592T1 (de) 1997-12-15
DE3650659D1 (de) 1998-01-08
HK1012681A1 (en) 1999-08-06
DE3689442D1 (de) 1994-02-03
ATE99002T1 (de) 1994-01-15
SG52645A1 (en) 1998-09-28
EP0544650B1 (fr) 1997-11-26
EP0228151A1 (fr) 1987-07-08
EP0544650A1 (fr) 1993-06-02
DE3689442T2 (de) 1994-06-16

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