EP1155163B1 - Method for phosphatizing zinc or aluminium surfaces - Google Patents

Method for phosphatizing zinc or aluminium surfaces Download PDF

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Publication number
EP1155163B1
EP1155163B1 EP00905014A EP00905014A EP1155163B1 EP 1155163 B1 EP1155163 B1 EP 1155163B1 EP 00905014 A EP00905014 A EP 00905014A EP 00905014 A EP00905014 A EP 00905014A EP 1155163 B1 EP1155163 B1 EP 1155163B1
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EP
European Patent Office
Prior art keywords
phosphating
zinc
phosphating solution
hydroxylamine
phosphate
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EP00905014A
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German (de)
French (fr)
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EP1155163A1 (en
Inventor
Thomas Nitschke
Werner Rentsch
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Chemetall GmbH
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Chemetall GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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 invention relates to a method for phosphating zinc or Aluminum surfaces with a phosphating solution based on zinc and nickel as cations and hydroxylamine as accelerators, which additionally Can contain fluoride and / or complex-bound fluoride.
  • the zinc surfaces are part of workpieces made of zinc or Zinc alloys exist, or they are made by hot dip galvanizing or by electrolytic galvanizing on workpieces containing iron, especially on Workpieces made of iron and steel, applied.
  • the aluminum surfaces are Part of workpieces made of aluminum or aluminum alloys consist. Can on the phosphated zinc and aluminum surfaces Varnishes, paints, plastic layers or oils are applied, and with surfaces provided with such an order are provided by the Phosphating much better protected against corrosion.
  • EP-A 0 315 059 discloses a process for phosphating surfaces made of iron, which works with a phosphating solution which contains 0.5 to 50 g / l hydroxylamine and 0.2 to 2.0 g / l Zn 2+ and 3 contains up to 25 g / l phosphate.
  • the phosphating solution can additionally contain iron, manganese, nickel, nitrate, fluoride and / or complex fluorides.
  • the known method is suitable not only for phosphating surfaces made of iron, but also surfaces made of zinc, zinc alloys, aluminum and aluminum alloys. This method has the disadvantage that it works with higher hydroxylamine concentrations which are equal to or> 0.5 g / l, because hydroxylamine is relatively expensive and comparatively unstable.
  • DE-A 195 38 778 describes a method for phosphating surfaces made of steel, galvanized steel, alloy galvanized steel and aluminum known in which the metal surface for a period between 1 and 8 Minutes in a phosphating solution containing 0.5 to 2 g / l zinc ions, 2 up to 25 g / l phosphate ions and 1.2 to 5 g / l hydroxylamine in free, ionic or contains complex bound form, a free acid content between 0 and 1.5 points and has a temperature in the range of 32 to 93 ° C.
  • This phosphating solution can additionally contain 0.2 to 1.5 g / l of manganese ions, 0.2 up to 1.5 g / l nickel ions and additional fluoride in free and / or complex bound form in amounts up to 2.5 g / l total fluoride. Finally the phosphating solution should not contain more than 0.5 g / l nitrate ions. Also this process works with relatively high hydroxylamine concentrations and limits the nitrate content to less than 0.5 g / l.
  • DE-A 196 06 018 describes a process for phosphating Metal surfaces made of steel, galvanized or alloy galvanized steel and / or aluminum, in which the metal surfaces are sprayed or Dive for a time between 3 seconds and 8 minutes with a zinc-containing one Phosphating solution in contact that contains 0.2 to 3 g / l zinc ions, 3 to 50 g / l Phosphate ions, 1 to 100 mg / l nickel ions, one or more accelerators, z. B. 0.01 to 0.2 g / l nitrite and 0.1 to 10 g / l hydroxylamine, wherein the The nitrate content of this solution is ⁇ 0.5 g / l.
  • the solution can additionally 0.1 to 4 g / l Manganese ions and up to 2.5 g / l total fluoride.
  • the in DE-A 196 Examples given in 06 018 show that the known method with comparatively high hydroxylamine concentrations (1.7 g / l Hydroxylammoniumsulfat) works and avoids a nitrate content.
  • DE-A 196 21 184 discloses a method for phosphating Metal surfaces made of steel, galvanized or alloy galvanized steel, Aluminum and / or aluminum-magnesium alloys, in which the Metal surfaces by spraying or dipping for a time between 3 Seconds and 8 minutes in contact with a zinc-containing phosphating solution brings the 0.2 to 3 g / l zinc ions, 3 to 50 g / l phosphate ions, 0.001 to 4 g / l Manganese ions, 0.001 to 0.5 g / l of one or more polymers and one or several accelerators, e.g. B.
  • phosphating solution used has a nitrate content that is not 0.5 g / l exceeds.
  • DE-A 197 05 701 describes a process for the phosphating of Surfaces made of steel, galvanized steel and / or aluminum and / or Alloys containing at least 50% by weight of iron, zinc or aluminum exist, with a zinc-containing acid phosphating solution works, which is free of copper ions and the 0.3 to 3 g / l zinc ions, 0.001 to 0.1 g / l nickel ions, 5 to 40 g / l phosphate ions and at least one accelerator, z. B. 0.1 to 10 g / l hydroxylamine. contains. This solution can additionally up to 4 g / l manganese ions and up to 2.5 g / l total fluoride.
  • a phosphating solution is known from WO 93/03 198 which is used for Phosphating of steel, zinc alloys and aluminum is used and the 5 to 25 g / l phosphate ions, 0.5 to 2 g / l zinc ions, 0.2 to 1.5 g / l Nickel ions, 0.2 to 1.5 g / l of manganese ions and 1 to 2.5 g / l of a hydroxylamine compound, Contains 0 to 1.5 g / l fluoride and 0 to 2 g / l nitrate.
  • This too Phosphating solution contains a large amount of hydroxylamine and limited the nitrate content to 2 g / l.
  • DE-A 196 39 596 discloses a process for phosphating Steel band or galvanized on one or both sides or galvanized alloy Steel strip by spray or dip treatment for a period of time in the area from 2 to 15 seconds at a temperature of 40 to 70 ° C with a Phosphating solution containing 1 to 4 g / l zinc ions, 0.8 to 3.5 g / l manganese ions, 10 to 30 g / l phosphate ions, 0.1 to 3 g / l hydroxylamine and not more than 1 g / l Contains nitrate ions and the free acid content in the range of 0.4 to 4 Has points.
  • This phosphating solution can additionally 0.8 to 3.5 g / l Contain nickel ions and up to 0.8 g / l total fluoride. If the Phosphating solution used in the phosphating of galvanized steel their nitrate content should not exceed 0.1 g / l.
  • the prior art gives the skilled worker the knowledge that the Hydroxylamine accelerator can also be used alone and then in the Usually is particularly effective if it is in the phosphating solution in a Concentration> 0.5 g / l is present.
  • the state of the art also conveys this Expert the knowledge that the nitrate concentration of Phosphating solution should generally be ⁇ 1 g / l, namely especially when the phosphating solution for phosphating Zinc surfaces are used because in this case the nitrate content should be even ⁇ 0.5 g / l, since the person skilled in the art assumes that higher nitrate contents the formation of the very disadvantageous, so-called Favor "specks".
  • nitrates of zinc, nickel and manganese are readily water-soluble and can be easily procured and handled easily, and the Free acid content (FS) can optionally be obtained in a simple manner Nitric acid can be adjusted.
  • the invention is therefore based on the object of a phosphating process to create that for phosphating zinc and aluminum surfaces is suitable for the workpieces to be phosphated, especially if they are after phosphating with varnishes, paints, plastic layers or oils coated, gives good corrosion properties and one Phosphating solution used compared to the known All in all, hydroxylamine-containing phosphating solutions are cheaper works without the quality of the phosphate layers produced, for example by the formation of specks on zinc surfaces or by not closed layers on aluminum surfaces, is reduced.
  • the object on which the invention is based is achieved by creating a method for phosphating zinc or aluminum surfaces by means of a phosphating solution which contains 0.5 to 2.0 g / l of Zn 2+ , 0.3 to 2.0 g / l of Ni 2+ , 0.1 to 0.3 g / l NH 2 OH, at least 3.0 g / l NO 3 - and 10.0 to 20.0 g / l phosphate (calculated as P 2 O 5 ) and the is applied to the surfaces by dipping or spraying at 35 to 75 ° C., the dipping time being 0.5 to 10 minutes and the spraying time being 3 seconds to 5 minutes.
  • the zinc surfaces phosphated according to the invention have no disadvantageous specks, although the phosphating solution used according to the invention has a high nitrate content of> 3 g / l, and that the phosphate layers produced on aluminum surfaces are completely closed, which is particularly due to the beneficial effect of the high nitrate content is attributed.
  • the phosphate layers produced by the process according to the invention give the workpieces in particular, which are coated with lacquers, paints, plastic layers or oils after phosphating, very good corrosion protection.
  • the phosphating solution used to carry out the method according to the invention additionally contains 0.4 to 1.5 g / l Mn 2+ .
  • the manganese content improves the positive corrosion protection effect of zinc phosphate layers in a known manner.
  • the phosphating of zinc surfaces is carried out in accordance with the method according to the invention with a phosphating solution which does not necessarily contain fluoride and complex-bound fluoride
  • the phosphating of aluminum surfaces is carried out with a phosphating solution which contains fluoride and / or complex-bound fluoride
  • the complex-bound fluoride for example in the form of SiF 6 2- or BF 4 - can be used.
  • SiF 6 2- is particularly suitable as a complex-bound fluoride for carrying out the process according to the invention and that a certain range must be observed with regard to the content of fluoride and complex-bound fluoride.
  • the phosphating solution used to carry out the process according to the invention additionally contains 0.2 to 1.5 g / l F - and / or 0.5 to 2.5 g / l SiF 6 2- .
  • the presence of such amounts of simple and / or complex-bound fluoride is advantageous in the phosphating of aluminum surfaces, since the aforementioned fluorides have a positive influence on the quality of the phosphate layers deposited on aluminum surfaces.
  • the simple fluoride F - can be in the form of hydrofluoric acid HF or its salts.
  • the zinc content is preferably 0.5 to 1.7 g / l.
  • the phosphating solution used for dipping contains 1 to 2 g / l Zn 2+ and the phosphating solution used for spraying contains 0.5 to 1.5 g / l Zn 2+ .
  • the method according to the invention produces particularly good results when the phosphating solution contains 3 to 15 g / l NO 3 - .
  • a phosphating solution which, in addition to the components already mentioned, preferably 0.5 to 1.3 g / l Ni 2+ , 12 to 16 g / l phosphate (calculated as P 2 O 5 ), 0, Contains 5 to 1.3 g / l Mn 2+ and 0.2 to 1.0 g / l F - and / or 0.8 to 2.0 g / l SiF 6 2- .
  • Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating solution or the concentrate of this solution, it will largely be present as hydroxylammonium ion due to the acidic nature of these solutions. When using hydroxylammonium salts, the sulfates and phosphates are particularly suitable. The hydroxylamine content is preferably up to 0.3 g / l.
  • the nitrate can be added to the phosphating solution as HNO 3 or as the nitrate of zinc, manganese and / or nickel.
  • Zinc, manganese and nickel can also be used in the form of their oxides and / or carbonates for the preparation of the phosphating solution.
  • the phosphate is used as phosphoric acid or in the form of soluble phosphates.
  • SiF 6 2- is z. B. used as H 2 SiF 6 for the preparation of the phosphating solution.
  • the phosphating solution can contain alkali metal and / or ammonium cations in order to adjust the free acid (FS) content, which is in the range from 0.5 to 3.5 points in the process according to the invention ,
  • free acid is in the field of phosphating commonly used.
  • the free acid score is the number of ml that results if 10 ml of phosphating solution, which has been reduced to 50 ml were diluted with 0.1 normal sodium hydroxide solution up to a pH of 4.2 be titrated, the sample to be titrated then KCI until saturation is added if there is complex-bound fluoride in the sample, to avoid dissociation as much as possible.
  • Sheet metal used made of electrolytically galvanized steel and made of the alloy AlMgSi (AA6016) passed.
  • the sheets were first cleaned, being were immersed in an aqueous solution at 60 ° C for 10 minutes, the 20 g / l of the alkaline cleaner BONDER V 854 / 5M contained. Then were the sheets are rinsed with tap water by immersion. Then there was a Activation by treating the sheets with an aqueous solution that is 1.0 g / l contained the titanium phosphate-containing activating agent GARDOLENE V 6513. The activation was carried out by immersing the sheets for 30 seconds.
  • the Cleaning and activation are well known and known in phosphating common procedural steps. BONDER and GARDOLENE are registered trademarks of Chemetall GmbH, Frankfurt am Main.

Abstract

The invention relates to a method for phosphatizing zinc or aluminium surfaces with a phosphatizing solution containing 0.5 to 2.0 g/l Zn<2+>, 0.3 to 2.0 g/l Ni<2+>, 0.1 to 0.4 g/l NH2OH, at least 3.0 g/l NO3<-> and 10.0 to 20.0 g/l phosphate (calculated as P2O5). Said solution is applied to the surfaces by immersion or spraying at 35 to 75 DEG C, the immersion time being 0.5 to 10 minutes and the spraying time being 3 seconds to 5 minutes.

Description

Die Erfindung betrifft ein Verfahren zur Phosphatierung von Zink- oder Aluminiumoberflächen mit einer Phosphatierungslösung auf der Basis von Zink und Nickel als Kationen und Hydroxylamin als Beschleuniger, die zusätzlich Fluorid und/oder komplex gebundenes Fluorid enthalten kann.The invention relates to a method for phosphating zinc or Aluminum surfaces with a phosphating solution based on zinc and nickel as cations and hydroxylamine as accelerators, which additionally Can contain fluoride and / or complex-bound fluoride.

Die Zinkoberflächen sind Bestandteil von Werkstücken, die aus Zink oder Zinklegierungen bestehen, oder sie werden durch Feuerverzinkung oder durch elektrolytische Verzinkung auf eisenhaltige Werkstücke, insbesondere auf Werkstücke aus Eisen und Stahl, aufgebracht. Die Aluminiumoberflächen sind Bestandteil von Werkstücken, die aus Aluminium oder Aluminiumlegierungen bestehen. Auf die phosphatierten Zink- und Aluminiumoberflächen können Lacke, Anstriche, Kunststoffschichten oder Öle aufgetragen werden, und die mit einem derartigen Auftrag versehenen Oberflächen werden durch die Phosphatierung erheblich besser vor Korrosion geschützt.The zinc surfaces are part of workpieces made of zinc or Zinc alloys exist, or they are made by hot dip galvanizing or by electrolytic galvanizing on workpieces containing iron, especially on Workpieces made of iron and steel, applied. The aluminum surfaces are Part of workpieces made of aluminum or aluminum alloys consist. Can on the phosphated zinc and aluminum surfaces Varnishes, paints, plastic layers or oils are applied, and with surfaces provided with such an order are provided by the Phosphating much better protected against corrosion.

Seit einigen Jahren sind Verfahren zur Phosphatierung metallischer Werkstoffe bekannt, die mit einer Phosphatierungslösung arbeiten, welche als Beschleuniger Hydroxylamin enthält. So offenbart die EP-A 0 315 059 ein Verfahren zur Phosphatierung von Oberflächen aus Eisen, das mit einer Phosphatierungslösung arbeitet, die 0,5 bis 50 g/l Hydroxylamin und 0,2 bis 2,0 g/l Zn2+ sowie 3 bis 25 g/l Phosphat enthält. Die Phosphatierungslösung kann zusätzlich Eisen, Mangan, Nickel, Nitrat, Fluorid und/oder komplexe Fluoride enthalten. Das bekannte Verfahren eignet sich nicht nur zur Phosphatierung von Oberflächen aus Eisen, sondern auch von Oberflächen aus Zink, Zinklegierungen, Aluminium und Aluminiumlegierungen. Dieses Verfahren hat den Nachteil, daß es mit höheren Hydroxylamin-Konzentrationen arbeitet, die gleich oder > 0,5 g/l sind, denn Hydroxylamin ist relativ teuer und vergleichsweise instabil. Processes for phosphating metallic materials have been known for some years, which work with a phosphating solution which contains hydroxylamine as an accelerator. For example, EP-A 0 315 059 discloses a process for phosphating surfaces made of iron, which works with a phosphating solution which contains 0.5 to 50 g / l hydroxylamine and 0.2 to 2.0 g / l Zn 2+ and 3 contains up to 25 g / l phosphate. The phosphating solution can additionally contain iron, manganese, nickel, nitrate, fluoride and / or complex fluorides. The known method is suitable not only for phosphating surfaces made of iron, but also surfaces made of zinc, zinc alloys, aluminum and aluminum alloys. This method has the disadvantage that it works with higher hydroxylamine concentrations which are equal to or> 0.5 g / l, because hydroxylamine is relatively expensive and comparatively unstable.

Aus der DE-A 195 38 778 ist ein Verfahren zur Phosphatierung von Oberflächen aus Stahl, verzinktem Stahl, legierungsverzinktem Stahl sowie aus Aluminium bekannt, bei dem die Metalloberfläche für eine Zeitdauer zwischen 1 und 8 Minuten in eine Phosphatierungslösung eintaucht, die 0,5 bis 2 g/l Zinkionen, 2 bis 25 g/l Phosphationen und 1,2 bis 5 g/l Hydroxylamin in freier, ionischer oder komplex gebundener Form enthält, einen Gehalt an freier Säure zwischen 0 und 1,5 Punkten hat und eine Temperatur im Bereich von 32 bis 93°C aufweist. Diese Phosphatierungslösung kann zusätzlich 0,2 bis 1,5 g/l Manganionen, 0,2 bis 1,5 g/l Nickelionen sowie zusätzlich Fluorid in freier und/oder komplex gebundener Form in Mengen bis zu 2,5 g/l Gesamt-Fluorid enthalten. Schließlich soll die Phosphatierungslösung nicht mehr als 0,5 g/l Nitrationen enthalten. Auch dieses Verfahren arbeitet mit relativ hohen Hydroxylamin-Konzentrationen und begrenzt den Nitratgehalt auf weniger als 0,5 g/l.DE-A 195 38 778 describes a method for phosphating surfaces made of steel, galvanized steel, alloy galvanized steel and aluminum known in which the metal surface for a period between 1 and 8 Minutes in a phosphating solution containing 0.5 to 2 g / l zinc ions, 2 up to 25 g / l phosphate ions and 1.2 to 5 g / l hydroxylamine in free, ionic or contains complex bound form, a free acid content between 0 and 1.5 points and has a temperature in the range of 32 to 93 ° C. This phosphating solution can additionally contain 0.2 to 1.5 g / l of manganese ions, 0.2 up to 1.5 g / l nickel ions and additional fluoride in free and / or complex bound form in amounts up to 2.5 g / l total fluoride. Finally the phosphating solution should not contain more than 0.5 g / l nitrate ions. Also this process works with relatively high hydroxylamine concentrations and limits the nitrate content to less than 0.5 g / l.

Die DE-A 196 06 018 beschreibt ein Verfahren zum Phosphatieren von Metalloberflächen aus Stahl, verzinktem oder legierungsverzinktem Stahl und/oder aus Aluminium, bei dem man die Metalloberflächen durch Spritzen oder Tauchen für eine Zeit zwischen 3 Sekunden und 8 Minuten mit einer zinkhaltigen Phosphatierlösung in Berührung bringt, die 0,2 bis 3 g/l Zinkionen, 3 bis 50 g/l Phosphationen, 1 bis 100 mg/l Nickelionen, einen oder mehrere Beschleuniger, z. B. 0,01 bis 0,2 g/l Nitrit und 0,1 bis 10 g/l Hydroxylamin, enthält, wobei der Nitratgehalt dieser Lösung < 0,5 g/l ist. Die Lösung kann zusätzlich 0,1 bis 4 g/l Manganionen sowie bis zu 2,5 g/l Gesamt-Fluorid enthalten. Die in der DE-A 196 06 018 angegebenen Ausführungsbeispiele zeigen, daß das bekannte Verfahren mit vergleichsweise hohen Hydroxylamin-Konzentrationen (1,7 g/l Hydroxylammoniumsulfat) arbeitet und einen Nitratgehalt vermeidet.DE-A 196 06 018 describes a process for phosphating Metal surfaces made of steel, galvanized or alloy galvanized steel and / or aluminum, in which the metal surfaces are sprayed or Dive for a time between 3 seconds and 8 minutes with a zinc-containing one Phosphating solution in contact that contains 0.2 to 3 g / l zinc ions, 3 to 50 g / l Phosphate ions, 1 to 100 mg / l nickel ions, one or more accelerators, z. B. 0.01 to 0.2 g / l nitrite and 0.1 to 10 g / l hydroxylamine, wherein the The nitrate content of this solution is <0.5 g / l. The solution can additionally 0.1 to 4 g / l Manganese ions and up to 2.5 g / l total fluoride. The in DE-A 196 Examples given in 06 018 show that the known method with comparatively high hydroxylamine concentrations (1.7 g / l Hydroxylammoniumsulfat) works and avoids a nitrate content.

Die DE-A 196 21 184 offenbart ein Verfahren zum Phosphatieren von Metalloberflächen aus Stahl, verzinktem oder legierungsverzinktem Stahl, Aluminium und/oder aus Aluminium-Magnesium-Legierungen, bei dem man die Metalloberflächen durch Spritzen oder Tauchen für eine Zeit zwischen 3 Sekunden und 8 Minuten mit einer zinkhaltigen Phosphatierlösung in Berührung bringt, die 0,2 bis 3 g/l Zinkionen, 3 bis 50 g/l Phosphationen, 0,001 bis 4 g/l Manganionen, 0,001 bis 0,5 g/l eines oder mehrerer Polymere und einen oder mehrere Beschleuniger, z. B. 0,01 bis 0,2 g/l Nitrit und 0,1 bis 10 g/l Hydroxylamin, enthält, wobei die Lösung zusätzlich 1 bis 50 mg/l Nickelionen und bis zu 2,5 g/l Gesamt-Fluorid enthalten kann. Auch die bei diesem Verfahren verwendete Phosphatierungslösung hat einen Nitratgehalt, der 0,5 g/l nicht übersteigt.DE-A 196 21 184 discloses a method for phosphating Metal surfaces made of steel, galvanized or alloy galvanized steel, Aluminum and / or aluminum-magnesium alloys, in which the Metal surfaces by spraying or dipping for a time between 3 Seconds and 8 minutes in contact with a zinc-containing phosphating solution brings the 0.2 to 3 g / l zinc ions, 3 to 50 g / l phosphate ions, 0.001 to 4 g / l Manganese ions, 0.001 to 0.5 g / l of one or more polymers and one or several accelerators, e.g. B. 0.01 to 0.2 g / l nitrite and 0.1 to 10 g / l Contains hydroxylamine, the solution additionally 1 to 50 mg / l nickel ions and can contain up to 2.5 g / l total fluoride. Even those with this procedure The phosphating solution used has a nitrate content that is not 0.5 g / l exceeds.

Die DE-A 197 05 701 beschreibt ein Verfahren zur Phosphatierung von Oberflächen aus Stahl, verzinktem Stahl und/oder Aluminium und/oder aus Legierungen, die zu mindestens 50 Gew.-% aus Eisen, Zink oder Aluminium bestehen, wobei man mit einer zinkhaltigen sauren Phosphatierungslösung arbeitet, die frei von Kupferionen ist und die 0,3 bis 3 g/l Zinkionen, 0,001 bis 0,1 g/l Nickelionen, 5 bis 40 g/l Phosphationen und mindestens einen Beschleuniger, z. B. 0,1 bis 10 g/l Hydroxylamin. enthält. Diese Lösung kann zusätzlich bis zu 4 g/l Manganionen und bis zu 2,5 g/l Gesamt-Fluorid enthalten. Aus den in der DE-A 197 05 701 angegebenen Ausführungsbeispielen geht hervor, daß das bekannte Verfahren mit relativ hohen Hydroxylamin-Konzentrationen (1,8 g/l Hydroxylammoniumsulfat) arbeitet, und außerdem ist in dieser Druckschrift gesagt, daß bei der Phosphatierung von verzinktem Stahl eine Nitratkonzentration von 0,5 g/l nicht überschritten werden sollte.DE-A 197 05 701 describes a process for the phosphating of Surfaces made of steel, galvanized steel and / or aluminum and / or Alloys containing at least 50% by weight of iron, zinc or aluminum exist, with a zinc-containing acid phosphating solution works, which is free of copper ions and the 0.3 to 3 g / l zinc ions, 0.001 to 0.1 g / l nickel ions, 5 to 40 g / l phosphate ions and at least one accelerator, z. B. 0.1 to 10 g / l hydroxylamine. contains. This solution can additionally up to 4 g / l manganese ions and up to 2.5 g / l total fluoride. From the in DE-A 197 05 701 specified embodiments shows that the known processes with relatively high hydroxylamine concentrations (1.8 g / l Hydroxylammoniumsulfat) works, and also in this publication said that in the phosphating of galvanized steel Nitrate concentration of 0.5 g / l should not be exceeded.

Aus der WO 93/03 198 ist eine Phosphatierungslösung bekannt, die zur Phosphatierung von Stahl, Zinklegierungen und Aluminium verwendet wird und die 5 bis 25 g/l Phosphationen, 0,5 bis 2 g/l Zinkionen, 0,2 bis 1,5 g/l Nickelionen, 0,2 bis 1,5 g/l Manganionen und 1 bis 2,5 g/l einer Hydroxylamin-Verbindung, 0 bis 1,5 g/l Fluorid und 0 bis 2 g/l Nitrat enthält. Auch diese Phosphatierungslösung enthält eine größere Menge Hydroxylamin und begrenzt den Nitratgehalt auf 2 g/l. A phosphating solution is known from WO 93/03 198 which is used for Phosphating of steel, zinc alloys and aluminum is used and the 5 to 25 g / l phosphate ions, 0.5 to 2 g / l zinc ions, 0.2 to 1.5 g / l Nickel ions, 0.2 to 1.5 g / l of manganese ions and 1 to 2.5 g / l of a hydroxylamine compound, Contains 0 to 1.5 g / l fluoride and 0 to 2 g / l nitrate. This too Phosphating solution contains a large amount of hydroxylamine and limited the nitrate content to 2 g / l.

Schließlich offenbart die DE-A 196 39 596 ein Verfahren zum Phosphatieren von Stahlband oder von ein- oder beidseitig verzinktem oder legierungsverzinktem Stahlband durch Spritz- oder Tauchbehandlung für eine Zeitdauer im Bereich von 2 bis 15 Sekunden bei einer Temperatur von 40 bis 70°C mit einer Phosphatierungslösung, die 1 bis 4 g/l Zinkionen, 0,8 bis 3,5 g/l Manganionen, 10 bis 30 g/l Phosphationen, 0,1 bis 3 g/l Hydroxylamin und nicht mehr als 1 g/l Nitrationen enthält und die einen Gehalt an freier Säure im Bereich von 0,4 bis 4 Punkten hat. Diese Phosphatierungslösung kann zusätzlich 0,8 bis 3,5 g/l Nickelionen sowie bis zu 0,8 g/l Gesamt-Fluorid enthalten. Wenn die Phosphatierungslösung bei der Phosphatierung von verzinktem Stahl verwendet wird, soll ihr Nitratgehalt nicht mehr als 0,1 g/l betragen.Finally, DE-A 196 39 596 discloses a process for phosphating Steel band or galvanized on one or both sides or galvanized alloy Steel strip by spray or dip treatment for a period of time in the area from 2 to 15 seconds at a temperature of 40 to 70 ° C with a Phosphating solution containing 1 to 4 g / l zinc ions, 0.8 to 3.5 g / l manganese ions, 10 to 30 g / l phosphate ions, 0.1 to 3 g / l hydroxylamine and not more than 1 g / l Contains nitrate ions and the free acid content in the range of 0.4 to 4 Has points. This phosphating solution can additionally 0.8 to 3.5 g / l Contain nickel ions and up to 0.8 g / l total fluoride. If the Phosphating solution used in the phosphating of galvanized steel their nitrate content should not exceed 0.1 g / l.

Der Stand der Technik vermittelt dem Fachmann die Erkenntnis, daß der Beschleuniger Hydroxylamin auch allein verwendet werden kann und dann in der Regel besonders gut wirksam ist, wenn er in der Phosphatierungslösung in einer Konzentration > 0,5 g/l vorliegt. Femer vermittelt der Stand der Technik dem Fachmann die Erkenntnis, daß die Nitratkonzentration der Phosphatierungslösung in der Regel < 1 g/l betragen sollte, und zwar insbesondere dann, wenn die Phosphatierungslösung zur Phosphatierung von Zinkoberflächen verwendet wird, denn in diesem Fall sollte der Nitratgehalt sogar < 0,5 g/l sein, da der Fachmann davon ausgeht, daß höhere Nitratgehalte auf verzinkten Oberflächen die Bildung der sehr nachteiligen, sogenannten "Stippen" begünstigen. Andererseits ist dem Fachmann bewußt, daß ein signifikanter Nitratgehalt in der Phosphatierungslösung durchaus vorteilhaft sein könnte, denn die Nitrate des Zinks, Nickels und Mangans sind gut wasserlöslich und können leicht beschafft sowie problemlos gehandhabt werden, und der Gehalt an freier Säure (FS) kann gegebenenfalls auf einfache Weise mittels Salpetersäure eingestellt werden.The prior art gives the skilled worker the knowledge that the Hydroxylamine accelerator can also be used alone and then in the Usually is particularly effective if it is in the phosphating solution in a Concentration> 0.5 g / l is present. The state of the art also conveys this Expert the knowledge that the nitrate concentration of Phosphating solution should generally be <1 g / l, namely especially when the phosphating solution for phosphating Zinc surfaces are used because in this case the nitrate content should be even <0.5 g / l, since the person skilled in the art assumes that higher nitrate contents the formation of the very disadvantageous, so-called Favor "specks". On the other hand, the skilled worker is aware that a significant nitrate content in the phosphating solution can be quite advantageous could, because the nitrates of zinc, nickel and manganese are readily water-soluble and can be easily procured and handled easily, and the Free acid content (FS) can optionally be obtained in a simple manner Nitric acid can be adjusted.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Phosphatierungsverfahren zu schaffen, das sich zur Phosphatierung von Zink- und Aluminiumoberflächen eignet, das den zu phosphatierenden Werkstücken, insbesondere wenn sie nach der Phosphatierung mit Lacken, Anstrichen, Kunststoffschichten oder Ölen beschichtet werden, gute Korrosionseigenschaften verleiht und das eine Phosphatierungslösung verwendet, die im Vergleich zu den bekannten hydroxylaminhaltigen Phosphatierungslösungen insgesamt kostengünstiger arbeitet, ohne daß die Qualität der erzeugten Phosphatschichten, zum Beispiel durch die Bildung von Stippen auf Zinkoberflächen oder durch nicht geschlossene Schichten auf Aluminiumoberflächen, vermindert wird.The invention is therefore based on the object of a phosphating process to create that for phosphating zinc and aluminum surfaces is suitable for the workpieces to be phosphated, especially if they are after phosphating with varnishes, paints, plastic layers or oils coated, gives good corrosion properties and one Phosphating solution used compared to the known All in all, hydroxylamine-containing phosphating solutions are cheaper works without the quality of the phosphate layers produced, for example by the formation of specks on zinc surfaces or by not closed layers on aluminum surfaces, is reduced.

Die der Erfindung zugrunde liegende Aufgabe wird durch die Schaffung eines Verfahrens zur Phosphatierung von Zink- oder Aluminiumoberflächen mittels einer Phosphatierungslösung gelöst, die 0,5 bis 2,0 g/l Zn2+, 0,3 bis 2,0 g/l Ni2+, 0,1 bis 0,3 g/l NH2OH, mindestens 3,0 g/l NO3 - und 10,0 bis 20,0 g/l Phosphat (berechnet als P2O5) enthält und die durch Tauchen oder Spritzen bei 35 bis 75°C auf die Oberflächen aufgebracht wird, wobei die Tauchzeit 0,5 bis 10 Minuten und die Spritzzeit 3 Sekunden bis 5 Minuten beträgt.The object on which the invention is based is achieved by creating a method for phosphating zinc or aluminum surfaces by means of a phosphating solution which contains 0.5 to 2.0 g / l of Zn 2+ , 0.3 to 2.0 g / l of Ni 2+ , 0.1 to 0.3 g / l NH 2 OH, at least 3.0 g / l NO 3 - and 10.0 to 20.0 g / l phosphate (calculated as P 2 O 5 ) and the is applied to the surfaces by dipping or spraying at 35 to 75 ° C., the dipping time being 0.5 to 10 minutes and the spraying time being 3 seconds to 5 minutes.

Mit dem erfindungsgemäßen Verfahren werden gleichmäßige, einwandfreie, feinkristalline, geschlossene Phosphatschichten mit einem Schichtgewicht von 2 bis 5 g/m2 erzeugt. In überraschender Weise wurde gefunden, daß die erfindungsgemäß phosphatierten Zinkoberflächen keine nachteiligen Stippen aufweisen, obwohl die entsprechend der Erfindung eingesetzte Phosphatierungslösung einen hohen Nitratgehalt von > 3 g/l aufweist, und daß auch die auf Aluminiumoberflächen erzeugten Phosphatschichten vollständig geschlossen sind, was insbesondere auf die vorteilhafte Wirkung des hohen Nitratgehalts zurückgeführt wird. Die nach dem erfindungsgemäßen Verfahren hergestellten Phosphatschichten verleihen insbesondere den Werkstücken, die nach der Phosphatierung mit Lacken, Anstrichen, Kunststoffschichten oder Ölen beschichtet werden, einen sehr guten Korrosionsschutz.With the method according to the invention, uniform, perfect, finely crystalline, closed phosphate layers with a layer weight of 2 to 5 g / m 2 are produced. Surprisingly, it was found that the zinc surfaces phosphated according to the invention have no disadvantageous specks, although the phosphating solution used according to the invention has a high nitrate content of> 3 g / l, and that the phosphate layers produced on aluminum surfaces are completely closed, which is particularly due to the beneficial effect of the high nitrate content is attributed. The phosphate layers produced by the process according to the invention give the workpieces in particular, which are coated with lacquers, paints, plastic layers or oils after phosphating, very good corrosion protection.

Durch den relevanten Stand der Technik zieht sich wie ein roter Faden das Vorurteil, daß der hohe Nitratgehalt einer Phosphatierungslösung für die nachteilige Stippenbildung auf phosphatierten Zinkoberflächen verantwortlich ist und daß daher der Nitratgehalt möglichst < 1 g/l, vorzugsweise < 0,5 g/l betragen muß (siehe z. B. DE-A 195 38 778, Seite 3, Zeilen 43 bis 49; DE-A 196 06 018, Seite 4, Zeilen 8 bis 11; DE-A 196 21 184, Seite 4, Zeilen 41 bis 44; DE-A 197 05 701, Seite 4, Zeilen 38 bis 43; DE-A 196 39 596, Seite 3, Zeilen 1 bis 7). Es ist das Verdienst der Erfindung, erkannt zu haben, daß zinkhaltige Phosphatierungslösungen, die einen Hydroxylamingehalt von nur 0,1 bis 0,3 g/l und einen Nitratgehalt von > 3 g/l aufweisen, vorteilhaft zur Phosphatierung von Zink- und Aluminiumoberflächen verwendet werden können, denn einerseits ist die Beschleunigungswirkung der sehr niedrigen Hydroxylamin-Konzentration wegen der synergistischen Beschleunigungswirkung des Nitrats völlig ausreichend, so daß die zur Durchführung des erfindungsgemäßen Verfahrens verwendete Phosphatierungslösung keinen weiteren Beschleuniger enthält, und andererseits führt die vergleichsweise hohe Nitratkonzentration bei Zinkoberflächen nicht zur nachteiligen Stippenbildung und unterstützt die Ausbildung einer geschlossenen Phosphatschicht auch auf Aluminiumoberflächen. Daraus folgt auch, daß Nitrate und gegebenenfalls Salpetersäure ohne weiteres zur Herstellung der Konzentrate verwendet werden können, aus denen durch Verdünnung die erfindungsgemäßen Phosphatierungslösungen hergestellt werden.Through the relevant state of the art, this is a common thread Prejudice that the high nitrate content of a phosphating solution for the disadvantageous speck formation on phosphated zinc surfaces is responsible and that the nitrate content should therefore be <1 g / l, preferably <0.5 g / l must (see e.g. DE-A 195 38 778, page 3, lines 43 to 49; DE-A 196 06 018, Page 4, lines 8 to 11; DE-A 196 21 184, page 4, lines 41 to 44; DE-A 197 05 701, page 4, lines 38 to 43; DE-A 196 39 596, page 3, lines 1 to 7). It is the merit of the invention to have recognized that zinc-containing Phosphating solutions that have a hydroxylamine content of only 0.1 to 0.3 g / l and have a nitrate content of> 3 g / l, advantageous for phosphating Zinc and aluminum surfaces can be used because on the one hand the accelerating effect of the very low hydroxylamine concentration because of the synergistic acceleration effect of the nitrate sufficient so that to carry out the method according to the invention used phosphating solution contains no further accelerator, and on the other hand, the comparatively high nitrate concentration contributes Zinc surfaces do not cause disadvantageous speck formation and support the Formation of a closed phosphate layer also on Aluminum surfaces. It also follows that nitrates and optionally Nitric acid can easily be used to prepare the concentrates can from which by dilution the invention Phosphating solutions are prepared.

Nach der Erfindung ist ferner vorgesehen, daß die zur Durchführung des erfindungsgemäßen Verfahrens verwendete Phosphatierungslösung zusätzlich 0,4 bis 1,5 g/l Mn2+ enthält. Der Mangangehalt verbessert in bekannter Weise die positive Korrosionsschutzwirkung von Zinkphosphatschichten.According to the invention it is further provided that the phosphating solution used to carry out the method according to the invention additionally contains 0.4 to 1.5 g / l Mn 2+ . The manganese content improves the positive corrosion protection effect of zinc phosphate layers in a known manner.

Während die Phosphatierung von Zinkoberflächen entsprechend dem erfindungsgemäßen Verfahren mit einer Phosphatierungslösung erfolgt, die Fluorid und komplex gebundenes Fluorid nicht zwingend enthält, wird die Phosphatierung von Aluminiumoberflächen mit einer Phosphatierungslösung durchgeführt, die Fluorid und/oder komplex gebundenes Fluorid beinhaltet, wobei das komplex gebundene Fluorid beispielsweise in Form von SiF6 2- oder BF4 - eingesetzt werden kann. Allerdings wurde gefunden, daß sich zur Durchführung des erfindungsgemäßen Verfahrens als komplex gebundenes Fluorid besonders das SiF6 2- eignet und daß bezüglich des Gehalts an Fluorid und komplex gebundenem Fluorid ein bestimmter Bereich einzuhalten ist. Daher ist nach der Erfindung vorgesehen, daß die zur Durchführung des erfindungsgemäßen Verfahrens verwendete Phosphatierungslösung zusätzlich 0,2 bis 1,5 g/l F- und/oder 0,5 bis 2,5 g/l SiF6 2- enthält. Die Anwesenheit solcher Mengen an einfachem und/oder komplex gebundenem Fluorid ist bei der Phosphatierung von Aluminiumoberflächen vorteilhaft, da die vorgenannten Fluoride die Qualität der auf Aluminiumoberflächen abgeschiedenen Phosphatschichten positiv beeinflussen. Das einfache Fluorid F- kann in Form der Flußsäure HF oder ihrer Salze vorliegen. Vorzugsweise liegt der Zinkgehalt bei 0,5 bis 1,7 g/l.While the phosphating of zinc surfaces is carried out in accordance with the method according to the invention with a phosphating solution which does not necessarily contain fluoride and complex-bound fluoride, the phosphating of aluminum surfaces is carried out with a phosphating solution which contains fluoride and / or complex-bound fluoride, the complex-bound fluoride for example in the form of SiF 6 2- or BF 4 - can be used. However, it was found that SiF 6 2- is particularly suitable as a complex-bound fluoride for carrying out the process according to the invention and that a certain range must be observed with regard to the content of fluoride and complex-bound fluoride. It is therefore provided according to the invention that the phosphating solution used to carry out the process according to the invention additionally contains 0.2 to 1.5 g / l F - and / or 0.5 to 2.5 g / l SiF 6 2- . The presence of such amounts of simple and / or complex-bound fluoride is advantageous in the phosphating of aluminum surfaces, since the aforementioned fluorides have a positive influence on the quality of the phosphate layers deposited on aluminum surfaces. The simple fluoride F - can be in the form of hydrofluoric acid HF or its salts. The zinc content is preferably 0.5 to 1.7 g / l.

Als besonders vorteilhaft hat es sich nach der Erfindung erwiesen, wenn die zum Tauchen verwendete Phosphatierungslösung 1 bis 2 g/l Zn2+ und die zum Spritzen verwendete Phosphatierungslösung 0,5 bis 1,5 g/l Zn2+ enthält. Das erfindungsgemäße Verfahren erbringt besonders gute Arbeitsergebnisse, wenn die Phosphatierungslösung 3 bis 15 g/l NO3 - enthält.It has proven particularly advantageous according to the invention if the phosphating solution used for dipping contains 1 to 2 g / l Zn 2+ and the phosphating solution used for spraying contains 0.5 to 1.5 g / l Zn 2+ . The method according to the invention produces particularly good results when the phosphating solution contains 3 to 15 g / l NO 3 - .

Schließlich wird das erfindungsgemäße Verfahren mit einer Phosphatierungslösung durchgeführt, die neben den bereits genannten Komponenten bevorzugt 0,5 bis 1,3 g/l Ni2+, 12 bis 16 g/l Phosphat (ber. als P2O5), 0,5 bis 1,3 g/l Mn2+ sowie 0,2 bis 1,0 g/l F- und/oder 0,8 bis 2,0 g/l SiF6 2- enthält.Finally, the process according to the invention is carried out with a phosphating solution which, in addition to the components already mentioned, preferably 0.5 to 1.3 g / l Ni 2+ , 12 to 16 g / l phosphate (calculated as P 2 O 5 ), 0, Contains 5 to 1.3 g / l Mn 2+ and 0.2 to 1.0 g / l F - and / or 0.8 to 2.0 g / l SiF 6 2- .

Hydroxylamin kann als freie Base, als Hydroxylaminkomplex oder in Form von Hydroxylammoniumsalzen eingesetzt werden. Wird der Phosphatierungslösung bzw. dem Konzentrat dieser Lösung freies Hydroxylamin zugefügt, wird es aufgrund des sauren Charakters dieser Lösungen weitgehend als Hydroxylammoniumion vorliegen. Bei einer Verwendung von Hydroxylammoniumsalzen sind die Sulfate und Phosphate besonders geeignet. Der Hydroxylamin-Gehalt beträgt vorzugsweise bis zu 0,3 g/l. Das Nitrat kann der Phosphatierungslösung als HNO3 oder als Nitrat des Zinks, Mangans und/oder des Nickels zugegeben werden. Zink, Mangan und Nickel können auch in Form ihrer Oxide und/oder Carbonate zur Herstellung der Phosphatierungslösung verwendet werden. Das Phosphat wird als Phosphorsäure oder in Form löslicher Phosphate eingesetzt. SiF6 2- wird z. B. als H2SiF6 zur Herstellung der Phosphatierungslösung verwendet. Außer den Kationen des Zinks, Nickels und Mangans kann die Phosphatierungslösung Alkalimetall- und/oder Ammonium-Kationen enthalten, um den Gehalt an freier Säure (FS) einzustellen, der beim erfindungsgemäßen Verfahren in einem Bereich von 0,5 bis 3,5 Punkten liegt.Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating solution or the concentrate of this solution, it will largely be present as hydroxylammonium ion due to the acidic nature of these solutions. When using hydroxylammonium salts, the sulfates and phosphates are particularly suitable. The hydroxylamine content is preferably up to 0.3 g / l. The nitrate can be added to the phosphating solution as HNO 3 or as the nitrate of zinc, manganese and / or nickel. Zinc, manganese and nickel can also be used in the form of their oxides and / or carbonates for the preparation of the phosphating solution. The phosphate is used as phosphoric acid or in the form of soluble phosphates. SiF 6 2- is z. B. used as H 2 SiF 6 for the preparation of the phosphating solution. In addition to the cations of zinc, nickel and manganese, the phosphating solution can contain alkali metal and / or ammonium cations in order to adjust the free acid (FS) content, which is in the range from 0.5 to 3.5 points in the process according to the invention ,

Der Begriff der "freien Säure" (FS) ist auf dem Gebiet der Phosphatierung allgemein gebräuchlich. Die Punktzahl der freien Säure ist die Anzahl an ml, die sich ergibt, wenn 10 ml Phosphatierlösung, die mit vollentsalztem Wasser auf 50 ml verdünnt wurden, mit 0,1-normaler Natronlauge bis zu einem pH-Wert von 4,2 titriert werden, wobei der zu titrierenden Probe dann KCI bis zur Sättigung hinzugefügt wird, wenn in der Probe komplex gebundenes Fluorid vorhanden ist, um dessen Dissoziation weitestgehend zu vermeiden.The term "free acid" (FS) is in the field of phosphating commonly used. The free acid score is the number of ml that results if 10 ml of phosphating solution, which has been reduced to 50 ml were diluted with 0.1 normal sodium hydroxide solution up to a pH of 4.2 be titrated, the sample to be titrated then KCI until saturation is added if there is complex-bound fluoride in the sample, to avoid dissociation as much as possible.

Der Gegenstand der Erfindung wird nachfolgend anhand von Vergleichs- und Ausführungsbeispielen näher erläutert. Zur Durchführung der Beispiele wurden Bleche verwendet, die aus elektrolytisch verzinktem Stahl und aus der Legierung AlMgSi (AA6016) bestanden. Die Bleche wurden zunächst gereinigt, wobei sie bei 60°C während 10 Minuten in eine wässrige Lösung getaucht wurden, die 20 g/l des alkalischen Reinigers BONDER V 854/5M enthielt. Anschließend wurden die Bleche durch Tauchen mit Leitungswasser gespült. Danach erfolgte eine Aktivierung durch Behandlung der Bleche mit einer wässrigen Lösung, die 1,0 g/l des titanphosphat- haltigen Aktivierungsmittels GARDOLENE V 6513 enthielt. Die Aktivierung erfolgte durch Tauchen der Bleche während 30 Sekunden. Die Reinigung und Aktivierung sind bei der Phosphatierung allgemein bekannte und gebräuchliche Verfahrensschritte. BONDER und GARDOLENE sind eingetragene Marken der Chemetall GmbH, Frankfurt am Main.The object of the invention is described below with reference to Embodiments explained in more detail. To carry out the examples Sheet metal used, made of electrolytically galvanized steel and made of the alloy AlMgSi (AA6016) passed. The sheets were first cleaned, being were immersed in an aqueous solution at 60 ° C for 10 minutes, the 20 g / l of the alkaline cleaner BONDER V 854 / 5M contained. Then were the sheets are rinsed with tap water by immersion. Then there was a Activation by treating the sheets with an aqueous solution that is 1.0 g / l contained the titanium phosphate-containing activating agent GARDOLENE V 6513. The activation was carried out by immersing the sheets for 30 seconds. The Cleaning and activation are well known and known in phosphating common procedural steps. BONDER and GARDOLENE are registered trademarks of Chemetall GmbH, Frankfurt am Main.

Die Bleche wurden dann durch Tauchen während 2,5 Minuten bei 55°C mit unterschiedlich zusammengesetzten Phosphatierungslösungen behandelt, anschließend durch Tauchen mit Leitungswasser gespült und danach mit Pressluft bei Raumtemperatur getrocknet. Die Tabelle 1 gibt die Zusammensetzung der verwendeten Phosphatierungslösungen sowie die bei der Phosphatierung erzielten Ergebnisse an. Bei den Beispielen 1 bis 4 handelt es sich um Vergleichsbeispiele, während die Beispiele 5 und 6 entsprechend dem erfindugsgemäßen Verfahren ausgeführt worden sind. Die Phosphatierungsergebnisse zeigen folgendes:

  • a) Die Vergleichsbeispiele 1 und 3, die - wie vom Stand der Technik empfohlen - einen geringen Nitratgehalt aufweisen, sind erwartungsgemäß stippenfrei, während das erfindungsgemäße Beispiel 5 in überraschender Weise stippenfrei ist. Bei den Beispielen 2,4 und 6 ist das Problem der Stippenbildung nicht relevant, da auf Al-Oberflächen ohnehin keine Stippen gebildet werden.
  • b) Die Vergleichsbeispiele 2 und 4 haben - obwohl sie nach dem Stand der Technik ausgeführt wurden - eine nicht geschlossene und damit eine unbrauchbare Phosphatschicht, da die Schicht nur 20% der Al-Oberfläche bedeckt; folglich konnte auch das Schichtgewicht nicht bestimmt werden. Das erfindungsgemäße Beispiel 6 hat eine geschlossene Phosphatschicht mit einem vorteilhaften Schichtgewicht, obwohl die Phosphatierungslösung nur einen geringen Hydroxylamingehalt und einen hohen Nitratgehalt hatte.
  • c) Das Vergleichsbeispiel 1 hat - da es in bekannter Weise einen hohen Hydroxylamingehalt und einen niedrigen Nitratgehalt verwendete - eine geschlossene Phosphatschicht mit vorteilhaftem Schichtgewicht. Allerdings weist die Phosphatschicht eine relativ dunkle Färbung auf. Dies ist dann nachteilig, wenn nach der Phosphatierung helle Einschichtlacke auf das Substrat aufgetragen werden sollen. Nachteilig ist auch, daß beim Vergleichsbeispiel 1 mit einem hohen Hydroxylamingehalt gearbeitet wird. Das Vergleichsbeispiel 3 hat zwar eine geschlossene Phosphatschicht, aber das Schichtgewicht ist zu hoch, obwohl die Phosphatierungslösung sowohl einen niedrigen Hydroxylamingehalt als auch einen niedrigen Nitratgehalt hatte. Außerdem hat die Phosphatschicht eine unerwünschte dunkelgraue Farbe. Das erfindungsgemäße Beispiel 5 hat eine geschlossene Phosphatschicht mit einem vorteilhaftem Schichtgewicht und ist in erwünschter Weise hellgrau gefärbt.
    • The sheets were then treated by dipping for 2.5 minutes at 55 ° C. with phosphating solutions of different compositions, then rinsed by dipping with tap water and then dried with compressed air at room temperature. Table 1 shows the composition of the phosphating solutions used and the results obtained in the phosphating. Examples 1 to 4 are comparative examples, while Examples 5 and 6 were carried out in accordance with the method according to the invention. The phosphating results show the following:
  • a) Comparative Examples 1 and 3, which - as recommended by the prior art - have a low nitrate content, are, as expected, free of specks, while Example 5 according to the invention is surprisingly free of specks. In Examples 2, 4 and 6, the problem of speck formation is not relevant since no specks are formed on Al surfaces anyway.
  • b) Comparative Examples 2 and 4 - although they were carried out according to the prior art - have a non-closed and therefore unusable phosphate layer, since the layer only covers 20% of the Al surface; consequently the layer weight could not be determined either. Example 6 according to the invention has a closed phosphate layer with an advantageous layer weight, although the phosphating solution had only a low hydroxylamine content and a high nitrate content.
  • c) Comparative Example 1 - since it used a high hydroxylamine content and a low nitrate content in a known manner - has a closed phosphate layer with an advantageous layer weight. However, the phosphate layer has a relatively dark color. This is disadvantageous if bright single-layer lacquers are to be applied to the substrate after phosphating. It is also disadvantageous that comparative example 1 uses a high hydroxylamine content. Comparative Example 3 has a closed phosphate layer, but the layer weight is too high, although the phosphating solution had both a low hydroxylamine content and a low nitrate content. In addition, the phosphate layer has an undesirable dark gray color. Example 5 according to the invention has a closed phosphate layer with an advantageous layer weight and is colored light gray in the desired manner.

    • Zur Herstellung der Phosphatierungslösungen, mit denen die erfindungsgemäßen Beispiele 5 und 6 ausgeführt worden sind, wurden jeweils 60 g der in Tabelle 2 angegebenen Konzentrate mit vollentsalztem Wasser auf 1 I aufgefüllt. Der Gehalt an freier Säure wurde in den Phosphatierungs- lösungen durch Zugabe von verdünnter Natronlauge eingestellt. Zur Herstellung der Konzentrate wurden in vorteilhafter Weise die Nitrate des Zinks, Nickels und Mangans verwendet. Phospathierungslösung
    (g/l)     Beispiele     1 2 3 4 5 6 Zn2+ 1,5 1,5 1,5 1,5 1,5 1,5 Ni2+ 1,0 1,0 1,0 1,0 1,0 1,0 Mn2+ 0,8 0,8 0,8 0,8 0,8 0,8 P2O5 14 14 14 14 14 14 F- -- 0,5 -- 0,5 -- 0,5 Si F6 2- -- 1,5 -- 1,5 -- 1,5 NO3 - 0,1 0,1 0,1 0,1 6,0 6,0 NH2OH 1,0 1,0 0,2 0,2 0,2 0,2 FS 1,9 1,9 1,9 1,9 2,0 2,0 Substrat Zn Al Zn Al Zn Al Schichtgewicht (g/m2) 3,3 nb 7,0 nb 3,5 4,3 Bedeckung % 100 20 100 20 100 100 Stippen -- -- -- -- -- -- Schichtfarbe dg nb dg nb hg nb dg = dunkelgrau, hg= hellgrau, nb = nicht bestimmbar     Bestandteil Konzentrat für Beispiel 5 (g) Beispiel 6 (g) H3PO4(65%P2O5) 358 358 ZnO 8,34 8,34 Ni(NO3)2.6H2O 82,7 82,7 Mn(NO3)2.4H2O 60,8 60,8 Zn(NO3)2.4H2O 73,2 73,2 H2SiF6(31%ig) -- 80,6 NH4HF2 -- 0,75 H2O, vollentsalzt 410,36 329,01 NH2OH(50%ig) 6,6 6,6 Summe 1000 1000     To prepare the phosphating solutions with which Examples 5 and 6 according to the invention were carried out, 60 g each of the concentrates given in Table 2 were made up to 1 liter with deionized water. The free acid content in the phosphating solutions was adjusted by adding dilute sodium hydroxide solution. The nitrates of zinc, nickel and manganese were advantageously used to prepare the concentrates. Phospathierungslösung
    (g / l)     Examples     1 2 3 4 5 6 Zn 2+ 1.5 1.5 1.5 1.5 1.5 1.5 Ni 2+ 1.0 1.0 1.0 1.0 1.0 1.0 Mn 2+ 0.8 0.8 0.8 0.8 0.8 0.8 P 2 O 5 14 14 14 14 14 14 F - - 0.5 - 0.5 - 0.5 Si F 6 2- - 1.5 - 1.5 - 1.5 NO 3 - 0.1 0.1 0.1 0.1 6.0 6.0 NH 2 OH 1.0 1.0 0.2 0.2 0.2 0.2 FS 1.9 1.9 1.9 1.9 2.0 2.0 substratum Zn al Zn al Zn al Layer weight (g / m 2 ) 3.3 nb 7.0 nb 3.5 4.3 Coverage% 100 20 100 20 100 100 dip - - - - - - coating color dg nb dg nb hg nb dg = dark gray, hg = light gray, nb = not determinable     component Concentrate for Example 5 (g) Example 6 (g) H 3 PO 4 (65% P 2 O 5 ) 358 358 ZnO 8.34 8.34 Ni (NO 3 ) 2 .6H 2 O 82.7 82.7 Mn (NO 3) 2 .4H 2 O 60.8 60.8 Zn (NO 3 ) 2 .4H 2 O 73.2 73.2 H 2 SiF 6 (31%) - 80.6 NH 4 HF 2 - 0.75 H 2 O, fully desalinated 410.36 329.01 NH 2 OH (50%) 6.6 6.6 total 1000 1000

    Claims (9)

    1. Method for phosphating zinc surfaces or aluminium surfaces with a phosphating solution which is based on zinc and nickel as cations and hydroxylamine as an accelerator and may contain in addition fluoride and/or complexed fluoride, characterised in that the phosphating solution contains 0.5 to 2.0 g/l Zn2+, 0.3 to 2.0 g/l Ni2+, 0.1 to 0.3 g/l NH2OH, at least 3.0 g/l NO3 - and 10.0 to 20.0 g/l phosphate (calculated as P2O5) and is applied to the surfaces by immersion or spraying at 35°C to 75°C, the immersion time being 0.5 to 10 minutes and the spraying time being 3 seconds to 5 minutes.
    2. Method according to claim 1, characterised in that the phosphating solution contains in addition 0.4 to 1.5 g/l Mn2+.
    3. Method according to claim 1, characterised in that the phosphating solution contains in addition 0.2 to 1.5 g/l F- and/or 0.5 to 2.5 g/l SiF6 2-.
    4. Method according to claim 1, characterised in that the phosphating solution used for immersion contains 1.0 to 2.0 g/l Zn2+ and the phosphating solution used for spraying contains 0.5 to 1.5 g/l Zn2+.
    5. Method according to claim 1, characterised in that the phosphating solution contains 3 to 15 g/l NO3 -.
    6. Method according to claims 1 to 5, characterised in that the phosphating solution contains 0.5 to 1.3 g/l Ni2+.
    7. Method according to claims 1 to 5, characterised in that the phosphating solution contains 12 to 16 g/l phosphate (calculated as P2O5).
    8. Method according to claims 1 to 5, characterised in that the phosphating solution contains 0.5 to 1.3 g/l Mn2+.
    9. Method according to claims 1 to 5, characterised in that the phosphating solution contains 0.2 to 1.0 g/l F- and/or 0.8 to 2.0 g/l SiF6 2-.
    EP00905014A 1999-02-10 2000-02-03 Method for phosphatizing zinc or aluminium surfaces Expired - Lifetime EP1155163B1 (en)

    Applications Claiming Priority (3)

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    DE19905479 1999-02-10
    DE19905479A DE19905479A1 (en) 1999-02-10 1999-02-10 Process for the phosphatisation of zinc or aluminum surfaces
    PCT/EP2000/000865 WO2000047799A1 (en) 1999-02-10 2000-02-03 Method for phosphatizing zinc or aluminium surfaces

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    EP1155163B1 true EP1155163B1 (en) 2003-11-05

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    EP2014793B1 (en) 2007-06-14 2013-11-20 Atotech Deutschland GmbH Anti-corrosion treatment for conversion coatings
    CN104361836B (en) * 2014-11-20 2017-01-11 无锡科思电子科技有限公司 Pickling and phosphating method of light-emitting diode (LED) display screen cast iron box body
    CN109609940B (en) * 2019-01-10 2021-01-29 廊坊师范学院 Preparation method of metal piece abrasion-resistant silicification liquid and workpiece silicification process
    CN113490767A (en) 2019-02-28 2021-10-08 德国艾托特克公司 Aqueous post-treatment composition and corrosion protection method

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    DE3712339A1 (en) * 1987-04-11 1988-10-20 Metallgesellschaft Ag METHOD FOR PHOSPHATIZING BEFORE ELECTROPLATING
    US4865653A (en) * 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process
    US5261973A (en) * 1991-07-29 1993-11-16 Henkel Corporation Zinc phosphate conversion coating and process
    IT1274594B (en) * 1994-08-05 1997-07-18 Itb Srl ACID WATER PHOSPHATIC SOLUTION AND METALLIC SURFACE PHOSPHATION PROCESS USING IT
    DE19538778A1 (en) * 1995-10-18 1997-04-24 Henkel Kgaa Layer weight control in hydroxylamine-accelerated phosphating systems
    DE19606018A1 (en) * 1996-02-19 1997-08-21 Henkel Kgaa Zinc phosphating with low levels of nickel and / or cobalt
    DE19621184A1 (en) * 1996-05-28 1997-12-04 Henkel Kgaa Zinc phosphating with integrated post-passivation
    DE19735314C2 (en) * 1996-09-13 2001-05-23 Bayerische Motoren Werke Ag Process for the pretreatment of components
    DE19639597C2 (en) * 1996-09-26 2000-01-20 Henkel Kgaa Process for the phosphating of running strips made of cold or hot rolled steel in high-speed conveyor systems
    DE19639596A1 (en) * 1996-09-26 1998-04-02 Henkel Kgaa Process for phosphating steel strips
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    EP1155163A1 (en) 2001-11-21
    DE19905479A1 (en) 2000-08-17

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