EP2319957B1 - Black passivation of zinc and zinc-iron layers - Google Patents

Black passivation of zinc and zinc-iron layers Download PDF

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Publication number
EP2319957B1
EP2319957B1 EP10175959.5A EP10175959A EP2319957B1 EP 2319957 B1 EP2319957 B1 EP 2319957B1 EP 10175959 A EP10175959 A EP 10175959A EP 2319957 B1 EP2319957 B1 EP 2319957B1
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Prior art keywords
zinc
solution
passivation
ions
layers
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EP10175959.5A
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German (de)
French (fr)
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EP2319957A1 (en
Inventor
Dr. Manfred Jordan
Dr. Roland Pfiz
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Dr Ing Max Schloetter GmbH and Co KG
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Dr Ing Max Schloetter GmbH and Co KG
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Priority to SI201031381A priority Critical patent/SI2319957T1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

  • the invention relates to an acidic, aqueous reaction solution for producing a black passivation layer on zinc and zinc iron layers, to a method in which this reaction solution is used, and to the black passivation layer obtainable by this method.
  • the galvanic coating of components made of iron or steel with zinc or zinc alloys is carried out on a large scale and has a high economic importance.
  • the deposited layers protect the base material against corrosion and thus lead to a high increase in the value of the components.
  • the corrosion protection of iron or steel by zinc or zinc alloys is based on the anodic protection mechanism. Zinc or zinc alloys are less electrochemical than the base material. The corrosion attack therefore begins on the coating and the base material remains protected against corrosion as long as a closed zinc or zinc alloy surface is present.
  • the applied less noble zinc or Zinc alloy coatings are therefore also known as Called "sacrificial layers".
  • a zinc nickel layer with> 16% nickel is the nobler component compared to iron or steel and therefore can no longer provide anodic corrosion protection. The deposition of such a layer on iron or steel would therefore lead to preferred base material corrosion inhomogeneities of the coating (pitting corrosion).
  • the color of the chromating layers can be varied by composition of the solutions and by the working parameters in the treatment. You can create blue, yellow or olive colored surfaces. In this order, the layer thickness of the conversion layers and thus the corrosion protection increases.
  • black chromating layers Furthermore, it is also possible to produce black chromating layers.
  • the black chromations for pure zinc coatings were often added silver salts in very low concentrations. By reaction with the zinc surface, the Silver ions reduced to metallic silver. This resulting in very finely divided form silver is incorporated into the forming chromate layer and acts there as a black pigment.
  • Black chromations can produce deep black, uniform surfaces that can be used for decorative purposes.
  • the incorporation of small amounts of silver in the layer can have a detrimental effect on the corrosion protection, since silver is a very noble metal and therefore corrosion can lead to local element formation and thereby deterioration of the corrosion protection.
  • the alloying partners iron, cobalt or nickel can be converted into their oxides by suitable composition of the chromating solutions. These then act as black pigments in the chromating layer. Addition of silver salts to produce black pigments is not required in these cases.
  • the problem of the decomposition of these sulfur compounds also remains, if one does not use the free acids, but their salts.
  • the acids underlying the salts are weaker acids than e.g. Nitric acid or sulfuric acid used to adjust the pH of passivation solutions. The dissociation of the corresponding salts is thereby shifted to the side of the free acids, which then in turn uses the decomposition of the compounds.
  • WO 2005/068684 A1 The formation of the black passivation layer leads to the formation of iron-sulfur pigments. Although the method should also be suitable for the black passivation of pure zinc coatings, this hardly seems possible because they contain no iron and thus no iron-sulfur pigments can be formed.
  • a black corrosion resistant coating on zinc alloys and a method for its production is disclosed in US Pat EP 1 409 157 B1 described.
  • the layers are generated in a two-step process. First, a passivation layer is formed in a passivation solution based on trivalent chromium compounds. This layer does not have a black appearance yet. In a second process step is then in a sealing solution, the Contains black pigments, submerged. Although it is possible to achieve layers with the desired black appearance, such a two-step process is undesirable in practice. The application of a seal based on organic compounds is not permitted in all applications. It is therefore more advantageous if the black optic can already be achieved by the passivation layer and not only by the additional step of sealing.
  • EP 1 484 432 A1 claims a treatment solution and method for depositing black passivation layers on zinc or zinc alloy layers.
  • a disadvantage of this method is the relatively complicated composition of the treatment solution.
  • the deposition of black passivation layers requires a very close ratio of nitrate to chromium.
  • the ratio NO - 3 / Cr 3+ should be less than 0.5 / 1.
  • the chromium concentration is preferably 0.5 to 10 g / l, corresponding to 0.001 to 0.19 mol / l. This results in a resulting nitrate concentration of not more than 0.0005 to 0.095 mol / l or 0.03 to 5.9 g / l.
  • the analysis of such low nitrate concentrations is very difficult with the analytical methods that are commonly available in a galvanic plant operation laboratory. Furthermore, the formation of the passivation layer continuously consumes chromium, which shifts the ratio NO - 3 / Cr 3+ . The operation of the solution, which requires a tight NO - 3 / Cr 3+ ratio, thereby becomes unstable.
  • the solution also contains complexing agents from the group of monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, hydroxycarboxylic acids or aminocarboxylic acids. These form partially stable complexes with the metal ions contained in the solution. These cause difficulties in wastewater treatment and are therefore undesirable.
  • EP 1 571 238 A1 describes a Cr (III) -containing passivating solution containing Cr (III) ions and at least two types of ions selected from sulfate ions, nitrate ions, chloride ions, oxyacid ions of chlorine and boron, oxyacid ions of phosphorus and fluoride ions.
  • this solution may also contain a sulfur compound.
  • Such a solution is used to make a coating for aluminum components.
  • WO 2010/035819 A1 relates to a passivation solution and the use of this black passivation solution.
  • the passivating solution is an aqueous solution containing a Cr (III) -containing substance, a cobalt-containing substance, a sulfur compound, an organophosphonic acid compound and, if necessary, a nickel-containing substance, the passivating solution being substantially free of Cr (VI ).
  • the present invention relates to the above-described acidic aqueous passivating solution containing Cr (III) ions, fluoride ions, nitrate ions and dithiodiglycolic acid, or a salt thereof, and a method for producing black passivation layers on zinc or zinc iron alloy layers, in which a workpiece provided with a zinc or zinc iron alloy layer is brought into contact with the passivation solution of the present invention. Moreover, the present invention relates to a black passivation layer obtainable by the method according to this invention.
  • the passivation solution contains a dithiodiglycolic acid (HOOC-CH 2 -SS-CH 2 -COOH) or a salt of this acid.
  • a dithiodiglycolic acid HOOC-CH 2 -SS-CH 2 -COOH
  • Any salts of dithiodiglycolic acid can be used. Examples of these are the sodium or disodium salt, the potassium or dipotassium salt and the ammonium or diammonium salt. Particularly preferred is the use of the diammonium salt of dithiodiglycolic acid.
  • the passivation solution according to the invention contains the dithiodiglycolic acid or a salt of this acid in a concentration, based on the free acid, of preferably 2-10 g / l of passivating solution, more preferably 4-6 g / l of passivating solution.
  • Cr (III) ions all soluble chromium (III) compounds can be used. Examples which may be mentioned are chromium (III) chloride, CrCl 3 .H 2 O, basic chromium (III) sulfate, CrOHSO 4 , potassium chromium sulfate, KCr (SO 4 ) 2 .6H 2 O and chromium nitrate, Cr (NO 3 ). 3 x 9H 2 O. Preferred is chromium nitrate, Cr (NO 3 ) 3 .9H 2 O.
  • the Cr (III) ions are present in the passivation solution in an amount of 1-10 g / l passivating solution, more preferably 4-5 g / l passivating solution.
  • the passivating solution according to this invention contains fluoride ions.
  • the fluoride ions are present in the passivation solution in an amount of 0.3-3 g / l passivating solution, more preferably 1-1.5 g / l passivating solution.
  • fluoride ions all soluble fluoride compounds can be used. Preferred are sodium fluoride, NaF, potassium fluoride, KF, ammonium fluoride, NH 4 F, sodium bifluoride, NaF ⁇ HF, potassium bifluoride, KF ⁇ HF, ammonium bifluoride, NH 4 F ⁇ HF. Very particularly preferred is the use of sodium fluoride, NaF.
  • the passivation solution according to the present invention also contains nitrate ions.
  • the amount of nitrate ion is 3-35 g / l passivating solution, more preferably 15-25 g / l.
  • the nitrate ions can be added to the passivating solution in any form of soluble nitrate salt. It is also possible to use a combination of several different soluble nitrate salts.
  • the nitrate ions may be added together with the Cr (III) ions as the chromium nitrate, Cr (NO 3 ) 3 .9H 2 O.
  • Another suitable nitrate salt is, for example, sodium nitrate.
  • the nitrate ion addition is in the form of sodium nitrate, it should be considered in terms of the preferred total nitrate concentration in which form the addition of the chromium compound occurs.
  • a passivating solution which comprises Cr (III) ions in an amount of 1-10 g / l passivating solution, fluoride ions in an amount of 0.3-3 g / l passivating solution, nitrate ions in an amount of 3 - 35 g / l passivation solution and dithiodiglycolic acid or a salt thereof in an amount, based on dithiodiglycolic acid, of g / l.
  • an acidic, aqueous passivating solution containing the following constituents is very particularly preferred: Cr (III) ions in an amount of 4-5 g / l passivating solution, fluoride ions in an amount of 1-1.5 g / Passivation solution, nitrate ions in an amount of 15-25 g / l passivating solution and dithiodiglycolic acid or a salt thereof in an amount, based on dithiodiglycolic acid, of 4-6 g / l.
  • the passivation solution of the present invention may contain cobalt ions.
  • the incorporation of cobalt ions in passivations based on trivalent chromium compounds is known and serves to further improve the corrosion resistance.
  • the concentration of cobalt ions in the passivating solution is preferably 0.1-10 g / l passivating solution, more preferably 0.5-5 g / l.
  • the addition of the cobalt ions can be carried out in any form of water-soluble cobalt salts. Preference is given to cobalt sulfate, cobalt chloride or cobalt nitrate.
  • the pH of the passivating solution of the present invention is suitably adjusted to a preferred range of 1.8 to 2.2, more preferably 1.9 to 2.1.
  • the present invention further provides a process for producing black passivation layers on zinc and zinc iron layers using the passivation solution described above.
  • a workpiece provided with a zinc or zinc iron layer is brought into contact with the passivating solution.
  • the contacting may be spraying, swelling or dipping.
  • dipping is used in the art.
  • the reaction temperature is preferably 10 to 70 ° C. Particularly preferred is a temperature range of 15-50 ° C, more preferably 20-50 ° C.
  • the workpieces are with the Passivation for a period of preferably 60- 90 seconds, more preferably 75 seconds, brought into contact. That is, when the workpieces are dipped in the passivation solution, the dipping time is preferably 60-90 seconds.
  • the black passivation layer may be formed on a zinc or zinc iron alloy layer.
  • a sealing layer a so-called “topcoat”
  • a sealing layer is known and improves corrosion resistance.
  • the workpiece is brought into contact with a sealing solution.
  • a sealing solution It is an aqueous solution containing organic, water-soluble or dispersible polymers.
  • organic, water-soluble or dispersible polymers For example, copolymers of acrylic acid or methacrylic acid with ethylene, commercially available under the name Lugalavan DC Fa. BASF, are used.
  • Inorganic sealant solutions contain colloidal silicic acids. It is also possible to prepare mixtures of aqueous solutions with organic polymers and aqueous solutions with colloidal silicas and to use these as a sealing solution.
  • the present invention also provides a black passivation layer obtainable by the method described above.
  • the black passivation layer is formed on a pure zinc layer.
  • the mixture is heated to 65 ° C for 30 minutes, then cooled to room temperature. It is then made up to 1 liter with deionized water.
  • the volume was made up to approximately 1 liter with deionized water, then the pH was reduced with conc. Nitric acid (53 wt.%) Adjusted to 1.8 to 1.9 and made up to the final volume of 1 liter.
  • test sheet was rinsed in deionized water, immersed in dilute nitric acid solution (10 ml / l HNO 3 53% by weight) for 5 seconds and then in the above immersed in the following conditions: Temperature: 25 ° C PH value: 1.8 - 1.9 Dive time: 60 seconds
  • test sheet was then rinsed with deionized water and dried in a drying oven at 80 ° C for 15 minutes. The appearance of the test sheet was then deep black with slightly brownish iridescent spots.
  • Example 1 was repeated as described. After passivation and rinsing, it was immersed in a sealing solution (SLOTOFIN 70 from Dr.-Ing. Max Schlötter, aqueous dispersion of a copolymer of acrylic acid and ethylene).
  • SLOTOFIN 70 from Dr.-Ing. Max Schlötter, aqueous dispersion of a copolymer of acrylic acid and ethylene.
  • test sheet was dried without rinsing at 80 ° C for 15 minutes in a drying oven.
  • the sealed test sheet had a uniform deep black, semi-glossy appearance.
  • Test panels which were prepared according to Examples 1 and 2, were tested in a corrosion test in the neutral salt spray test according to DIN EN ISO 9227. Following DIN 50 979, 1 sample was tested without additional heat treatment and 1 sample was annealed at 120 ° C. for 24 hours. corrosion protection without heat treatment with heat treatment (120 ° C / 24h) example 1 72 h 72 h Example 2 > 240 h > 240 h
  • the volume was made up to approximately 1 liter with deionized water, then the pH was reduced with conc. Nitric acid (53 wt.%) Adjusted to 1.8 to 1.9 and made up to the final volume of 1 liter.
  • a passivation solution was prepared as in Comparative Example 1, but thiodiglycolic acid was replaced by 4 g of cystine. The passivation reaction did not result in blackening.

Description

Technisches GebietTechnical area

Die Erfindung betrifft eine saure, wässrige Reaktionslösung zur Erzeugung einer schwarzen Passivierungsschicht auf Zink- und Zinkeisenschichten, ein Verfahren, bei dem diese Reaktionslösung verwendet wird, sowie die durch dieses Verfahren erhältliche schwarze Passivierungsschicht.The invention relates to an acidic, aqueous reaction solution for producing a black passivation layer on zinc and zinc iron layers, to a method in which this reaction solution is used, and to the black passivation layer obtainable by this method.

Stand der TechnikState of the art

Die galvanische Beschichtung von Bauteilen aus Eisen oder Stahl mit Zink- oder Zinklegierungen wird in großem Umfang durchgeführt und hat eine hohe wirtschaftliche Bedeutung. Die abgeschiedenen Schichten schützen das Grundmaterial vor Korrosion und führen dadurch zu einer hohen Wertsteigerung der Bauteile. Der Korrosionsschutz für Eisen oder Stahl durch Zink- oder Zinklegierungen beruht auf dem anodischen Schutzmechanismus. Zink- oder Zinklegierungen sind elektrochemisch unedler als das Grundmaterial. Der Korrosionsangriff beginnt daher am Überzug, und das Grundmaterial bleibt vor Korrosion geschützt, solange eine geschlossene Zink- oder Zinklegierungsoberfläche vorliegt.
Die aufgebrachten unedleren Zink- bzw.
Zinklegierungsschichten werden daher auch als
"Opferschichten" bezeichnet.The galvanic coating of components made of iron or steel with zinc or zinc alloys is carried out on a large scale and has a high economic importance. The deposited layers protect the base material against corrosion and thus lead to a high increase in the value of the components. The corrosion protection of iron or steel by zinc or zinc alloys is based on the anodic protection mechanism. Zinc or zinc alloys are less electrochemical than the base material. The corrosion attack therefore begins on the coating and the base material remains protected against corrosion as long as a closed zinc or zinc alloy surface is present.
The applied less noble zinc or
Zinc alloy coatings are therefore also known as
Called "sacrificial layers".

Bei Anwendung einer Zinklegierung, z.B. Zink-Nickel, muss darauf geachtet werden, dass das elektrochemische Potential der Legierung noch unedel in Bezug auf das Grundmaterial bleibt. Eine Zinknickelschicht mit > 16 % Nickel ist gegenüber Eisen oder Stahl die edlere Komponente und kann daher keinen anodischen Korrosionsschutz mehr liefern. Die Abscheidung einer solchen Schicht auf Eisen oder Stahl würde daher zur bevorzugten Grundmaterialkorrosion an Inhomogenitäten des Überzuges führen (Lochfraßkorrosion).When using a zinc alloy, eg zinc-nickel, care must be taken that the electrochemical potential the alloy still remains non-noble in relation to the base material. A zinc nickel layer with> 16% nickel is the nobler component compared to iron or steel and therefore can no longer provide anodic corrosion protection. The deposition of such a layer on iron or steel would therefore lead to preferred base material corrosion inhomogeneities of the coating (pitting corrosion).

Um den Korrosionsangriff auf die Opferschichten aus Zink oder einer Zinklegierung noch hinaus zu zögern und damit den Korrosionsschutz insgesamt zu verbessern, ist es im Stand der Technik bekannt, auf die Zink- oder Zinklegierungsschichten noch eine zusätzliche Konversionsschicht aufzubringen. Hier war es in der Vergangenheit üblich, solche Konversionsschichten durch Behandlung der Bauteile in sauren, chromathaltigen Lösungen zu erzeugen. Nachteilig ist bei diesen Schichten, dass darin auch sechswertige Chromverbindungen eingelagert werden. Diese sind teilweise wasserlöslich und können dadurch aus den Schichten ausgelaugt werden. Wegen der hohen Giftigkeit der Chrom(VI) -verbindungen stellen solche Schichten eine Gefahr für Mensch und Umwelt dar. Die Verfahren auf Basis sechswertiger Chromverbindungen werden daher zunehmend durch Verfahren auf Basis ungiftiger Chrom(III)-verbindungen ersetzt.In order to delay the corrosion attack on the sacrificial layers of zinc or a zinc alloy even further and thus improve the overall corrosion protection, it is known in the art to apply an additional conversion layer to the zinc or zinc alloy layers. Here, it has been customary in the past to produce such conversion layers by treating the components in acidic, chromate-containing solutions. A disadvantage of these layers is that also hexavalent chromium compounds are incorporated therein. These are partially water-soluble and can be leached out of the layers. Because of the high toxicity of chromium (VI) compounds, such layers pose a hazard to humans and the environment. The hexavalent chromium compound processes are therefore increasingly being replaced by non-toxic chromium (III) compound based processes.

Die Farbe der Chromatierungsschichten kann durch Zusammensetzung der Lösungen und durch die Arbeitsparameter bei der Behandlung variiert werden. Es können blaue, gelbe oder olivfarbene Oberflächen erzeugt werden. In dieser Reihenfolge nimmt auch die Schichtdicke der Konversionsschichten und somit der Korrosionsschutz zu.The color of the chromating layers can be varied by composition of the solutions and by the working parameters in the treatment. You can create blue, yellow or olive colored surfaces. In this order, the layer thickness of the conversion layers and thus the corrosion protection increases.

Weiterhin ist es auch möglich, schwarze Chromatierungsschichten zu erzeugen. Den Schwarzchromatierungen für Reinzinkschichten wurden dabei häufig Silbersalze in sehr geringen Konzentrationen zugesetzt. Durch Reaktion mit der Zinkoberfläche werden die Silberionen zu metallischem Silber reduziert. Dieses in sehr fein verteilter Form anfallende Silber wird in die sich bildende Chromatschicht eingebaut und wirkt dort als Schwarzpigment. Durch Schwarzchromatierungen können tiefschwarze, gleichmäßige Oberflächen erzeugt werden, die zu dekoraktiven Zwecken eingesetzt werden können. Der Einbau geringer Mengen an Silber in die Schicht kann sich jedoch nachteilig auf den Korrosionsschutz auswirken, da Silber ein sehr edles Metall ist und es bei der Korrosion daher zu Lokalelementbildung und dadurch Verschlechterung des Korrosionsschutzes kommen kann.Furthermore, it is also possible to produce black chromating layers. The black chromations for pure zinc coatings were often added silver salts in very low concentrations. By reaction with the zinc surface, the Silver ions reduced to metallic silver. This resulting in very finely divided form silver is incorporated into the forming chromate layer and acts there as a black pigment. Black chromations can produce deep black, uniform surfaces that can be used for decorative purposes. However, the incorporation of small amounts of silver in the layer can have a detrimental effect on the corrosion protection, since silver is a very noble metal and therefore corrosion can lead to local element formation and thereby deterioration of the corrosion protection.

Bei Zinklegierungsschichten wie Zink-Eisen, Zink-Cobalt oder Zink-Nickel können durch geeignete Zusammensetzung der Chromatierungslösungen die Legierungspartner Eisen, Cobalt oder Nickel in ihre Oxide überführt werden. Diese wirken dann als Schwarzpigmente in der Chromatierungsschicht. Ein Zusatz von Silbersalzen zur Erzeugung von Schwarzpigmenten ist in diesen Fällen nicht erforderlich.For zinc alloy layers such as zinc-iron, zinc-cobalt or zinc-nickel, the alloying partners iron, cobalt or nickel can be converted into their oxides by suitable composition of the chromating solutions. These then act as black pigments in the chromating layer. Addition of silver salts to produce black pigments is not required in these cases.

Auf dem Gebiet der Verfahren zur Ausbildung von Passivierungsschichten aus Lösungen auf der Basis von dreiwertigen Chromverbindungen besteht jedoch Bedarf an weitere Verfahren für die Schwarzpassivierung von Zinkschichten.However, in the field of methods for forming passivation layers from solutions based on trivalent chromium compounds, there is a need for further methods for the black passivation of zinc layers.

Ein Verfahren zur Schwarzpassivierung von Zink- oder Zinklegierungsschichten ist in WO 2005/068684 A1 offenbart. Es wird dort beschrieben, zu Passivierungslösungen auf Basis dreiwertiger Chromverbindungen anorganische und/oder organische Schwefelverbindungen zuzusetzen. Als geeignete Schwefelverbindungen werden speziell genannt:

  • Hyposchwefelige Säure (H2SO2)
  • Schwefelige Säure (H2SO3)
  • Schwefelwasserstoffsäure (H2S)
  • Thioschwefelsäure (H2S2O3) und
  • Dischweflige Säure (H2S2O5)
A method for black passivation of zinc or zinc alloy layers is in WO 2005/068684 A1 disclosed. It describes how to add inorganic and / or organic sulfur compounds to passivating solutions based on trivalent chromium compounds. Suitable sulfur compounds are specifically named:
  • Hyposulphurous acid (H 2 SO 2 )
  • Sulfurous acid (H 2 SO 3 )
  • Hydrosilicic acid (H 2 S)
  • Thiosulfuric acid (H 2 S 2 O 3 ) and
  • Dischweflige acid (H 2 S 2 O 5 )

Es handelt sich bei allen diesen genannten Verbindungen um solche, die im sauren Bereich um pH 2, bei dem üblicherweise gearbeitet wird, nicht stabil sind. Im sauren Bereich werden in einigen Fällen toxische Gase freigesetzt (SO2, H2S). Zum einen führt die Zersetzung der Schwefelverbindung zu unstabilen Prozessen und zum anderen bedingt die Freisetzung der toxischen Gase eine Gefährdung des Bedienungspersonales an solchen Anlagen.All of these compounds mentioned are those which are not stable in the acidic range around pH 2, which is usually used. In the acidic area, toxic gases are released in some cases (SO 2 , H 2 S). On the one hand, the decomposition of the sulfur compound leads to unstable processes and, on the other hand, the release of the toxic gases poses a threat to the operating personnel of such plants.

Das Problem der Zersetzung dieser Schwefelverbindungen bleibt natürlich auch bestehen, wenn man nicht die freien Säuren, sondern deren Salze einsetzt. Die den Salzen zugrundeliegenden Säuren sind schwächere Säuren als z.B. Salpetersäure oder Schwefelsäure, die zum Einstellen des pH-Wertes von Passivierungslösungen verwendet werden. Die Dissoziation der entsprechenden Salze wird dadurch auf die Seite der freien Säuren verschoben, wodurch dann wiederum die Zersetzung der Verbindungen einsetzt.Of course, the problem of the decomposition of these sulfur compounds also remains, if one does not use the free acids, but their salts. The acids underlying the salts are weaker acids than e.g. Nitric acid or sulfuric acid used to adjust the pH of passivation solutions. The dissociation of the corresponding salts is thereby shifted to the side of the free acids, which then in turn uses the decomposition of the compounds.

WO 2005/068684 A1 führt die Bildung der schwarzen Passivierungsschicht auf die Bildung von Eisen-Schwefel-Pigmenten zurück. Obwohl das Verfahren auch für die Schwarzpassivierung von Reinzinkschichten geeignet sein soll, so erscheint dies schwerlich möglich, weil diese kein Eisen enthalten und somit keine Eisen-Schwefel-Pigmente gebildet werden können. WO 2005/068684 A1 The formation of the black passivation layer leads to the formation of iron-sulfur pigments. Although the method should also be suitable for the black passivation of pure zinc coatings, this hardly seems possible because they contain no iron and thus no iron-sulfur pigments can be formed.

Ein schwarzer korrosionsbeständiger Überzug auf Zinklegierungen und ein Verfahren zu seiner Herstellung wird in EP 1 409 157 B1 beschrieben. Die Schichten werden dabei in einem zweistufigen Verfahren erzeugt. Es wird zunächst eine Passivierungsschicht in einer Passivierungslösung auf Basis von dreiwertigen Chromverbindungen gebildet. Diese Schicht hat noch kein schwarzes Aussehen. In einem zweiten Verfahrensschritt wird dann in einer Versiegelungslösung, die Schwarzpigmente enthält, nachgetaucht. Obwohl sich damit Schichten mit der gewünschten schwarzen Optik erzielen lassen, ist ein solches zweistufiges Verfahren in der Praxis unerwünscht. Die Aufbringung einer Versiegelung auf Basis organischer Verbindungen ist nicht bei allen Anwendungen zulässig. Es ist daher vorteilhafter, wenn die schwarze Optik bereits durch die Passivierungsschicht erreicht werden kann und nicht erst durch den zusätzlichen Schritt einer Versieglung.A black corrosion resistant coating on zinc alloys and a method for its production is disclosed in US Pat EP 1 409 157 B1 described. The layers are generated in a two-step process. First, a passivation layer is formed in a passivation solution based on trivalent chromium compounds. This layer does not have a black appearance yet. In a second process step is then in a sealing solution, the Contains black pigments, submerged. Although it is possible to achieve layers with the desired black appearance, such a two-step process is undesirable in practice. The application of a seal based on organic compounds is not permitted in all applications. It is therefore more advantageous if the black optic can already be achieved by the passivation layer and not only by the additional step of sealing.

EP 1 484 432 A1 beansprucht eine Behandlungslösung und ein Verfahren zur Abscheidung von schwarzen Passivierungsschichten auf Zink oder Zinklegierungsschichten. Nachteilig bei diesem Verfahren ist die relativ komplizierte Zusammensetzung der Behandlungslösung. Für die Abscheidung schwarzer Passivierungsschichten ist ein sehr enges Verhältnis von Nitrat zu Chrom erforderlich. Das Verhältnis NO- 3/Cr3+ soll weniger als 0,5/1 betragen. Die Chromkonzentration beträgt vorzugsweise 0,5 bis 10 g/l, entsprechend 0,001 bis 0,19 mol/l. Daraus ergibt sich eine resultierende Nitratkonzentration von maximal 0,0005 bis 0,095 mol/l oder 0,03 bis 5,9 g/l. Die Analyse derart niedriger Nitratkonzentrationen ist mit den Analysenmethoden, die üblicherweise in einem Betriebslabor von Galvanobetrieben zur Verfügung stehen, sehr schwierig. Ferner wird durch die Ausbildung der Passivierungsschicht kontinuierlich Chrom verbraucht, wodurch sich das Verhältnis NO- 3/Cr3+ verschiebt. Die Arbeitsweise der Lösung, für die ein enges NO- 3/Cr3+-Verhältnis erforderlich ist, wird dadurch unstabil. Die Lösung enthält weiterhin Komplexbildner aus der Gruppe der Monocarbonsäuren, Dicarbonsäuren, Tricarbonsäuren, Hydroxycarbonsäuren oder Aminocarbonsäuren. Diese bilden mit den in der Lösung enthaltenen Metallionen z.T. stabile Komplexe. Diese bereiten bei der Abwasserbehandlung Schwierigkeiten und sind daher unerwünscht. EP 1 484 432 A1 claims a treatment solution and method for depositing black passivation layers on zinc or zinc alloy layers. A disadvantage of this method is the relatively complicated composition of the treatment solution. The deposition of black passivation layers requires a very close ratio of nitrate to chromium. The ratio NO - 3 / Cr 3+ should be less than 0.5 / 1. The chromium concentration is preferably 0.5 to 10 g / l, corresponding to 0.001 to 0.19 mol / l. This results in a resulting nitrate concentration of not more than 0.0005 to 0.095 mol / l or 0.03 to 5.9 g / l. The analysis of such low nitrate concentrations is very difficult with the analytical methods that are commonly available in a galvanic plant operation laboratory. Furthermore, the formation of the passivation layer continuously consumes chromium, which shifts the ratio NO - 3 / Cr 3+ . The operation of the solution, which requires a tight NO - 3 / Cr 3+ ratio, thereby becomes unstable. The solution also contains complexing agents from the group of monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, hydroxycarboxylic acids or aminocarboxylic acids. These form partially stable complexes with the metal ions contained in the solution. These cause difficulties in wastewater treatment and are therefore undesirable.

Ferner wird in der EP 1 571 238 A1 eine Cr(III)-haltige Passivierungslösung beschrieben, die Cr(III)-Ionen und mindestens zwei Ionentypen ausgewählt aus Sulfationen, Nitrationen, Chloridionen, Oxysäure-Ionen von Chlor und Bor, Oxysäure-Ionen von Phosphor und Fluoridionen enthält. Fakultativ kann diese Lösung auch eine Schwefel-Verbindung enthalten. Gemäß der Lehre der EP 1 571 238 8 A1 wird eine solche Lösung zur Herstellung eines Überzugs für Aluminiumbauteile verwendet.Furthermore, in the EP 1 571 238 A1 describes a Cr (III) -containing passivating solution containing Cr (III) ions and at least two types of ions selected from sulfate ions, nitrate ions, chloride ions, oxyacid ions of chlorine and boron, oxyacid ions of phosphorus and fluoride ions. Optionally, this solution may also contain a sulfur compound. According to the teaching of EP 1 571 238 8 A1 Such a solution is used to make a coating for aluminum components.

US 2007/196632 A1 beschreibt eine Passivierungslösung zur Schwarzfärbung von Zink oder Zinklegierungen, wobei diese Lösung zur Schwarzfärbung Thioglykolsäure enthält. US 2007/196632 A1 describes a passivation solution for the blackening of zinc or zinc alloys, this solution for blackening containing thioglycolic acid.

WO 2010/035819 A1 betrifft eine Passivierungslösung und die Verwendung dieser Lösung zur Schwarzpassivierung. Die Passivierungslösung ist eine wässrige Lösung enthaltend eine Cr(III)-haltige Substanz, eine Cobalt-haltige Substanz, eine Schwefelverbindung, eine Organophosphonsäure-Verbindung und, wenn notwendig, eine Nickel-haltige Substanz, wobei die Passivierungslösung im Wesentlichen frei von Cr(VI) ist. WO 2010/035819 A1 relates to a passivation solution and the use of this black passivation solution. The passivating solution is an aqueous solution containing a Cr (III) -containing substance, a cobalt-containing substance, a sulfur compound, an organophosphonic acid compound and, if necessary, a nickel-containing substance, the passivating solution being substantially free of Cr (VI ).

In EP 1 484 432 A1 wird ferner ein Verfahren zur Abscheidung schwarzer Konversionsschichten beschrieben, die aus einer Lösung erhalten werden, bestehend aus Nitrationen und dreiwertigen Chromionen in einem Molverhältnis NO- 3/Cr3+ von weniger als 0,5/1. Zusätzlich enthält die Lösung noch Phosphationen. Bei der Schichtbildungsreaktion kommt es an der Substratoberfläche zu pH-Verschiebungen. Dadurch werden unlösliche Phosphorverbindung aus den in der Lösung befindlichen Metallionen (z.B. zn2+, Cr3+, Ni2+ oder CO2+) gebildet. Nachteilig ist bei solchen phosphathaltigen Lösungen, dass sie nur eine geringe Standzeit haben. Bereits nach kurzer Einsatzdauer kommt es zur Ausbildung bräunlich bis grünlich irisierender Schichten, der gewünschte tiefschwarze Farbton ist schwierig zu erreichen.In EP 1 484 432 A1 Furthermore, a method for depositing black conversion layers obtained from a solution consisting of nitrate ions and trivalent chromium ions in a molar ratio NO - 3 / Cr 3+ of less than 0.5 / 1 is described. In addition, the solution still contains phosphate ions. In the layer formation reaction, pH shifts occur at the substrate surface. As a result, insoluble phosphorus compound from the metal ions in the solution (eg Zn 2+ , Cr 3+ , Ni 2+ or CO 2+ ) are formed. A disadvantage of such phosphate-containing solutions that they have only a short life. After only a short period of use, brownish to greenish iridescent layers are formed; the desired deep black hue is difficult to achieve.

Das Problem der unzureichenden Schwarzfärbung soll durch ein Verfahren entsprechend der EP 1 995 348 A1 gelöst werden. Dort wird eine Lösung beansprucht, welche Zinkionen, dreiwertige Chromionen, Komplexbildner, die mit den dreiwertigen Chromionen wasserlösliche Komplexe bilden, Schwefelverbindungen und Phosphit-ionen enthält. Die einzelnen Komponenten müssen dabei in einem bestimmten Verhältnis zueinander stehen. Abweichungen davon führen entweder zu ungenügender Schwarzfärbung der Schichten oder zu einer geringen Korrosionsbeständigkeit. Bei einer Passivierungslösung reichert sich im laufenden Betrieb Zink an, gleichzeitig wird durch die Ausbildung der Konversionsschicht Chrom verbraucht. Dadurch verändert sich das Verhältnis Zink : Chrom in der Lösung ständig. Die Überwachung einer solchen Passivierungslösung ist daher sehr aufwendig.The problem of insufficient blackening is said to be due to a method according to the EP 1 995 348 A1 be solved. There, a solution is claimed which contains zinc ions, trivalent chromium ions, complexing agents which form water-soluble complexes with the trivalent chromium ions, sulfur compounds and phosphite ions. The individual components must be in a certain relationship to each other. Deviations from this lead either to insufficient blackening of the layers or to a low corrosion resistance. During a passivation solution, zinc accumulates during operation, while chromium is consumed by the formation of the conversion layer. As a result, the ratio of zinc to chromium in the solution is constantly changing. The monitoring of such a passivation solution is therefore very expensive.

Es besteht daher Bedarf an stabilen Passivierungslösungen, die in einem einfachen und sicheren Verfahren im laufenden Dauerbetrieb die Abscheidung tiefschwarzer Passivierungsschichten auf Zink- oder Zinklegierungsschichten mit guten Korrosionsbeständigkeiten ermöglichen.There is therefore a need for stable passivation solutions which enable the deposition of deep black passivation layers on zinc or zinc alloy layers with good corrosion resistance in a simple and reliable continuous operation operation.

Zusammenfassung der ErfindungSummary of the invention

Überraschenderweise wurde gefunden, dass die Zugabe von Dithiodiglykolsäure oder eines Salzes dieser Säure zu einer sauren, wässrigen Passivierungslösung, die Cr(III)-Ionen, Fluoridionen und Nitrationen enthält, zu tiefschwarzen Konversionsschichten auf Zink- und Zinkeisenlegierungsschichten führt, die bereits ohne eine anschließende Versiegelung ausgezeichnete Beständigkeiten im Salzsprühtest nach DIN EN ISO 9227 erreichen. Mit anschließender Versiegelung wird eine Beständigkeit von > 240 Stunden erreicht.Surprisingly, it has been found that the addition of dithiodiglycolic acid or a salt of this acid to an acidic, aqueous passivating solution containing Cr (III) ions, fluoride ions and nitrate ions results in deep black conversion layers on zinc and zinc iron alloy layers already without subsequent sealing achieve excellent resistance in the salt spray test according to DIN EN ISO 9227. Subsequent sealing achieves a durability of> 240 hours.

Daher betrifft die vorliegende Erfindung die oben beschriebene saure, wässrige Passivierungslösung, die Cr(III)-Ionen, Fluoridionen, Nitrationen und Dithiodiglykolsäure, oder ein Salz dieser Säure enthält, sowie ein Verfahren zur Erzeugung von schwarzen Passivierungsschichten auf Zink- oder Zinkeisenlegierungsschichten, bei dem ein Werkstück, das mit einer Zink- oder Zinkeisenlegierungsschicht versehen ist, mit der erfindungsgemäßen Passivierungslösung in Kontakt gebracht wird. Außerdem betrifft die vorliegende Erfindung eine schwarze Passivierungsschicht, die durch das Verfahren gemäß dieser Erfindung erhältlich ist.Therefore, the present invention relates to the above-described acidic aqueous passivating solution containing Cr (III) ions, fluoride ions, nitrate ions and dithiodiglycolic acid, or a salt thereof, and a method for producing black passivation layers on zinc or zinc iron alloy layers, in which a workpiece provided with a zinc or zinc iron alloy layer is brought into contact with the passivation solution of the present invention. Moreover, the present invention relates to a black passivation layer obtainable by the method according to this invention.

Detaillierte Beschreibung der ErfindungDetailed description of the invention

Für Schwarzpassivierungen auf Zink gibt es z.Z. noch keine genormten Anforderungen. Für die Praxis sollten aber mindestens die Werte erreicht werden, die bereits im Stand der Technik für Schwarzpassivierungsschichten auf Zinkeisenlegierungen erreicht werden. Für solche Schichten betragen die Anforderungen nach DIN 50 979 bei Anwendung von zusätzlichen Versiegelungen für Gestellware mindestens 168 Stunden Beständigkeit im Salzsprühtest nach DIN EN ISO 9227. Mit dem erfindungsgemäßen Verfahren wird diese Anforderung bereits von Reinzinkschichten erreicht. Die erfindungsgemäße Reaktionslösung eignet sich zur Ausbildung von schwarzen Konversionsschichten auf sowohl Reinzinkschichten als auch Zinkeisenschichten. Die Anwendung von Reinzinkschichten ist jedoch bevorzugt, weil ein wesentlich größerer Vorteil darin besteht, wenn Reinzinkschichten direkt schwarzpassiviert werden können.There are currently no standardized requirements for black passivation on zinc. In practice, however, at least the values which have already been achieved in the prior art for black passivation layers on zinc-iron alloys should be achieved. For such layers, the requirements according to DIN 50 979 apply when using additional sealings for rack material at least 168 hours resistance in salt spray test according to DIN EN ISO 9227. With the method according to the invention this requirement is already reached by pure zinc coatings. The reaction solution according to the invention is suitable for the formation of black conversion layers on both pure zinc layers and zinc iron layers. However, the use of pure zinc coatings is preferred because there is a much greater advantage if pure zinc coatings can be directly black passivated.

Erfindungsgemäß enthält die Passivierungslösung eine Dithiodiglykolsäure (HOOC-CH2-S-S-CH2-COOH) oder ein Salz dieser Säure. Es können jegliche Salze der Dithiodiglykolsäure verwendet werden. Beispiele dafür sind das Natrium- bzw. Dinatriumsalz, das Kalium- bzw. Dikaliumsalz und das Ammonium- bzw. Diammoniumsalz. Besonders bevorzugt ist die Verwendung des Diammoniumsalzes der Dithiodiglykolsäure.According to the invention, the passivation solution contains a dithiodiglycolic acid (HOOC-CH 2 -SS-CH 2 -COOH) or a salt of this acid. Any salts of dithiodiglycolic acid can be used. Examples of these are the sodium or disodium salt, the potassium or dipotassium salt and the ammonium or diammonium salt. Particularly preferred is the use of the diammonium salt of dithiodiglycolic acid.

In der erfindungsgemäßen Passivierungslösung ist die Dithiodiglykolsäure, oder ein Salz dieser Säure in einer Konzentration, bezogen auf die freie Säure, von vorzugsweise 2 - 10 g/l Passivierungslösung, besonders bevorzugt 4 - 6 g/l Passivierungslösung, enthalten.The passivation solution according to the invention contains the dithiodiglycolic acid or a salt of this acid in a concentration, based on the free acid, of preferably 2-10 g / l of passivating solution, more preferably 4-6 g / l of passivating solution.

Für die Cr(III)-Ionen können alle löslichen Chrom(III)-Verbindungen eingesetzt werden. Als Beispiele können genannt werden Chrom(III)-chlorid, CrCl3·H2O, basisches Chrom(III)-sulfat, CrOHSO4, Kaliumchromsulfat, KCr(SO4)2·6H2O und Chromnitrat, Cr(NO3)3·9H2O. Bevorzugt ist Chromnitrat, Cr(NO3)3·9H2O.For the Cr (III) ions, all soluble chromium (III) compounds can be used. Examples which may be mentioned are chromium (III) chloride, CrCl 3 .H 2 O, basic chromium (III) sulfate, CrOHSO 4 , potassium chromium sulfate, KCr (SO 4 ) 2 .6H 2 O and chromium nitrate, Cr (NO 3 ). 3 x 9H 2 O. Preferred is chromium nitrate, Cr (NO 3 ) 3 .9H 2 O.

Die Cr(III)-Ionen sind in der Passivierungslösung in einer Menge von 1 - 10 g/l Passivierungslösung, besonders bevorzugt 4 - 5 g/l Passivierungslösung, vorhanden.The Cr (III) ions are present in the passivation solution in an amount of 1-10 g / l passivating solution, more preferably 4-5 g / l passivating solution.

Ferner enthält die Passivierungslösung gemäß dieser Erfindung Fluoridionen. Die Fluoridionen liegen in der Passivierungslösung in einer Menge von 0,3 - 3 g/l Passivierungslösung, besonders bevorzugt 1 - 1,5 g/l Passivierungslösung vor.Further, the passivating solution according to this invention contains fluoride ions. The fluoride ions are present in the passivation solution in an amount of 0.3-3 g / l passivating solution, more preferably 1-1.5 g / l passivating solution.

Als Fluoridionen können alle löslichen Fluoridverbindungen eingesetzt werden. Bevorzugt verwendet werden Natriumfluorid, NaF, Kaliumfluorid, KF, Ammoniumfluorid, NH4F, Natriumbifluorid, NaF·HF, Kaliumbifluorid, KF·HF, Ammoniumbifluorid, NH4F·HF. Ganz besonders bevorzugt ist die Verwendung von Natriumfluorid, NaF.As fluoride ions, all soluble fluoride compounds can be used. Preferred are sodium fluoride, NaF, potassium fluoride, KF, ammonium fluoride, NH 4 F, sodium bifluoride, NaF · HF, potassium bifluoride, KF · HF, ammonium bifluoride, NH 4 F · HF. Very particularly preferred is the use of sodium fluoride, NaF.

Die Passivierungslösung gemäß der vorliegenden Erfindung enthält außerdem Nitrationen. Die Menge an Nitrationen beträgt 3 - 35 g/l Passivierungslösung, besonders bevorzugt 15 - 25 g/l. Die Nitrationen können der Passivierungslösung in jeglicher Form eines löslichen Nitratsalzes zugegeben werden. Es kann auch eine Kombination aus mehreren unterschiedlichen löslichen Nitratsalzen verwendet werden. Beispielsweise können die Nitrationen zusammen mit den Cr(III)-Ionen als Chromnitrat, Cr(NO3)3·9H2O, zugefügt werden. Ein weiteres geeignetes Nitratsalz ist z.B. Natriumnitrat. Wenn die Zugabe der Nitrationen in Form von Natriumnitrat erfolgt, ist im Hinblick auf die bevorzugte Gesamtnitratkonzentration zu berücksichtigen, in welcher Form die Zugabe der Chromverbindung erfolgt.The passivation solution according to the present invention also contains nitrate ions. The amount of nitrate ion is 3-35 g / l passivating solution, more preferably 15-25 g / l. The nitrate ions can be added to the passivating solution in any form of soluble nitrate salt. It is also possible to use a combination of several different soluble nitrate salts. For example, the nitrate ions may be added together with the Cr (III) ions as the chromium nitrate, Cr (NO 3 ) 3 .9H 2 O. Another suitable nitrate salt is, for example, sodium nitrate. When the nitrate ion addition is in the form of sodium nitrate, it should be considered in terms of the preferred total nitrate concentration in which form the addition of the chromium compound occurs.

Nach der Erfindung in Anspruch 1 wird beansprucht eine Passivierungslösung, die Cr(III)-Ionen in einer Menge von 1 - 10 g/l Passivierungslösung, Fluoridionen in einer Menge von 0,3 - 3 g/l Passivierungslösung, Nitrationen in einer Menge von 3 - 35 g/l Passivierungslösung und Dithiodiglykolsäure oder ein Salz davon in einer Menge, bezogen auf Dithiodiglykolsäure, von g/l enthält.According to the invention in claim 1, a passivating solution is claimed which comprises Cr (III) ions in an amount of 1-10 g / l passivating solution, fluoride ions in an amount of 0.3-3 g / l passivating solution, nitrate ions in an amount of 3 - 35 g / l passivation solution and dithiodiglycolic acid or a salt thereof in an amount, based on dithiodiglycolic acid, of g / l.

Gemäß der vorliegenden Erfindung ist eine saure, wässrige Passivierungslösung, die folgende Bestandteile enthält, ganz besonders bevorzugt: Cr(III)-Ionen in einer Menge von 4 - 5 g/l Passivierungslösung, Fluoridionen in einer Menge von 1 - 1,5 g/l Passivierungslösung, Nitrationen in einer Menge von 15 - 25 g/l Passivierungslösung und Dithiodiglykolsäure oder ein Salz davon in einer Menge, bezogen auf Dithiodiglykolsäure, von 4 - 6 g/l.According to the present invention, an acidic, aqueous passivating solution containing the following constituents is very particularly preferred: Cr (III) ions in an amount of 4-5 g / l passivating solution, fluoride ions in an amount of 1-1.5 g / Passivation solution, nitrate ions in an amount of 15-25 g / l passivating solution and dithiodiglycolic acid or a salt thereof in an amount, based on dithiodiglycolic acid, of 4-6 g / l.

Außerdem kann die Passivierungslösung der vorliegenden Erfindung Cobaltionen enthalten. Der Einbau von Cobaltionen in Passivierungen auf Basis dreiwertiger Chromverbindungen ist bekannt und dient einer weiteren Verbesserung der Korrosionsbeständigkeit. Die Konzentration an Cobaltionen in der Passivierungslösung ist bevorzugt 0,1 - 10 g/l Passivierungslösung, besonders bevorzugt 0,5 - 5 g/l. Die Zugabe der Cobaltionen kann in jeglicher Form von wasserlöslichen Cobaltsalzen erfolgen. Bevorzugt sind Cobaltsulfat, Cobaltchlorid oder Cobaltnitrat.In addition, the passivation solution of the present invention may contain cobalt ions. The incorporation of cobalt ions in passivations based on trivalent chromium compounds is known and serves to further improve the corrosion resistance. The concentration of cobalt ions in the passivating solution is preferably 0.1-10 g / l passivating solution, more preferably 0.5-5 g / l. The addition of the cobalt ions can be carried out in any form of water-soluble cobalt salts. Preference is given to cobalt sulfate, cobalt chloride or cobalt nitrate.

Der pH-Wert der Passivierungslösung der vorliegenden Erfindung wird geeignet eingestellt auf einen bevorzugten Bereich von 1,8 bis 2,2, besonders bevorzugt 1,9 bis 2,1.The pH of the passivating solution of the present invention is suitably adjusted to a preferred range of 1.8 to 2.2, more preferably 1.9 to 2.1.

Mit der vorliegenden Erfindung wird weiterhin ein Verfahren zur Erzeugung von schwarzen Passivierungsschichten auf Zink- und Zinkeisenschichten unter Verwendung der oben beschriebenen Passivierungslösung zur Verfügung gestellt. In dem Verfahren der vorliegenden Erfindung wird dazu ein Werkstück, das mit einer Zink- oder Zinkeisenschicht versehen ist, mit der Passivierungslösung in Kontakt gebracht. Das Inkontaktbringen kann ein Sprühen, Schwallen oder Tauchen sein. Bevorzugt wird in der Technik das Tauchen eingesetzt. Die Reaktionstemperatur ist vorzugsweise 10 - 70 °C. Besonders bevorzugt ist ein Temperaturbereich von 15 - 50 °C, noch bevorzugter 20 - 50 °C. Die Werkstücke werden mit der Passivierungslösung für eine Dauer von vorzugsweise 60 - 90 Sekunden, besonders bevorzugt 75 Sekunden, in Kontakt gebracht. D.h., wenn die Werkstücke in die Passivierungslösung eingetaucht werden, beträgt die Tauchzeit vorzugsweise 60 - 90 Sekunden. Besonders bevorzugt ist eine Tauchzeit von 75 Sekunden. Gemäß der vorliegenden Erfindung kann die schwarze Passivierungsschicht auf einer Zink- oder Zinkeisenlegierungsschicht gebildet werden. Bevorzugt ist jedoch die Anwendung des erfindungsgemäßen Verfahrens auf Reinzinkschichten. Dadurch entfällt die aufwendige Prozesskontrolle, die verfahrensbedingt bei jedem Elektrolyten zur Abscheidung einer Legierung anfällt.The present invention further provides a process for producing black passivation layers on zinc and zinc iron layers using the passivation solution described above. In the method of the present invention, for this purpose, a workpiece provided with a zinc or zinc iron layer is brought into contact with the passivating solution. The contacting may be spraying, swelling or dipping. Preferably, dipping is used in the art. The reaction temperature is preferably 10 to 70 ° C. Particularly preferred is a temperature range of 15-50 ° C, more preferably 20-50 ° C. The workpieces are with the Passivation for a period of preferably 60- 90 seconds, more preferably 75 seconds, brought into contact. That is, when the workpieces are dipped in the passivation solution, the dipping time is preferably 60-90 seconds. Particularly preferred is a dive time of 75 seconds. According to the present invention, the black passivation layer may be formed on a zinc or zinc iron alloy layer. However, preference is given to the application of the method according to the invention to pure zinc coatings. This eliminates the costly process control, which is due to the process of each electrolyte for the deposition of an alloy.

Nachdem die Werkstücke mit der sauren, wässrigen Passivierungslösung der vorliegenden Erfindung in Kontakt gebracht und so die schwarze Passivierungsschicht erzeugt wurde, kann auf die schwarze Passivierungsschicht zusätzlich eine Versiegelungsschicht, ein sogenannter "Topcoat", aufgebracht werden. Solch eine Versiegelungsschicht ist bekannt und verbessert die Korrosionsbeständigkeit. Dazu wird das Werkstück mit einer Versiegelungslösung in Kontakt gebracht. Dabei handelt es sich um eine wässrige Lösung, die organische, wasserlösliche oder dispergierbare Polymere enthält. Beispielsweise werden Copolymere von Acrylsäure oder Methacrylsäure mit Ethylen, kommerziell erhältlich unter der Bezeichnung Lugalavan DC der Fa. BASF, eingesetzt. Anorganische Versiegelungslösungen enthalten kolloidale Kieselsäuren. Es ist weiterhin möglich, Mischungen aus wässrigen Lösungen mit organischen Polymeren und wässrigen Lösungen mit kolloidalen Kieselsäuren herzustellen und diese als Versiegelungslösung einzusetzen.After the workpieces have been brought into contact with the acidic, aqueous passivating solution of the present invention and thus the black passivation layer has been produced, a sealing layer, a so-called "topcoat", can additionally be applied to the black passivation layer. Such a sealing layer is known and improves corrosion resistance. For this purpose, the workpiece is brought into contact with a sealing solution. It is an aqueous solution containing organic, water-soluble or dispersible polymers. For example, copolymers of acrylic acid or methacrylic acid with ethylene, commercially available under the name Lugalavan DC Fa. BASF, are used. Inorganic sealant solutions contain colloidal silicic acids. It is also possible to prepare mixtures of aqueous solutions with organic polymers and aqueous solutions with colloidal silicas and to use these as a sealing solution.

Schließlich wird durch die vorliegende Erfindung auch eine schwarze Passivierungsschicht bereitgestellt, die durch das oben beschriebene Verfahren erhältlich ist. Vorzugsweise ist die schwarze Passivierungsschicht auf einer Reinzinkschicht gebildet.Finally, the present invention also provides a black passivation layer obtainable by the method described above. Preferably, the black passivation layer is formed on a pure zinc layer.

BeispieleExamples Beispiel 1example 1

Zunächst wird eine Lösung aus Cr(III) und Fluoridionen mit folgender Zusammensetzung hergestellt:

  • 233 g Chromnitrat

            (Cr(NO3) x 9H2O)

    20 g Natriumfluorid (NaF)
  • 250 g Wasser
First, a solution of Cr (III) and fluoride ions is prepared having the following composition:
  • 233 g of chromium nitrate

    (Cr (NO 3 ) x 9H 2 O)

    20 g sodium fluoride (NaF)
  • 250 g of water

Der Ansatz wird 30 Minuten auf 65 °C erwärmt, anschließend auf Raumtemperatur abgekühlt. Danach wird mit entionisiertem Wasser auf 1 Liter aufgefüllt.The mixture is heated to 65 ° C for 30 minutes, then cooled to room temperature. It is then made up to 1 liter with deionized water.

Zur Herstellung der Passivierungslösung wird die oben erhaltene Lösung mit folgenden Bestandteilen umgesetzt:

  • 130 ml der oben erhaltenen Lösung aus Cr-nitrat und NaF
  • 8 g Cobaltsulfat (CoSO4 x 7H2O)
  • 10 g Natriumnitrat (NaNO3)
  • 12 g Diammoniumdithiodiglykolatlösung (48 Gew.%)
To prepare the passivation solution, the solution obtained above is reacted with the following constituents:
  • 130 ml of the solution of Cr nitrate and NaF obtained above
  • 8 g cobalt sulphate (CoSO 4 .7H 2 O)
  • 10 g of sodium nitrate (NaNO 3 )
  • 12 g of diammonium dithiodiglycolate solution (48% by weight)

Das Volumen wurde mit entionisiertem Wasser auf annähernd 1 Liter aufgefüllt, anschließend wurde der pH-Wert mit konz. Salpetersäure (53 Gew.%) auf 1,8 - 1,9 eingestellt und zum Endvolumen von 1 Liter aufgefüllt.The volume was made up to approximately 1 liter with deionized water, then the pH was reduced with conc. Nitric acid (53 wt.%) Adjusted to 1.8 to 1.9 and made up to the final volume of 1 liter.

In einem alkalischen Zinkbad (ZINCASLOT 50 der Fa. Dr.-Ing. Max Schlötter) wurden Stahlbleche nach üblicher Vorbehandlung bei einer Stromdichte von 2 A/dm2 bei einer Dauer von 30 Minuten verzinkt. Die Schichtdicke betrug 8 µm. Nach der Abscheidung wurde das Testblech in entionisiertem Wasser gespült, 5 Sekunden in einer verdünnten Salpetersäurelösung (10 ml/l HNO3 53 Gew.%) getaucht und anschließend in der oben angegebenen Passivierungslösung bei folgenden Bedingungen getaucht: Temperatur: 25 °C pH-Wert: 1,8 - 1,9 Tauchzeit: 60 Sekunden In an alkaline zinc bath (ZINCASLOT 50 from Dr.-Ing. Max Schlötter), steel sheets were galvanized after conventional pretreatment at a current density of 2 A / dm 2 over a period of 30 minutes. The layer thickness was 8 μm. After deposition, the test sheet was rinsed in deionized water, immersed in dilute nitric acid solution (10 ml / l HNO 3 53% by weight) for 5 seconds and then in the above immersed in the following conditions: Temperature: 25 ° C PH value: 1.8 - 1.9 Dive time: 60 seconds

Das Testblech wurde anschließend mit entionisiertem Wasser gespült und in einem Trockenschrank bei 80 °C für 15 Minuten getrocknet. Das Aussehen des Testbleches war danach tiefschwarz mit geringfügig bräunlich irisierenden Stellen.The test sheet was then rinsed with deionized water and dried in a drying oven at 80 ° C for 15 minutes. The appearance of the test sheet was then deep black with slightly brownish iridescent spots.

Beispiel 2Example 2

Das Beispiel 1 wurde wie beschrieben wiederholt. Nach dem Passivieren und Spülen wurde in eine Versiegelungslösung getaucht (SLOTOFIN 70 der Fa. Dr.-Ing. Max Schlötter, wässrige Dispersion eines Copolymers aus Acrylsäure und Ethylen).Example 1 was repeated as described. After passivation and rinsing, it was immersed in a sealing solution (SLOTOFIN 70 from Dr.-Ing. Max Schlötter, aqueous dispersion of a copolymer of acrylic acid and ethylene).

Bedingungen:Conditions:

300 ml/l Versiegelungskonzentrat SLOTOFIN 71300 ml / l sealing concentrate SLOTOFIN 71 Tauchzeit:Dive time: 30 Sekunden30 seconds Abtropfzeit:Drip: 60 Sekunden60 seconds Temperatur:Temperature: 25 °C25 ° C

Nach dem Versiegeln wurde das Testblech ohne Spülen bei 80 °C für 15 Minuten in einem Trockenschrank getrocknet.After sealing, the test sheet was dried without rinsing at 80 ° C for 15 minutes in a drying oven.

Das versiegelte Testblech hatte ein gleichmäßig tiefschwarzes, halbglänzendes Aussehen.The sealed test sheet had a uniform deep black, semi-glossy appearance.

Korrosionsprüfungencorrosion tests

Testbleche, die entsprechend den Beispielen 1 und 2 hergestellt wurden, wurden in einer Korrosionsprüfung im neutralen Salzsprühtest nach DIN EN ISO 9227 geprüft. In Anlehnung an DIN 50 979 wurde 1 Probe ohne zusätzliche Wärmebehandlung geprüft und 1 Probe wurde 24 Stunden bei 120 °C getempert. Korrosionsschutz ohne Wärmebehandlung mit Wärmebehandlung (120 °C/24h) Beispiel 1 72 h 72 h Beispiel 2 > 240 h > 240 h Test panels, which were prepared according to Examples 1 and 2, were tested in a corrosion test in the neutral salt spray test according to DIN EN ISO 9227. Following DIN 50 979, 1 sample was tested without additional heat treatment and 1 sample was annealed at 120 ° C. for 24 hours. corrosion protection without heat treatment with heat treatment (120 ° C / 24h) example 1 72 h 72 h Example 2 > 240 h > 240 h

Vergleichsbeispiel 1Comparative Example 1

Entsprechend Beispiel 1 wurde zunächst eine Lösung aus Chromnitrat und Natriumfluorid hergestellt. Anschließend wurde eine Lösung mit folgender Zusammensetzung hergestellt.

  • 130 ml der Lösung aus Cr-nitrat und NaF gemäß Beispiel 1
  • 8 g Cobaltsulfat

            (CoSO4 × 7H2O)

  • 10 g Natriumnitrat

            (NaNO3)

  • 12 g Thiodiglykolsäure
According to Example 1, a solution of chromium nitrate and sodium fluoride was first prepared. Subsequently, a solution having the following composition was prepared.
  • 130 ml of the solution of Cr nitrate and NaF according to Example 1
  • 8 g of cobalt sulfate

    (CoSO 4 × 7H 2 O)

  • 10 g of sodium nitrate

    (NaNO 3 )

  • 12 g of thiodiglycolic acid

Das Volumen wurde mit entionisiertem Wasser auf annähernd 1 Liter aufgefüllt, anschließend wurde der pH-Wert mit konz. Salpetersäure (53 Gew.%) auf 1,8 - 1,9 eingestellt und zum Endvolumen von 1 Liter aufgefüllt.The volume was made up to approximately 1 liter with deionized water, then the pH was reduced with conc. Nitric acid (53 wt.%) Adjusted to 1.8 to 1.9 and made up to the final volume of 1 liter.

In einem alkalischen Zinkbad verzinkte Stahlbleche wurden, wie in Beispiel 1 angegeben, in der oben angegebenen Passivierungslösung behandelt. Es konnte keine Schwarzfärbung erzielt werden.Steel plates galvanized in an alkaline zinc bath were treated in the above-indicated passivation solution as indicated in Example 1. It could not be achieved blackening.

Vergleichsbeispiel 2Comparative Example 2

Es wurde eine Passivierungslösung wie in Vergleichsbeispiel 1 angesetzt, jedoch wurde Thiodiglykolsäure durch 4 g Cystin ersetzt. Bei der Passivierungsreaktion wurde keine Schwarzfärbung erzielt.A passivation solution was prepared as in Comparative Example 1, but thiodiglycolic acid was replaced by 4 g of cystine. The passivation reaction did not result in blackening.

Claims (6)

  1. Acid, aqueous passivation solution for generating black passivation layers on zinc or zinc-iron alloy layers containing
    - Cr(III) ions,
    - fluoride ions and
    - nitrate ions,
    characterised in that the passivation solution additionally contains dithiodiglycolic acid or a salt of this acid, and wherein
    - Cr(III) ions in a quantity of 1 - 10 g/l of passivation solution,
    - fluoride ions in a quantity of 0.3 - 3 g/l of passivation solution,
    - nitrate ions in a quantity of 3 - 35 g/l of passivation solution and
    - dithiodiglycolic acid or a salt thereof in a quantity, relative to dithiodiglycolic acid, of 2 - 10 g/l are present in the passivation solution.
  2. Passivation solution according to claim 1, wherein the passivation solution has a pH value of 1.8 to 2.2.
  3. Method for generating black passivation layers on a zinc or zinc-iron alloy layer, characterised in that a workpiece coated with a zinc or zinc-iron alloy layer is brought into contact with the acid, aqueous passivation solution according to one or more of claims 1-2.
  4. Method according to claim 3, wherein the workpiece is brought into contact with the passivation solution at a reaction temperature of 10 - 70°C.
  5. Method according to claim 3 or 4, wherein the workpiece is brought into contact with the passivation solution for a period of 60 - 90 seconds.
  6. Method according to one or more of claims 3-5, wherein the black passivation layer is formed on a pure zinc layer.
EP10175959.5A 2009-10-12 2010-09-09 Black passivation of zinc and zinc-iron layers Active EP2319957B1 (en)

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PL2784188T5 (en) 2013-03-26 2018-10-31 Atotech Deutschland Gmbh Process for corrosion protection of iron containing materials
CN103741128B (en) * 2014-01-06 2016-01-20 哈尔滨三泳金属表面技术有限公司 Electro-galvanizing floor height is anti-corrosion trivalent chromium colour passivator
DE102016114808B4 (en) * 2016-08-10 2023-06-07 Harting Electric Stiftung & Co. Kg Connector with connector housing protected against corrosion

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GB1532230A (en) * 1975-11-24 1978-11-15 Imasa Ltd Treatment of chromated metal surfaces with sulphur-compounds
FR2812307B1 (en) 2000-07-25 2003-02-14 Chemetall S A ANTI-CORROSIVE BLACK LAYER ON A ZINC ALLOY AND PROCESS FOR PREPARING THE SAME
JP3774415B2 (en) 2002-03-14 2006-05-17 ディップソール株式会社 A treatment solution for forming a black hexavalent chromium-free conversion coating on zinc and zinc alloy plating and a method of forming a black hexavalent chromium-free conversion coating on zinc and zinc alloy plating.
JP4508634B2 (en) * 2003-12-26 2010-07-21 株式会社タイホー Metal surface treatment agent, metal surface treatment liquid, corrosion-resistant colored film formed thereby, corrosion-resistant colored part having this corrosion-resistant colored film, and method for producing this corrosion-resistant colored part
DE102004001945A1 (en) 2004-01-14 2005-08-11 Ina-Schaeffler Kg Black passivation of zinc or zinc alloy surfaces
JP4628726B2 (en) * 2004-03-02 2011-02-09 日本表面化学株式会社 Aluminum member, method for producing the same, and chemical for production
WO2007094496A1 (en) 2006-02-17 2007-08-23 Dipsol Chemicals Co., Ltd. Treatment solution for forming of black trivalent chromium chemical coating on zinc or zinc alloy and method of forming black trivalent chromium chemical coating on zinc or zinc alloy
US7842403B2 (en) * 2006-02-23 2010-11-30 Atotech Deutschland Gmbh Antifriction coatings, methods of producing such coatings and articles including such coatings
JP4840790B2 (en) * 2008-09-29 2011-12-21 ユケン工業株式会社 Chemical conversion composition and method for producing member having black film using the composition

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