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EP0675972B1 - Im wesentlichen nickelfreier phosphatkonversionsüberzug-zusammensetzung und verfahren - Google Patents

Im wesentlichen nickelfreier phosphatkonversionsüberzug-zusammensetzung und verfahren Download PDF

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Publication number
EP0675972B1
EP0675972B1 EP94904428A EP94904428A EP0675972B1 EP 0675972 B1 EP0675972 B1 EP 0675972B1 EP 94904428 A EP94904428 A EP 94904428A EP 94904428 A EP94904428 A EP 94904428A EP 0675972 B1 EP0675972 B1 EP 0675972B1
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French (fr)
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EP0675972A4 (de
EP0675972A1 (de
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Robert W. Miller
Michael Petschel
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Henkel Corp
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Henkel Corp
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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
    • C23C22/12—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
    • C23C22/186—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
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/368—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 magnesium cations

Definitions

  • This invention relates to a composition and process for forming a phosphate conversion coating on active metal surfaces in order to increase the corrosion resistance of the surfaces, either as treated or after subsequent conventional overcoating of the conversion coating layer formed by an organic based protective coating such as a paint or lacquer.
  • a composition according to this invention is well adapted to treating any of a variety of base metals, including at least steel and galvanized steel and aluminum and aluminum based alloys.
  • phosphate conversion coating compositions and processes are already described in the art. Those believed to be generally considered of highest quality at present include zinc, nickel, and at least one other divalent metal such as manganese in the composition.
  • Nickel has been implicated as a carcinogen in some studies, so that avoidance of its use in metal finishing is desirable for health reasons. Nickel is also considered a serious pollutant, and at the levels of 0.5-1.5 grams per liter (hereinafter often abbreviated "g/L") at which it is conventionally used, nickel contributes significantly to the cost of the zinc phosphate conversation coating compositions. It is an object of this invention to minimize or eliminate the use of nickel, without worsening the quality of conversion coating obtained with conventional compositions containing zinc, nickel, and manganese.
  • g/L grams per liter
  • Fosfa-Col &c.'s French Patent No. 2,203,893 in the context of "normal-zinc" processes operating at Zn-concentrations of e.g. 2.94 g/L Zn, discloses Ni-free solutions which contain minimal concentrations of copper, which however must abide by the requirement that the ratio in gram-atoms of zinc to copper must lie in the range of from 100 to 1,500, exemplified as 0.011 and 0.019 mg/L.
  • Henkel KGaA's EPA 0,633,950 (corresponding to International Publication WO 93/20259) which was unpublished at the priority date of the present Application but is itself of earlier date discloses a composition and process for phosphatizing using an aqueous solution comprising 0.2 to 2 g/L Zn ions, 0.5 to 25 mg/L Cu ions, 5 to 30 g/L of phosphate (P 2 O 5 ) and 0.5 to 5 g/L hydroxylamine.
  • an aqueous liquid zinc phosphatizing composition which contains no more than 0.2 g/L of Ni +2 and otherwise comprises water together with:
  • compositions preferably contain from 5-20, still more preferably from 13-18 g/L of dissolved phosphate ions.
  • compositions preferably contain, with increasing preference in the order given, from 0.57 to 1.24, from 0.60 to 0.95, or from 0.71 to 0.87, g/L of dissolved Zn +2 ions.
  • compositions preferably contain from 26 to 60 milligrams per liter ("mg/L") of dissolved CU +2 ions.
  • an effective amount of a conventional hydroxylamine accelerator is from 0.1 to 10 g/L of hydroxylamine or a stoichiometrically-equivalent amount of at least one component capable of furnishing hydroxylamine in water solution.
  • compositions preferably contain, with increasing preference in the order given, from 7 to 25, from 13 to 24, from 16 to 22, or from 18 to 21 "points" of total acid.
  • a process according to this invention comprises at a minimum a step of contacting a metal surface to be treated with a composition according to the invention for a sufficient time to form on the metal surface a detectable conversion coating.
  • Conventional metal surface cleaning and/or activation steps before contact between the metal to be treated and compositions according to the invention may be used if desired, and are generally preferred, as part of a process according to this invention.
  • a process according to the invention also may, and usually preferably does, include conventional steps subsequent to the contact between the metal surface to be treated and the compositions according to the invention. These subsequent steps, e.g., may include rinsing with water, any conventional reactive post treatments, e.g., with compositions according to the teachings of U.S. Patent 4,963,596 or with chromate containing solutions, and painting or otherwise protecting the surface with an outer coating of an organic based solid material.
  • the phosphate ions required for the compositions according to this invention are preferably PO 4 -3 ions or other ions derivable from less complete ionization of ortho-phosphoric acid (H 3 PO 4 ). Any free unionized phosphoric acid that may be present is considered part of the content of phosphate ions, to the extent of its stoichiometric correspondence to PO 4 -3 ions. Other free phosphoric acids such a metaphosphoric acid and condensed phosphoric acids such as pyrophosphoric acid and all anions derivable from them may also be used to supply the necessary phosphate ions.
  • the phosphate ions are derived from orthophosphoric acid and/or its neutral or acid salts of the metal cations also specified above as part of the compositions according to this invention.
  • the zinc cations required as part of the compositions are preferably derived from neutral or acid zinc salts of orthophosphoric acid, which may be formed in situ by dissolving zinc or zinc oxide or hydroxide in a solution containing the acid.
  • cupric cations required as part of the compositions according to the invention may be derived from salts such as cupric sulfate and/or nitrate, or may be obtained by dissolving cupric oxide in part of the phosphoric acid used.
  • the accelerator component required in compositions according to the invention preferably is or includes from 0.5 to 6 g/L, or more preferably from 0.5 to 2.0, g/L, measured as its stoichiometric equivalent as hydroxylamine, of at least one component capable of furnishing hydroxylamine in water solution.
  • the accelerator is hydroxylamine sulfate (hereinafter often abbreviated "HAS”) or a similar safe and readily available source of dissolved hydroxylamine.
  • the acidity of the compositions according to the invention is preferably derived from phosphoric, sulfuric, and/or nitric acids.
  • the free fluoride may be derived from complex fluoride ions such as fluoborate (BF 4 -2 ), fluohafnate (HfF 6 -2 ), fluosilicate (SiF 6 -2 ), fluotitanate (TiF 6 -2 ), fluozirconate (ZrF 6 -2 ), and mixtures thereof; more preferably, from fluoborate and fluosilicate and mixtures thereof.
  • complex fluoride ions such as fluoborate (BF 4 -2 ), fluohafnate (HfF 6 -2 ), fluosilicate (SiF 6 -2 ), fluotitanate (TiF 6 -2 ), fluozirconate (ZrF 6 -2 ), and mixtures thereof; more preferably, from fluoborate and fluosilicate and mixtures thereof.
  • simple fluorides such as alkali metal fluorides are also entirely satisfactory sources of free fluoride.
  • compositions according to the invention contain no more than 0.2 g/L of Ni +2 , and with increasing preference in the order given they contain no more than 0.10, 0.07, 0.03, 0.01, 0.005, or 0.001 g/L of Ni +2 . Similarly, with increasing preference in the order given and with independent preference for each noted component, the compositions contain no more than 0.5, 0.2, 0.10, 0.07, 0.03, 0.01, 0.005, or 0.001 g/L of any cation with a valence of three or higher, chloride ions including complex chloride ions, and chlorate ions.
  • the ratio of the concentration in g/L of complex fluoride ions to the concentration in g/L of chloride ions have a value of at least 8:1, or more preferably a value of at least 14:1.
  • contact between the metal surface to be treated and a composition according to the invention may be accomplished by spraying, dipping, or any other convenient method or combination of methods.
  • the temperature during contact between the metal treated and the composition according to the invention preferably is, with increasing preference in the order given, in the range from 21 to 85, 25 to 55, or 31 to 44, °C.
  • the total time of contact between the composition according to the invention and the metal surface to be conversion coated preferably is, with increasing preference in the order given, in the range from 5 sec to 15 minutes (hereinafter often abbreviated "min"), 15 seconds (hereinafter often abbreviated "sec”) to 10 min, 30 sec to 5 min, or 90 to 120 sec.
  • the add-on mass of the phosphate coating formed preferably is, with increasing preference in the order given, in the range from 1.1 to 5.4, 1.6 to 4.3, or 2.2 to 3.8, grams per square meter (hereinafter "g/m 2 ") of surface treated.
  • the weight percent of copper in the coating formed preferably is, with increasing preference in the order given, from 0.50 to 10, 1.0 to 8.0, 2.0 to 6.0, 3.0 to 4.1,
  • compositions illustrate the use of HAS accelerator. Specific compositions are shown in Table 1 below. These compositions were prepared according to the following general procedure:
  • Test panels of cold rolled steel, galvanized steel, and/or conventional aluminum alloys used in automobile and appliance manufacture were used and subjected to the following general sequence of process steps: (1) Conventional alkaline cleaner for 120 sec at 43°C; (2) Water rinse at 38°C for 60 sec; (3) Conventional colloidal titanium phosphate activator for 30 sec at 38°C; (4) Contact with one of Compositions 1-12 from Table 1 below for 120 sec at 35°C or at 43°C; (5) Cold water rinse at 20-25°C for 60 sec; (6) Post treatment for 30 sec with a conventional commercial post treatment composition containing hexavalent and trivalent chromium; and (7) Rinse with deionized water for 30 sec at 20-25°C.

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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)
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  • Battery Electrode And Active Subsutance (AREA)

Claims (30)

  1. Wässrige, flüssige Zink-Phosphatierungs-Zusammensetzung, die nicht mehr als 0,2 g/l Ni2+ und sonst Wasser zusammen mit:
    (A) 3 bis 50 g/l gelösten Phosphationen;
    (B) 0,45 bis 2 g/l gelösten Zn2+-Ionen;
    (C) 26 bis 74 mg/l gelösten Cu2+-Ionen;
    (D) einem Hydroxylamin-Beschleuniger in Form einer Komponente, die dazu in der Lage ist, in einer wässrigen Lösung Hydroxylamin zu bilden, in einer Menge, die 0,1 bis 10 g/l Hydroxylamin stöchiometrisch äquivalent ist;
    (E) 5 bis 40 Punkten Gesamtsäure und
    (F) -0,5 bis +0,8 Punkten freie Säure
    umfaßt.
  2. Zusammensetzung nach Anspruch 1, die kein zugegebenes Ni2+ enthält.
  3. Zusammensetzung nach Anspruch 1 oder Anspruch 2, die ebenfalls enthält:
    (G) Mn2+- und/oder Co2+-Ionen in einer kombinierten Gesamt-Konzentration von bis zu 2 g/l.
  4. Zusammensetzung nach Anspruch 3, wobei die Konzentration der gesamten Hn2+- und Co2+-Ionen im Bereich von 0,1 bis 0,8 g/l liegt.
  5. Zusammensetzung nach Anspruch 4, wobei die Konzentration der gesamten Hn2+- und Co2+-Ionen im Bereich von 0,40 bis 0,65 g/l liegt.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ebenfalls enthält:
    (H) Mg2+-Ionen in einer Konzentration bis zu 2 g/l.
  7. Zusammensetzung nach Anspruch 6, wobei die Konzentration der Mg2+-Ionen im Bereich von 0,5 bis 1,0 g/l liegt.
  8. Zusammensetzung nach Anspruch 7, wobei die Konzentration der Mg2+-Ionen im Bereich von 0,70 bis 0,80 g/l liegt.
  9. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ebenfalls enthält:
    (J) freie Fluoridionen in einer Konzentration von bis zu 5,5 g/l, gemessen durch eine fluorempfindliche Elektrode.
  10. Zusammensetzung nach Anspruch 9, wobei die Konzentration des freien Fluorids im Bereich von 1,0 bis 4,0 g/l liegt.
  11. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ebenfalls enthält:
    (K) SO4 2--Ionen in einer Konzentration von nicht mehr als 40 g/l.
  12. Zusammensetzung nach Anspruch 11, wobei die Konzentration der SO4 2--Ionen nicht mehr als 11 g/l beträgt.
  13. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ebenfalls enthalt:
    NO3 --Ionen in einer Konzentration von nicht mehr als 3,4 g/l.
  14. Zusammensetzung nach Anspruch 13, wobei die Konzentration der NO3 --Ionen nicht mehr als 2,0 g/l beträgt.
  15. Zusammensetzung nach Anspruch 14, wobei die Konzentration der NO3 --Ionen nicht mehr als 1,8 g/l beträgt.
  16. Zusammensetzung nach Anspruch 15, wobei die Konzentration der NO3 --Ionen nicht mehr als 1,3 g/l beträgt.
  17. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei:
    (A) die Konzentration der gelösten Phosphationen im Bereich von 5 bis 20 g/l liegt und
    (B) die Konzentration der gelösten Zn2+-Ionen im Bereich von 0,60 bis 0,95 g/l liegt und
    (E) die Punkte der Gesamtsäure im Bereich von 7 bis 25 liegen.
  18. Zusammensetzung nach Anspruch 17, wobei:
    (B) die Konzentration der gelösten Zn2+-Ionen im Bereich von 0,57 bis 1,24 g/l liegt;
    (C) die Konzentration der Cu2+-Ionen im Bereich von 26 bis 60 mg/l liegt und
    (E) die Punkte der Gesamtsäure im Bereich von 13 bis 24 liegen.
  19. Zusammensetzung nach Anspruch 18, wobei:
    (D) der Hydroxylamin-Beschleuniger in einer Menge vorhanden ist, die 0,5 bis 6 g/l Hydroxylamin stöchiometrisch äquivalent ist;
    (E) die Punkte der Gesamtsäure im Bereich von 16 bis 22 liegen und
    (F) die Punkte der freien Säure im Bereich von 0,0 bis 0,8 liegen.
  20. Zusammensetzung nach Anspruch 18 oder Anspruch 19, wobei:
    (B) die Konzentration der gelösten Zn2+-Ionen im Bereich von 0,60 bis 0,95 g/l liegt.
  21. Zusammensetzung nach einem der Ansprüche 17 bis 20, wobei:
    (A) die Konzentration der gelösten Phosphationen im Bereich von 13 bis 18 g/l liegt;
    (B) die Konzentration der gelösten Zn2+-Ionen im Bereich von 0,71 bis 0,87 g/l liegt;
    (D) der Hydroxylamin-Beschleuniger Hydroxylaminsulfat ist, das in einer Menge vorhanden ist, die 0,5 bis 2 g/l Hydroxylamin stöchiometrisch äquivalent ist; und
    (E) die Punkte der Gesamtsäure im Bereich von 18 bis 21 liegen.
  22. Verfahren zur Bildung einer Phosphatbeschichtung auf der Oberfläche eines Metallsubstrats, wobei die Oberfläche des Substrats mit einer Zusammensetzung nach einem der vorhergehenden Ansprüche für einen Zeitraum im Bereich von 5 s bis 15 min bei einer Temperatur im Bereich von 21 °C bis 85 °C in Berührung gebracht wird, so daß die hinzukommende Masse der gebildeten Phosphatbeschichtung im Bereich von 1,1 bis 5,4 g/m2 liegt und der Gewichtsprozentwert des Kupfers in der gebildeten Phosphatbeschichtung im Bereich von 0,50 bis 10,0 % liegt.
  23. Verfahren nach Anspruch 22, wobei die Oberfläche des Substrats mit der Zusammensetzung für einen Zeitraum von 15 s bis 10 min bei einer Temperatur im Bereich von 25 °C bis 55 °C in Berührung gebracht wird, so daß der Gewichtsprozentwert des Kupfers in der gebildeten Phosphat-beschichtung im Bereich von 1,0 bis 8,0 % liegt.
  24. Verfahren nach Anspruch 22 oder Anspruch 23, durchgeführt auf der Oberfläche eines Metallsubstrats, das Aluminium als Teil seiner Oberfläche nicht umfaßt, wobei die Oberfläche mit einer Zusammensetzung in Berührung gebracht wird, die einen Wert für Punkte der freien Säure im Bereich von 0,0 bis 0,8 aufweist, für einen Zeitraum im Bereich von 30 s bis 5 min bei einer Temperatur im Bereich von 40 °C bis 55 °C, so daß die hinzukommende Masse der gebildeten Phosphat-Beschichtung im Bereich von 1,6 bis 4,3 g/m2 liegt und der Gewichtsprozentwert des Kupfers in der gebildeten Phosphatbeschichtung im Bereich von 2,0 bis 6,0 % liegt.
  25. Verfahren nach Anspruch 24, wobei die Zusammensetzung einen Wert für die Punkte der freien Säure im Bereich von 0,35 bis 0,65 aufweist.
  26. Verfahren nach Anspruch 24 oder Anspruch 25, wobei die aluminiumfreie Oberfläche mit der Zusammensetzung für einen Zeitraum im Bereich von 90 s bis 120 s bei einer Temperatur im Bereich von 40 °C bis 44 °C in Berührung gebracht wird, so daß die hinzukommende Masse der gebildeten Phosphatbeschichtung im Bereich von 2,2 bis 3,8 g/m2 liegt und der Gewichtsprozentwert von Kupfer in der gebildeten Phosphatbeschichtung im Bereich von 3,0 bis 4,1 % liegt.
  27. Verfahren nach Anspruch 22 oder Anspruch 23, durchgeführt auf der Oberfläche eines Metallsubstrats, das Aluminium als Teil seiner Oberfläche umfaßt, wobei die Oberfläche mit einer Zusammensetzung, die einen Wert für die Punkte freier Säure im Bereich von -0,5 bis 0,0 aufweist, für einen Zeitraum im Bereich von 30 s bis 5 min bei einer Temperatur im Bereich von 25 °C bis 55 °C in Berührung gebracht wird, so daß die hinzukommende Masse der gebildeten Phosphatbeschichtung im Bereich von 1,6 bis 4,3 g/m2 liegt und der Gewichtsprozentwert von Kupfer in der gebildeten Phosphatbeschichtung im Bereich von 2,0 bis 6,0 % liegt.
  28. Verfahren nach Anspruch 27, wobei die Zusammensetzung einen Wert für die Punkte freier Säure im Bereich von -0,5 bis -0,2 aufweist.
  29. Verfahren nach Anspruch 27 oder Anspruch 28, wobei die Oberfläche für einen Zeitraum im Bereich von 90 s bis 120 s bei einer Temperatur im Bereich von 31 °C bis 44 °C mit der Zusammensetzung in Berührung gebracht wird, so daß die hinzukommende Masse der gebildeten Phosphat-beschichtung im Bereich von 2,2 bis 3,8 g/m2 liegt und der Gewichtsprozentwert von Kupfer in der gebildeten Phosphatbeschichtung im Bereich von 3,0 bis 4,1 % liegt.
  30. Verfahren nach einem der Ansprüche 22 bis 29, umfassend die vorbereitenden Schritte des:
    (1) Reinigens der Oberfläche und
    (2) In-Berührung-Bringens der gereinigten Oberfläche mit einer kolloidales Titan enthaltenden Aktivierungs-Zusammensetzung, gefolgt vom beschichtungsbildenden Schritt des:
    (3) Bildens einer Phosphatbeschichtung auf der gereinigten und aktivierten Oberfläche durch das in einem der Ansprüche 21 bis 28 beanspruchte Verfahren; und danach gefolgt vom letzten Schritt des:
    (4) Auftragens einer äußeren, festen Beschichtung auf Basis organischer Verbindungen auf die im Schritt (3) oben gebildete Phosphatbeschichtung.
EP94904428A 1992-12-22 1993-12-15 Im wesentlichen nickelfreier phosphatkonversionsüberzug-zusammensetzung und verfahren Expired - Lifetime EP0675972B1 (de)

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US99546592A 1992-12-22 1992-12-22
PCT/US1993/012044 WO1994014999A1 (en) 1992-12-22 1993-12-15 Substantially nickel-free phosphate conversion coating composition and process
US995465 1997-10-06

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EP0675972A4 EP0675972A4 (de) 1995-11-02
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DE4440300A1 (de) * 1994-11-11 1996-05-15 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen
DE19511573A1 (de) * 1995-03-29 1996-10-02 Henkel Kgaa Verfahren zur Phosphatierung mit metallhaltiger Nachspülung
DE19538778A1 (de) * 1995-10-18 1997-04-24 Henkel Kgaa Schichtgewichtssteuerung bei Hydroxylamin-beschleunigten Phosphatiersystemen
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
DE19740953A1 (de) * 1997-09-17 1999-03-18 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
DE10320313B4 (de) * 2003-05-06 2005-08-11 Chemetall Gmbh Verfahren zum Beschichten von metallischen Körpern mit einer Phosphatierungslösung, Phosphatierungslösung und die Verwendung des beschichteten Gegenstandes
WO2006071226A1 (en) * 2004-12-28 2006-07-06 Henkel Kommanditgesellschaft Auf Aktien Iron phosphating process that reduces laser scale resulting in improved paint adhesion
DE102006052919A1 (de) * 2006-11-08 2008-05-15 Henkel Kgaa Zr-/Ti-haltige Phosphatierlösung zur Passivierung von Metallverbundoberflächen
CN103924226B (zh) * 2014-04-25 2016-06-15 山东大学 一种分级结构磷酸锌化学转化膜的制备方法
CN104032293B (zh) * 2014-06-11 2016-02-17 安徽江南机械有限责任公司 一种不含镍单组分高耐蚀性环保黑色磷化液
WO2024149790A1 (en) * 2023-01-11 2024-07-18 Chemetall Gmbh Composition for phosphatizing of ferrous surfaces and method making use thereof

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BR9307702A (pt) 1999-08-31
SG55084A1 (en) 1998-12-21
CN1090606A (zh) 1994-08-10
ZA939636B (en) 1994-08-15
ES2136726T3 (es) 1999-12-01
EP0675972A4 (de) 1995-11-02
ATE183247T1 (de) 1999-08-15
CZ287997B6 (cs) 2001-03-14
PL309404A1 (en) 1995-10-02
AU5848194A (en) 1994-07-19
CZ164995A3 (en) 1996-01-17
CN1092245C (zh) 2002-10-09
CA2150545A1 (en) 1994-07-07
EP0675972A1 (de) 1995-10-11
DE69326021T2 (de) 1999-12-23
JPH08504890A (ja) 1996-05-28
DE69326021D1 (de) 1999-09-16

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