EP1816234A1 - Aqueous passivating coating composition for zinc or zinc alloys and method for using same as well as the use of a compound selected from the group comprising nicotinic acid, its salts and derivates - Google Patents

Aqueous passivating coating composition for zinc or zinc alloys and method for using same as well as the use of a compound selected from the group comprising nicotinic acid, its salts and derivates Download PDF

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Publication number
EP1816234A1
EP1816234A1 EP06001930A EP06001930A EP1816234A1 EP 1816234 A1 EP1816234 A1 EP 1816234A1 EP 06001930 A EP06001930 A EP 06001930A EP 06001930 A EP06001930 A EP 06001930A EP 1816234 A1 EP1816234 A1 EP 1816234A1
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EP
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Prior art keywords
reaction solution
zinc
aqueous reaction
acid
workpieces
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EP06001930A
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German (de)
French (fr)
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EP1816234B1 (en
Inventor
Lee Capper
Andreas Noack
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to DE502006003710T priority Critical patent/DE502006003710D1/en
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to PL06001930T priority patent/PL1816234T3/en
Priority to EP06001930A priority patent/EP1816234B1/en
Priority to AT06001930T priority patent/ATE431442T1/en
Priority to US12/086,796 priority patent/US8262811B2/en
Priority to CN2007800013029A priority patent/CN101356301B/en
Priority to JP2008551736A priority patent/JP5130226B2/en
Priority to CA2624215A priority patent/CA2624215C/en
Priority to EP07703155A priority patent/EP1979507A1/en
Priority to PCT/EP2007/000805 priority patent/WO2007088030A1/en
Publication of EP1816234A1 publication Critical patent/EP1816234A1/en
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Publication of EP1816234B1 publication Critical patent/EP1816234B1/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
    • C23C22/82—After-treatment
    • C23C22/84—Dyeing
    • 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
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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

Definitions

  • the present invention relates to an aqueous reaction solution and a process for passivating zinc and zinc alloys and to a use of a compound selected from the group comprising nicotinic acid, its salts and their derivatives, for producing colored passivation layers on zinc and zinc alloys.
  • Metallic materials are galvanized or cemented to protect them from corrosive environmental influences.
  • the corrosion protection of zinc is based on the fact that it is still less noble than the base metal and therefore initially attracts only the corrosive attack, it acts as a sacrificial layer.
  • the base metal of the galvanized component in question remains intact while it is still completely covered with zinc, and the mechanical functionality is retained for longer periods of time than with non-galvanized parts.
  • thick zinc coatings provide a higher level of corrosion protection than thin layers - the corrosive removal of thick layers takes even longer.
  • the corrosive attack on the zinc layer in turn can be greatly delayed by the application of a chromating, and thus the base metal corrosion is pulled even further than by galvanizing alone.
  • the corrosion protection provided by the zinc / chromate coating system is considerably better than that afforded by a zinc layer of the same thickness.
  • the visual impairment of a component by environmental influences is also drawn by a chromating - even the corrosion products of zinc, the so-called white rust, have a disturbing effect on the appearance of a component.
  • the Blauchromatleiterstik is up to 80 nm thick, pale blue in the intrinsic color and has, depending on the layer thickness on a light refraction generated golden, reddish, bluish, greenish or yellow Irisier case. Very thin chromate layers with almost no inherent color are classified as colorless chromatographies (group A).
  • the chromating solution may in both cases consist of both hexavalent and trivalent chromates, as well as mixtures of both, and also of conducting salts and mineral acids. There are fluoride-containing and fluoride-free variants.
  • the chromating solutions are applied at room temperature.
  • the corrosion protection of unimpaired blue chromations amounts to 10 to 40 hours in a salt spray cabinet according to DIN 50021 SS until the first appearance of corrosion products.
  • the minimum requirement for process groups A and B according to DIN 50961 Chapter 10 Table 3 is 8 hours for drum products and 16 hours for rack goods.
  • the yellow chromating layer is about 0.25-1 ⁇ m thick, golden yellow in color and often strongly red-green iridescent.
  • the chromating solution consists essentially of hexavalent chromates, conductive salts and mineral acids dissolved in water.
  • the yellow one Color is due to the significant fraction (80-220 mg / m 2 ) of hexavalent chromium that is incorporated in addition to the trivalent chromium generated by the layering reaction by reduction.
  • the chromating solutions are applied at room temperature.
  • the corrosion protection of undamaged yellow chromations amounts to 100 - 200 h in salt spray cabinets according to DIN 50021 SS until the first appearance of corrosion products.
  • the minimum requirement for process group C according to DIN 50961 chapter 10, table 3 is 72 hours for drum products and 96 hours for rack goods.
  • the typical Olivchromatierungs slaughter is up to 1.5 microns thick, covering olive green to olive brown.
  • the chromating solution consists essentially of hexavalent chromates, conductive salts and mineral acids, in particular phosphates or phosphoric acid, dissolved in water, and may also contain formates. Substantial amounts of chromium (VI) (300-400 mg / m 2 ) are incorporated in the layer.
  • the chromating solutions are applied at room temperature.
  • the corrosion protection of undamaged olive chromations amounts to 200 - 400 h in Salzsprüh published according to DIN 50021 SS until the first occurrence of corrosion products.
  • the minimum requirement for process group D according to DIN 50961 Chapter 10 Table 3 is 72 hours for drum products and 120 hours for rack goods.
  • the black chromating layer is basically a yellow or olive chromating in which colloidal silver is incorporated as a pigment.
  • the chromating solutions have approximately the same composition as yellow or olive chromatids and additionally contain silver ions.
  • zinc alloy layers such as Zn / Fe, Zn / Ni or Zn / Co, with a suitable composition of the chromating solution, iron, nickel or cobalt oxide as black pigment accumulates in the chromate layer, so that in these cases silver is not required.
  • Significant amounts of chromium (VI) are incorporated in the chromate layers, depending on whether yellow or olive chromate is the base, between 80 and 400 mg / m 2 .
  • the chromating solutions are used at room temperature.
  • Tetravalent cerium is an even stronger oxidizing agent than hexavalent chromium, which is why Ce (IV) from Cr (III) will produce the Cr (VI) to be avoided.
  • Cr (VI) has a very strong yellow color and is known as a corrosion inhibitor.
  • the in the U.S. Patent 4,384,902 thus described layer is not free of hexavalent chromium.
  • U.S. Patent 4,359,348 also describes passivation layers that meet the above salt spray test requirements. Again, it is in all cases a cerium-containing layer having a yellowish coloration highlighted by the cerium (IV) ion. This document is therefore not over U.S. Patent 4,384,902 out.
  • GB-A-2 097 024 the treatment of metal surfaces to improve corrosion protection on zinc and zinc alloy surfaces with an aqueous acidic solution comprising an oxidizing agent and at least one metal selected from the group consisting of iron, cobalt, nickel, molybdenum, manganese, aluminum, lanthanum, lanthanide mixtures or cerium ions or mixtures thereof and in particular iron and cobalt ions.
  • an aqueous acidic solution comprising an oxidizing agent and at least one metal selected from the group consisting of iron, cobalt, nickel, molybdenum, manganese, aluminum, lanthanum, lanthanide mixtures or cerium ions or mixtures thereof and in particular iron and cobalt ions.
  • GB-A-2 097 024 the use of trivalent chromium ions and iron ions in combination with an additional metal selected from the group consisting of the abovementioned ions or cerium ions, but mainly describes combinations of chromium (III) in combination with an
  • chelating ligands form kinetically less stable complexes with chromium (III), from which this is released rapidly and stored at high reaction rate in the growing ZnCrO layer.
  • metal ions such as divalent cobalt ions in the form of soluble salts are added to increase the reaction rate and the thickness growth of the chromate layer.
  • the passivation layers produced in this way are chromium (VI) -free and allow corrosion protection of up to more than 100 h, which corresponds approximately to that of conventional yellow chromating.
  • the chromate layers produced in this way have a greenish, red-green iridescent color.
  • An alternative, in DE 41 35 524 A1 described method of passivation which is based on a chromium (III) oxalate complex, in turn provides a blue passivation film.
  • DE 103 05 449 A1 describes a mixture of substances and a process for producing colored passivation layers which are each based on a combination of a reaction solution containing chromium (III) ions with a quinoline dye.
  • the disadvantage here is the lack of resistance of the quinoline dye both in the reaction solution and in the passivation layer. Among other things, this is due to the lack of UV resistance of such compounds.
  • chromium (III) passivations still allow only limited applications.
  • chromium (III) passivation In addition to the usually weak in blue rippling corrosion protection and the risk of chromium (VI) residues are in particular the limited possibilities of achievable with chromium (III) passivation coloring of disadvantage.
  • the colors produced by chromium (III) passivation are essentially limited to blue and greenish chromate layers, whereas chromium (III) based yellow chromates do not allow a uniform and strong yellowing, but to bright, clearly iridescent or bluish or greenish going coatings to lead.
  • the present invention is therefore based on the object to provide a solution and a process for the preparation of chromium (III) -containing and chromium (VI) -free yellow passivation layers which are color intensive and long-term stable.
  • the invention is particularly suitable for producing yellow, largely chromium (VI) -free passivation layers on zinc and zinc alloys.
  • the effect of the yellow passivation is achieved according to the present invention by an aqueous reaction solution which reaches chromium (III) ions, at least one acid and at least one heteroaromatic compound selected from the group comprising nicotinic acid, its salts and their derivatives.
  • chromium (III) ions at least one acid and at least one heteroaromatic compound selected from the group comprising nicotinic acid, its salts and their derivatives.
  • the addition of the heteroaromatic compounds gives stable chemical compositions for the passivation of zinc and zinc alloys. Nicotinic acid is used as the preferred heteroaromatic compound.
  • salts in particular the sodium or potassium salt, can also be used. This facilitates the dissolution of the acid in aqueous solutions.
  • concentrations of the heteroaromatic acids are highly dependent on the desired color intensity of the yellow passivation and may generally be at least 0.5 g / l.
  • the upper concentration limit may be 40 g / l, preferably 30 g / l.
  • a preferred concentration of the heteroaromatic compounds is at least 10 g / l, more preferably at least 15 g / l.
  • the concentration of these compounds is preferably at most 20 g / l.
  • the higher the content of nicotinic acid the more intense is the yellow coloration.
  • concentration of more than 20 g / l nicotinic acid however, hardly any increase in color intensity is observed. If the aforementioned concentration limits are converted into mol / l, these also apply to the salts of nicotinic acid and their derivatives.
  • the yellow color is, among other things, of great practical use, since it is used in the processing of mass parts, for example in the automotive industry, to distinguish workpieces. For example, can be reliably and easily distinguished by targeted coloring with the composition of the invention right- and left-handed components. This enormously increases process reliability, especially when processing very similar components in large numbers.
  • the layer according to the invention is produced without an oxidizing agent and therefore free of hexavalent chromium.
  • Workpieces provided with such layers have a very high corrosion resistance which is comparable or even better than that of galvanized surfaces provided with yellow chromating.
  • the pH of the reaction solution used for carrying out may be, for example, at least about 1.5, preferably at least about 1.8.
  • the upper pH limit may be 3.0, preferably 2.2.
  • the desired pH value can be generated by adding hydrogen ions, ie by adding at least one acid, preferably nitric acid or another mineral or carboxylic acid, and then adjusted exactly with sodium hydroxide solution.
  • the concentration of the dissolved chromium (III) ions may be at least 0.2 g / l, preferably at least 1 g / l. It can be in a range up to a maximum of 30 g / l, preferably up to a maximum of 5 g / l.
  • the chromium (III) compounds can also be present in the reaction solution in a concentration up to the saturation limit. Chromium chloride (CrCl 3 ), chromium nitrate (Cr (NO 3 ) 3 ), chromium sulfate (Cr 2 (SO 4 ) 3 ) or another water-soluble chromium (III) salt may be used as the source of the chromium (III) ions.
  • These metal ions may be added to the reaction solution as soluble salts, preferably as nitrates, sulfates or halides.
  • cobalt (II) ions are contained in a concentration of at least about 0.1 g / L. Their concentration may preferably reach up to 5 g / l.
  • Co (NO 3 ) 2 Water-containing or anhydrous cobalt nitrates (Co (NO 3 ) 2 ), cobalt sulfates (CoSO 4 ) or cobalt chloride (CoCl 2 ) are examples of suitable cobalt (II) sources.
  • the chemical composition may contain at least one acid-stable water-soluble silicate in order to improve the passivating properties and to impart a higher hardness to the passivation layer.
  • concentration is preferably at least 0.5 g / l.
  • the upper concentration limit is preferably 10 g / l. These concentration values relate in each case to SiO 2 .
  • Usable silicates may be both inorganic and organic, as long as they are soluble in the reaction solution. Organic silicates are preferable because of their stabilizing property in terms of bath life. Useful inorganic silicates may be acid stable colloidal solutions of silica. Organic silicates can also be used.
  • Such silicates may in particular be tetramethylammonium silicate, phenyltrimethylammonium silicate, disilicate and trisilicate and also benzyltrimethylammonium silicate and disilicate.
  • Such organic silicates can be synthesized by conventional chemical methods. For example, methods of synthesis by Merrill and Spencer, "Some Quaternary Ammonium Silicates", Journal of Physical and Colloid Chemistry, 55, 187 (1951) and in U.S. Patent 3,993,548 described.
  • the reaction solution may contain halides, in particular chloride and fluoride, sulfate ions, nitrate ions, phosphoric acid, phosphoric acid esters or phosphate ions, silicates, silicic acids, amino acids, amines and surfactants.
  • Suitable surfactants are, for example, aliphatic fluorocarbonsulfonates, such as the Fluorad® products from 3M Comp., US, such as Fluorad FC 98.
  • chelating agents may be present for chromium (III) ions, such as malonic acid and oxalic acid.
  • the reaction solution according to the invention can preferably be used to provide workpieces with surfaces of zinc or zinc alloys with a passivation layer.
  • both workpieces are passivated, which are provided with a generated by alkaline cyanide or acidic non-cyanide zinc electroplating zinc coating, as well as workpieces that are galvanized by means of a melt or even made of zinc or of a zinc alloy.
  • Zinc alloys on the workpiece surfaces may be, for example, Zn / Fe, Zn / Ni and Zn / Co alloys.
  • reaction solution can also be used to treat workpieces in accordance with the invention in which, in addition to the zinc or zinc alloy surfaces, surfaces which are not zinc or a zinc alloy, for example iron-containing surfaces such as steel surfaces, are also exposed. These other surfaces can be passivated together with the zinc or zinc alloy surfaces.
  • reaction solution according to the invention also for the passage of aluminum, aluminum alloy surfaces and surfaces made of cadmium.
  • the passivation process involves contacting the surfaces of zinc or zinc alloyed workpieces with the reaction solution.
  • the reaction is preferably carried out from a minimum bath temperature of about 10 ° C.
  • the upper bath temperature may be, for example, 80 ° C.
  • Particularly preferred bath temperatures are in the range from 30 ° C to 50 ° C.
  • the workpieces may be contacted with the reaction solution preferably by dipping, i. the workpieces are immersed in the reaction solution contained in a container.
  • the workpieces can either be held on racks and immersed with the racks in the reaction solution or are in a drum or on a horde and immerse with the drum or the Horde in the reaction solution.
  • the workpieces are also contacted by spray dipping with the reaction solution.
  • the workpieces are also brought into contact by spraying with the reaction solution.
  • the workpieces can also be walled with the reaction solution, for example by means of a nozzle, from which a surge of the reaction solution emerges.
  • Yet another method of treatment is to apply the reaction solution to the workpiece surfaces by brushing, rolling or another application technique. The treatment can take place in conventional plants, in which the workpieces are treated batchwise, or in continuous plants, through which the workpieces are continuously passed and treated.
  • the treatment time may be in a range of 20 to 200 s; in a preferred embodiment, it is in the range of about 30 seconds to about 90 seconds. Depending on the technology with which the workpieces are brought into contact with the reaction solution, longer or shorter treatment times may be required.
  • the workpieces are optionally first cleaned before being brought into contact with the reaction solution. However, this can be omitted if the workpieces are brought into contact with the reaction solution immediately after the electrolytic galvanizing and subsequent rinsing of the galvanizing solution.
  • the workpieces are preferably dried, for example with warm air. In addition, the workpieces may also be rinsed before drying to remove excess reaction solution from the surface.
  • the pH of the reaction solution was adjusted to pH 2.0 with nitric acid or sodium hydroxide solution.
  • the solution was heated to 45 ° C. Galvanized parts were held on a rack for 60 seconds immersed in the reaction solution, then rinsed and dried.
  • the resulting passivation layer had a uniform yellow-green iridescent color.
  • Their corrosion resistance in accordance with DIN 50021 SS was determined to be approx. 72 h until the first occurrence of white corrosion.
  • Example 2 The experiment according to the description of Example 1 was repeated, wherein the solution was additionally added 0.5 g / l cobalt (II) nitrate.
  • the corrosion resistance The layer according to DIN 50021 SS was determined to 96 h until the occurrence of white corrosion.
  • the resulting passivation layer had a uniform yellow-green iridescent color.
  • Their corrosion resistance according to DIN 50021 SS was determined to approx. 96 h until the first appearance of white corrosion.

Abstract

Aqueous reaction solution contains trivalent chromium ions and nicotinic acid, its salts and derivatives. An independent claim is also included for a method for passivating surfaces of workpieces made from zinc and zinc alloys.

Description

Die vorliegende Erfindung betrifft eine wässrige Reaktionslösung und ein Verfahren zur Passivierung von Zink- und Zinklegierungen sowie eine Verwendung einer Verbindung, ausgewählt aus der Gruppe, umfassend Nicotinsäure, deren Salze und deren Derivate, zur Erzeugung farbiger Passivierungsschichten auf Zink- und Zinklegierungen.The present invention relates to an aqueous reaction solution and a process for passivating zinc and zinc alloys and to a use of a compound selected from the group comprising nicotinic acid, its salts and their derivatives, for producing colored passivation layers on zinc and zinc alloys.

Metallische Werkstoffe, insbesondere Eisen und Stahl, werden verzinkt oder verkadmet, um sie vor korrosiven Umwelteinflüssen zu schützen. Der Korrosionsschutz des Zinks beruht darauf, dass es noch unedler ist als das Grundmetall und deshalb den korrosiven Angriff zunächst ausschließlich auf sich zieht, es fungiert als Opferschicht. Das Grundmetall des betreffenden verzinkten Bauteils bleibt unversehrt, solange es noch durchgehend mit Zink bedeckt ist, und die mechanische Funktionalität bleibt über längere Zeiträume erhalten als bei unverzinkten Teilen. Dicke Zinkschichten gewähren natürlich einen höheren Korrosionsschutz als dünne Schichten - der korrosive Abtrag von dicken Schichten dauert eben länger.Metallic materials, especially iron and steel, are galvanized or cemented to protect them from corrosive environmental influences. The corrosion protection of zinc is based on the fact that it is still less noble than the base metal and therefore initially attracts only the corrosive attack, it acts as a sacrificial layer. The base metal of the galvanized component in question remains intact while it is still completely covered with zinc, and the mechanical functionality is retained for longer periods of time than with non-galvanized parts. Of course, thick zinc coatings provide a higher level of corrosion protection than thin layers - the corrosive removal of thick layers takes even longer.

Der korrosive Angriff auf die Zinkschicht ihrerseits kann durch das Aufbringen einer Chromatierung stark verzögert werden, und somit wird auch die Grundmetallkorrosion noch weiter hinausgezogen als durch eine Verzinkung alleine. Der Korrosionsschutz durch das Schichtsystem Zink/Chromatierung ist erheblich besser als derjenige, der durch eine nur gleich dicke Zinkschicht gewährt wird. Ferner wird durch eine Chromatierung auch die optische Beeinträchtigung eines Bauteils durch Umwelteinflüsse hinausgezogen - auch die Korrosionsprodukte von Zink, der so genannte Weißrost, wirken sich störend auf das Aussehen eines Bauteils aus.The corrosive attack on the zinc layer in turn can be greatly delayed by the application of a chromating, and thus the base metal corrosion is pulled even further than by galvanizing alone. The corrosion protection provided by the zinc / chromate coating system is considerably better than that afforded by a zinc layer of the same thickness. Furthermore, the visual impairment of a component by environmental influences is also drawn by a chromating - even the corrosion products of zinc, the so-called white rust, have a disturbing effect on the appearance of a component.

Die Vorteile einer aufgebrachten Chromatierung sind so groß, dass fast jede galvanisch verzinkte Oberfläche zusätzlich auch chromatiert wird. Der Stand der Technik kennt vier nach ihren Farben benannte Chromatierungen, die jeweils durch Behandeln (Tauchen, Spritzen, Rollen) einer verzinkten Oberflache mit der entsprechenden wässrigen Chromatierungslösung aufgebracht werden. Ferner sind Gelb- und Grünchromatierungen für Aluminium bekannt, die auf analoge Weise hergestellt werden. Es handelt sich jedenfalls um unterschiedlich dicke Schichten aus im Wesentlichen amorphem Zink/Chromoxid (bzw. Aluminium/Chromoxid) mit unstöchiometrischer Zusammensetzung, einem gewissen Wassergehalt und eingebauten Fremdionen. Bekannt und nach DIN 50960 Teil 1 in Verfahrensgruppen eingeteilt sind:The advantages of applied chromating are so great that almost every galvanized surface is additionally chromated. The prior art knows four colorations named after their colors, which are each applied by treatment (dipping, spraying, rolling) of a galvanized surface with the corresponding aqueous chromating solution. Furthermore, yellow and green chromations for aluminum are known, which are prepared in an analogous manner. In any case, these are layers of substantially amorphous zinc / chromium oxide (or aluminum / chromium oxide) with different stoichiometric composition, a certain water content and incorporated foreign ions. Known and classified according to DIN 50960 Part 1 in process groups:

1) Farblos- und Blauchromatierungen, Gruppen A und B:1) Colorless and blue chromations, groups A and B:

Die Blauchromatierungsschicht ist bis zu 80 nm dick, schwach blau in der Eigenfarbe und weist je nach Schichtdicke eine durch Lichtbrechung erzeugte goldene, rötliche, bläuliche, grünliche oder gelbe Irisierfarbe auf. Sehr dünne Chromatschichten fast ohne Eigenfarbe werden als Farbloschromatierungen (Gruppe A) eingestuft. Die Chromatierungslösung kann in beiden Fällen sowohl aus sechswertigen als auch aus dreiwertigen Chromaten sowie Gemischen aus beiden, ferner aus Leitsalzen und Mineralsäuren bestehen. Es gibt fluoridhaltige und fluoridfreie Varianten. Die Chromatierungslösungen werden bei Raumtemperatur angewendet. Der Korrosionsschutz von unverletzten Blauchromatierungen (Gruppe B) beläuft sich auf 10 - 40 h im Salzsprühschrank nach DIN 50021 SS bis zum ersten Auftreten von Korrosionsprodukten. Die Mindestforderung für die Verfahrensgruppen A und B nach DIN 50961 Kapitel 10 Tabelle 3 beträgt 8 h für Trommelware und 16 h für Gestellware.The Blauchromatierungsschicht is up to 80 nm thick, pale blue in the intrinsic color and has, depending on the layer thickness on a light refraction generated golden, reddish, bluish, greenish or yellow Irisierfarbe. Very thin chromate layers with almost no inherent color are classified as colorless chromatographies (group A). The chromating solution may in both cases consist of both hexavalent and trivalent chromates, as well as mixtures of both, and also of conducting salts and mineral acids. There are fluoride-containing and fluoride-free variants. The chromating solutions are applied at room temperature. The corrosion protection of unimpaired blue chromations (group B) amounts to 10 to 40 hours in a salt spray cabinet according to DIN 50021 SS until the first appearance of corrosion products. The minimum requirement for process groups A and B according to DIN 50961 Chapter 10 Table 3 is 8 hours for drum products and 16 hours for rack goods.

2) Gelbchromatierungen, Gruppe C:2) Yellow Chromatizations, Group C:

Die Gelbchromatierungsschicht ist etwa 0,25 - 1 µm dick, goldgelb gefärbt und häufig stark rotgrün irisierend. Die Chromatierungslösung besteht im Wesentlichen aus in Wasser gelösten sechswertigen Chromaten, Leitsalzen und Mineralsäuren. Die gelbe Farbe rührt von dem signifikanten Anteil (80 - 220 mg/m2) sechswertigen Chroms her, das neben dem bei der Schichtbildungsreaktion durch Reduktion erzeugten dreiwertigen Chrom, eingebaut wird. Die Chromatierungslösungen werden bei Raumtemperatur angewendet. Der Korrosionsschutz von unverletzten Gelbchromatierungen beläuft sich auf 100 - 200 h im Salzsprühschrank nach DIN 50021 SS bis zum ersten Auftreten von Korrosionsprodukten. Die Mindestforderung für die Verfahrensgruppe C nach DIN 50961 Kapitel 10 Tabelle 3 beträgt 72 h für Trommelware und 96 h für Gestellware.The yellow chromating layer is about 0.25-1 μm thick, golden yellow in color and often strongly red-green iridescent. The chromating solution consists essentially of hexavalent chromates, conductive salts and mineral acids dissolved in water. The yellow one Color is due to the significant fraction (80-220 mg / m 2 ) of hexavalent chromium that is incorporated in addition to the trivalent chromium generated by the layering reaction by reduction. The chromating solutions are applied at room temperature. The corrosion protection of undamaged yellow chromations amounts to 100 - 200 h in salt spray cabinets according to DIN 50021 SS until the first appearance of corrosion products. The minimum requirement for process group C according to DIN 50961 chapter 10, table 3 is 72 hours for drum products and 96 hours for rack goods.

3) Olivchromatierungen, Gruppe D:3) Olivchromatations, Group D:

Die typische Olivchromatierungsschicht ist bis zu 1,5 µm dick, deckend olivgrün bis olivbraun. Die Chromatierungslösung besteht im Wesentlichen aus in Wasser gelösten sechswertigen Chromaten, Leitsalzen und Mineralsäuren, insbesondere Phosphaten bzw. Phosphorsäure, und kann auch Formiate enthalten. In die Schicht werden erhebliche Mengen von Chrom(VI) (300 - 400 mg/m2) eingelagert. Die Chromatierungslösungen werden bei Raumtemperatur angewendet. Der Korrosionsschutz von unverletzten Olivchromatierungen beläuft sich auf 200 - 400 h im Salzsprühschrank nach DIN 50021 SS bis zum ersten Auftreten von Korrosionsprodukten. Die Mindestforderung für die Verfahrensgruppe D nach DIN 50961 Kapitel 10 Tabelle 3 beträgt 72 h für Trommelware und 120 h für Gestellware.The typical Olivchromatierungsschicht is up to 1.5 microns thick, covering olive green to olive brown. The chromating solution consists essentially of hexavalent chromates, conductive salts and mineral acids, in particular phosphates or phosphoric acid, dissolved in water, and may also contain formates. Substantial amounts of chromium (VI) (300-400 mg / m 2 ) are incorporated in the layer. The chromating solutions are applied at room temperature. The corrosion protection of undamaged olive chromations amounts to 200 - 400 h in Salzsprühschrank according to DIN 50021 SS until the first occurrence of corrosion products. The minimum requirement for process group D according to DIN 50961 Chapter 10 Table 3 is 72 hours for drum products and 120 hours for rack goods.

4) Schwarzchromatierungen, Gruppe F:4) Black Chromatizations, Group F:

Die Schwarzchromatierungsschicht ist im Grunde eine Gelb- oder Olivchromatierung, in die kolloidales Silber als Pigment eingelagert ist. Die Chromatierungslösungen haben in etwa die gleiche Zusammensetzung wie Gelb- oder Olivchromatierungen und enthalten zusätzlich Silberionen. Auf Zinklegierungsschichten wie Zn/Fe, Zn/Ni oder Zn/Co lagert sich bei geeigneter Zusammensetzung der Chromatierungslösung Eisen-, Nickel- oder Cobaltoxid als Schwarzpigment in die Chromatschicht ein, so dass in diesen Fällen Silber nicht erforderlich ist. In die Chromatschichten werden erhebliche Mengen Chrom(VI) eingebaut, und zwar je nach dem, ob eine Gelb- oder eine Olivchromatierung die Basis darstellt, zwischen 80 und 400 mg/m2. Die Chromatierungslösungen werden bei Raumtemperatur angewendet. Der Korrosionsschutz von unverletzten Schwarzchromatierungen auf Zink beläuft sich auf 50 - 150 h im Salzsprühschrank nach DIN 50021 SS bis zum ersten Auftreten von Korrosionsprodukten. Die Mindestforderung für die Verfahrensgruppe F nach DIN 50961 Kapitel 10 Tabelle 3 beträgt 24 h für Trommelware und 48 h für Gestellware. Schwarzchromatierungen auf Zinklegierungen liegen erheblich oberhalb der genannten Werte.The black chromating layer is basically a yellow or olive chromating in which colloidal silver is incorporated as a pigment. The chromating solutions have approximately the same composition as yellow or olive chromatids and additionally contain silver ions. On zinc alloy layers such as Zn / Fe, Zn / Ni or Zn / Co, with a suitable composition of the chromating solution, iron, nickel or cobalt oxide as black pigment accumulates in the chromate layer, so that in these cases silver is not required. Significant amounts of chromium (VI) are incorporated in the chromate layers, depending on whether yellow or olive chromate is the base, between 80 and 400 mg / m 2 . The chromating solutions are used at room temperature. The corrosion protection of undamaged black chromations on zinc amounts to 50 - 150 h in Salzsprühschrank according to DIN 50021 SS until the first appearance of corrosion products. The minimum requirement for process group F according to DIN 50961 chapter 10 table 3 is 24 hours for drum products and 48 hours for rack goods. Black chromations on zinc alloys are significantly above the stated values.

5) Grünchromatierungen für Aluminium, Gruppe E:5) Green Chromations for Aluminum, Group E:

Nach dem Stand der Technik lassen sich dicke Chromatschichten mit hohem Korrosionsschutz > 100 h im Salzsprühschrank nach DIN 50021 SS bzw. ASTM B 117-73 bis zum Auftreten von ersten Korrosionsprodukten nach DIN 50961 (Juni 1987) Kapitel 10, insbesondere Kapitel 10.2.1.2, ohne Versiegelung und weitere besondere Nachbehandlung (DIN 50961, Kapitel 9) nur durch Behandlung mit gelösten ausgesprochen giftigen Chrom(VI)-Verbindungen herstellen. Dementsprechend enthalten die Chromatschichten mit den genannten Anforderungen an den Korrosionsschutz noch diese ausgesprochen giftigen und karzinogenen Chrom(VI)-Verbindungen, die zudem nicht vollständig in der Schicht immobilisert sind. Die Chomatierung mit Chrom(VI)-Verbindungen ist hinsichtlich des Arbeitsschutzes problematisch. Der Gebrauch von verzinkten und mit Chrom(VI)-Verbindungen hergestellten Chromatierungen, wie z.B. die weit verbreiteten Gelbchromatierungen z.B. auf Schrauben, stellt ein Gefährdungspotential der Bevölkerung dar und erhöht das allgemeine Krebsrisiko.According to the state of the art, it is possible to obtain thick chromate layers with high corrosion protection> 100 h in a salt spray cabinet in accordance with DIN 50021 SS or ASTM B 117-73 until the occurrence of first corrosion products according to DIN 50961 (June 1987) Chapter 10, in particular Chapter 10.2.1.2, without sealing and further special aftertreatment (DIN 50961, Chapter 9) only by treatment with dissolved extremely toxic chromium (VI) compounds. Accordingly, the chromate layers with the stated requirements for corrosion protection still contain these extremely toxic and carcinogenic chromium (VI) compounds, which moreover are not completely immobilized in the layer. The chromating with chromium (VI) compounds is problematic in terms of occupational safety. The use of galvanized and chromium (VI) compound chromations, e.g. the widespread yellow chromations, e.g. on screws, represents a potential hazard to the population and increases the overall cancer risk.

Deshalb sind im Stand der Technik Passivierungsverfahren beschrieben, bei denen auf die Verwendung von Chrom(VI)-Verbindungen ganz oder teilweise verzichtet wird.Therefore, the prior art passivation processes are described in which the use of chromium (VI) compounds is completely or partially omitted.

US-Patent 4,384,902 beschreibt insbesondere mit den Beispielen 1, 2, 4 und 5 Passivierungsschichten, die den Anforderungen im Salzsprühtest genügen. Es handelt sich dabei in allen Fällen um eine Cer-haltige Schicht, die eine durch das Cer(IV)-lon hervorgehobene gelbliche Färbung aufweist. Die Beispiele enthalten in der Badlösung nur Cer(III) sowie Wasserstoffperoxid als Oxidationsmittel. In der Beschreibung ist diskutiert, dass Wasserstoffperoxid im Sauren zwar kein Oxidationsmittel für Ce(III) darstellt, dass der pH-Wert an der Oberfläche während der Abscheidung jedoch so weit ansteigt, dass eine ausreichende Menge Ce(IV) entstehen kann. Die gelbliche Farbe, die mit der beschriebenen Badzusammensetzung erreicht worden ist, deutet in der Tat darauf hin, dass eine Oxidation stattgefunden hat, allerdings nur eine Oxidation von Cer(III) zu Cer(IV). Vierwertiges Cer ist ein noch stärkeres Oxidationsmittel als sechswertiges Chrom, weshalb Ce(IV) aus Cr(III) das zu vermeidende Cr(VI) erzeugen wird. Cr(VI) hat eine sehr starke gelbe Farbe und ist als Korrosionsschutzmittel bekannt. Die in dem US-Patent 4,384,902 beschriebene Schicht ist somit nicht frei von sechswertigem Chrom. U.S. Patent 4,384,902 describes in particular with Examples 1, 2, 4 and 5 Passivierungsschichten that meet the requirements in the salt spray test. It is in all cases a cerium-containing layer which has a yellowish coloration highlighted by the cerium (IV) ion. The examples contain in the bath solution only cerium (III) and hydrogen peroxide as the oxidant. In the description is discussed Although hydrogen peroxide in the acid does not represent an oxidizing agent for Ce (III), the pH at the surface during the deposition increases so much that a sufficient amount of Ce (IV) can form. The yellowish color achieved with the bath composition described, in fact, indicates that oxidation has taken place but only oxidation of cerium (III) to cerium (IV). Tetravalent cerium is an even stronger oxidizing agent than hexavalent chromium, which is why Ce (IV) from Cr (III) will produce the Cr (VI) to be avoided. Cr (VI) has a very strong yellow color and is known as a corrosion inhibitor. The in the U.S. Patent 4,384,902 thus described layer is not free of hexavalent chromium.

US-Patent 4,359,348 beschreibt ebenfalls Passivierungsschichten, die den oben genannten Anforderungen im Salzsprühtest genügen. Auch hier handelt es sich in allen Fällen um eine Cer-haltige Schicht, die eine durch das Cer(IV)-lon hervorgehobene gelbliche Färbung aufweist. Dieses Dokument geht daher nicht über US-Patent 4,384,902 hinaus. U.S. Patent 4,359,348 also describes passivation layers that meet the above salt spray test requirements. Again, it is in all cases a cerium-containing layer having a yellowish coloration highlighted by the cerium (IV) ion. This document is therefore not over U.S. Patent 4,384,902 out.

Ferner offenbart GB-A-2 097 024 die Behandlung von Metalloberflächen zur Verbesserung des Korrosionsschutzes auf Zink und Zinklegierungsoberflächen mit einer wässrigen sauren Lösung, die ein Oxidationsmittel und wenigstens ein Metall, ausgewählt aus der Gruppe, bestehend aus Eisen, Kobalt, Nickel, Molybdän, Mangan, Aluminium, Lanthan, Lanthaniden-Mischungen oder Cerionen oder Mischungen davon und insbesondere Eisen- und Kobaltionen, enthält. Ferner offenbart GB-A-2 097 024 die Verwendung von dreiwertigen Chromionen und Eisenionen in Kombination mit einem zusätzlichen Metall, ausgewählt aus der Gruppe, bestehend aus den oben genannten Ionen oder Cerionen, jedoch werden hauptsächlich Kombinationen von Chrom(III) in Kombination mit einem Oxidationsmittel und Cer- oder Lanthanionen beschrieben.Further disclosed GB-A-2 097 024 the treatment of metal surfaces to improve corrosion protection on zinc and zinc alloy surfaces with an aqueous acidic solution comprising an oxidizing agent and at least one metal selected from the group consisting of iron, cobalt, nickel, molybdenum, manganese, aluminum, lanthanum, lanthanide mixtures or cerium ions or mixtures thereof and in particular iron and cobalt ions. Further disclosed GB-A-2 097 024 the use of trivalent chromium ions and iron ions in combination with an additional metal selected from the group consisting of the abovementioned ions or cerium ions, but mainly describes combinations of chromium (III) in combination with an oxidizing agent and cerium or lanthanum ions.

DE 196 15 664 A1 beschreibt ein Verfahren, Chrom(VI)-freie Passivierungsschichten mit größerer Schichtdicke und höherem Korrosionsschutz zu erzeugen. Dabei werden der Reaktionslösung organische Chelatliganden, insbesondere Dicarbonsäuren, Tricarbonsäuren und Hydroxycarbonsäuren, wie etwa Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebazinsäure, Maleinsäure, Phthalsäure, Terephthalsäure, Ascorbinsäure, Apfelsäure, Weinsäure, oder Zitronensäure, zugesetzt. Diese Chelatliganden bilden kinetisch wenig stabile Komplexe mit Chrom(III), aus denen dieses rasch freigesetzt und mit hoher Reaktionsgeschwindigkeit in die wachsende ZnCrO-Schicht eingelagert wird. Als zusätzlicher Katalysator werden Metallionen wie etwa zweiwertige Cobaltionen in Form löslicher Salze zugegeben, die die Reaktionsgeschwindigkeit und das Dickenwachstum der Chromatschicht steigern sollen. Die derart erzeugten Passivierungsschichten sind Chrom(VI)-frei und erlauben einen Korrosionsschutz von bis zu über 100 h, der etwa dem einer herkömmlichen Gelbchromatierung entspricht. Die so erzeugten Chromatschichten weisen eine grünliche, rot-grün irisierende Farbe auf. Ein alternatives, in DE 41 35 524 A1 beschriebenes Verfahren der Passivierung, das auf einem Chrom(III)-Oxalatkomplex basiert, liefert wiederum einen blauen Passivierungsfilm. DE 196 15 664 A1 describes a method of producing chromium (VI) -free passivation layers with greater layer thickness and higher corrosion protection. In this case, the reaction solution, organic chelate ligands, especially dicarboxylic acids, tricarboxylic acids and hydroxycarboxylic acids such as oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, phthalic, terephthalic, ascorbic, malic, tartaric or citric acid. These chelating ligands form kinetically less stable complexes with chromium (III), from which this is released rapidly and stored at high reaction rate in the growing ZnCrO layer. As an additional catalyst, metal ions such as divalent cobalt ions in the form of soluble salts are added to increase the reaction rate and the thickness growth of the chromate layer. The passivation layers produced in this way are chromium (VI) -free and allow corrosion protection of up to more than 100 h, which corresponds approximately to that of conventional yellow chromating. The chromate layers produced in this way have a greenish, red-green iridescent color. An alternative, in DE 41 35 524 A1 described method of passivation, which is based on a chromium (III) oxalate complex, in turn provides a blue passivation film.

DE 103 05 449 A1 beschreibt ein Stoffgemisch und ein Verfahren zur Erzeugung farbiger Passivierungsschichten, welche jeweils auf einer Kombination einer Chrom(III)-lonen enthaltenen Reaktionslösung mit einem Chinolinfarbstoff basieren. Nachteilig ist hier die mangelnde Beständigkeit des Chinolinfarbstoffes sowohl in der Reaktionslösung als auch in der Passivierungsschicht. Unter anderem ist dies auf die mangelnde UV-Beständigkeit solcher Verbindungen zurückzuführen. DE 103 05 449 A1 describes a mixture of substances and a process for producing colored passivation layers which are each based on a combination of a reaction solution containing chromium (III) ions with a quinoline dye. The disadvantage here is the lack of resistance of the quinoline dye both in the reaction solution and in the passivation layer. Among other things, this is due to the lack of UV resistance of such compounds.

Die oben genannten Beispiele zeigen, dass Chrom(III)- Passivierungen nach wie vor nur begrenzte Anwendungsmöglichkeiten erlauben. Neben dem bei Blauchromatierungen meist schwachen Korrosionsschutz und dem Risiko von Chrom(VI)-Rückständen sind insbesondere die begrenzten Möglichkeiten der mit Chrom(III)-Passivierungen erreichbaren Farbgebung von Nachteil. Die durch Chrom(III)-Passivierung erzeugten Farben beschränken sich im Wesentlichen auf blaue und grünliche Chromatschichten, während Gelbchromatierungen auf Chrom(III)-Basis keine einheitliche und kräftige Gelbfärbung erlauben, sondern zu hellen, deutlich irisierenden oder ins bläuliche bzw. grünliche gehenden Beschichtungen führen.The above examples show that chromium (III) passivations still allow only limited applications. In addition to the usually weak in blue rippling corrosion protection and the risk of chromium (VI) residues are in particular the limited possibilities of achievable with chromium (III) passivation coloring of disadvantage. The colors produced by chromium (III) passivation are essentially limited to blue and greenish chromate layers, whereas chromium (III) based yellow chromates do not allow a uniform and strong yellowing, but to bright, clearly iridescent or bluish or greenish going coatings to lead.

Daher wurden wiederholt Versuche unternommen, gelbe Passivierungsschichten zu erzeugen, die nur einen geringen Chrom(VI)-Anteil aufweisen oder frei von Chrom(VI) sind. Die intensiv gelbe Färbung bei herkömmlichen Gelbchromatierungen wird durch Chrom(VI) selbst hervorgerufen.Therefore, attempts have been repeatedly made to produce yellow passivation layers which have only a low chromium (VI) content or are free of chromium (VI). The intense yellow coloration in conventional yellow chromations is caused by chromium (VI) itself.

Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, eine Lösung sowie ein Verfahren zur Herstellung von Chrom(III)-haltigen und Chrom(VI)-freien gelben Passivierungsschichten bereitzustellen, die farbintensiv und langzeitstabil sind.The present invention is therefore based on the object to provide a solution and a process for the preparation of chromium (III) -containing and chromium (VI) -free yellow passivation layers which are color intensive and long-term stable.

Diese Aufgabe wird gelöst durch die wässrige Reaktionslösung gemäß Anspruch 1, durch das Verfahren zur Passivierung von Oberflächen aus Zink- und Zinklegierungen aufweisenden Werkstücken nach Anspruch 13 sowie durch die Verwendung einer Verbindung, ausgewählt aus der Gruppe, umfassend Nicotinsäure, deren Salze und deren Derivate, zur Erzeugung farbiger Passivierungsschichten auf Zink- und Zinklegierungen nach Anspruch 18. Bevorzugte Ausführungsformen der Erfindung sind in den Unteransprüchen gegeben.This object is achieved by the aqueous reaction solution according to claim 1, by the method for passivating surfaces of zinc and zinc alloyed workpieces according to claim 13 and by the use of a compound selected from the group comprising nicotinic acid, its salts and their derivatives, for producing colored passivation layers on zinc and zinc alloys according to claim 18. Preferred embodiments of the invention are given in the subclaims.

Die Erfindung ist insbesondere geeignet zur Erzeugung gelber, weitgehend Chrom(VI)-freier Passivierungsschichten auf Zink und Zinklegierungen. Der Effekt der Gelbpassivierung wird gemäß der vorliegenden Erfindung durch eine wässrige Reaktionslösung erreicht, die Chrom(III)-lonen, mindestens eine Säure sowie mindestens eine heteroaromatische Verbindung, ausgewählt aus der Gruppe, umfassend Nicotinsäure, deren Salze und deren Derivate, erreicht. Durch den Zusatz der heteroaromatischen Verbindungen werden stabile chemische Zusammensetzungen zur Passivierung von Zink und Zinklegierungen erhalten. Als bevorzugte heteroaromatische Verbindung wird Nicotinsäure verwendet. Statt der freien Säure können auch ihre Salze, insbesondere das Natrium- oder Kaliumsalz, eingesetzt werden. Dies erleichtert die Auflösung der Säure in wässrigen Lösungen.The invention is particularly suitable for producing yellow, largely chromium (VI) -free passivation layers on zinc and zinc alloys. The effect of the yellow passivation is achieved according to the present invention by an aqueous reaction solution which reaches chromium (III) ions, at least one acid and at least one heteroaromatic compound selected from the group comprising nicotinic acid, its salts and their derivatives. The addition of the heteroaromatic compounds gives stable chemical compositions for the passivation of zinc and zinc alloys. Nicotinic acid is used as the preferred heteroaromatic compound. Instead of the free acid, its salts, in particular the sodium or potassium salt, can also be used. This facilitates the dissolution of the acid in aqueous solutions.

Vorteilhafte Konzentrationen der heteroaromatischen Säuren hängen stark von der gewünschten Farbintensität der Gelbpassivierung ab und können im allgemeinem bei mindestens 0,5 g/l liegen. Die obere Konzentrationsgrenze kann 40 g/l, vorzugsweise 30 g/l, betragen. Eine bevorzugte Konzentration der heteroaromatischen Verbindungen liegt bei mindestens 10 g/l, weiter bevorzugt bei mindestens 15 g/l. Die Konzentration dieser Verbindungen liegt vorzugsweise bei höchstens 20 g/l. Allgemein gilt, dass die Gelbfärbung umso intensiver ist je höher der Gehalt der Nicotinsäure gewählt wird. Bei einer Konzentration von über 20 g/l Nicotinsäure wird jedoch kaum noch eine Zunahme der Farbintensität beobachtet. Sofern die vorgenannten Konzentrationsgrenzen in mol/l umgerechnet werden, gelten diese auch für die Salze der Nicotinsäure und für deren Derivate.Advantageous concentrations of the heteroaromatic acids are highly dependent on the desired color intensity of the yellow passivation and may generally be at least 0.5 g / l. The upper concentration limit may be 40 g / l, preferably 30 g / l. A preferred concentration of the heteroaromatic compounds is at least 10 g / l, more preferably at least 15 g / l. The concentration of these compounds is preferably at most 20 g / l. In general, the higher the content of nicotinic acid, the more intense is the yellow coloration. At a concentration of more than 20 g / l nicotinic acid, however, hardly any increase in color intensity is observed. If the aforementioned concentration limits are converted into mol / l, these also apply to the salts of nicotinic acid and their derivatives.

Die gelbe Farbe ist unter anderem deshalb von großem praktischem Nutzen, da sie in der Verarbeitung von Massenteilen, beispielsweise in der Automobilindustrie, zur Unterscheidung von Werkstücken dient. Beispielsweise können durch gezielte Einfärbung mit der erfindungsgemäßen Zusammensetzung rechts- und linkshändige Bauteile zuverlässig und einfach unterschieden werden. Dies erhöht die Prozesssicherheit enorm, insbesondere bei der Verarbeitung sehr ähnlicher Bauteile in großen Stückzahlen.The yellow color is, among other things, of great practical use, since it is used in the processing of mass parts, for example in the automotive industry, to distinguish workpieces. For example, can be reliably and easily distinguished by targeted coloring with the composition of the invention right- and left-handed components. This enormously increases process reliability, especially when processing very similar components in large numbers.

Die erfindungsgemäße Schicht ist jedoch ohne Oxidationsmittel hergestellt und daher frei von sechswertigem Chrom. Mit derartigen Schichten versehene Werkstücke weisen eine sehr hohe Korrosionsbeständigkeit auf, die mit derjenigen von mit einer Gelbchromatierung versehenen verzinkten Oberflächen vergleichbar oder sogar besser als diese ist.However, the layer according to the invention is produced without an oxidizing agent and therefore free of hexavalent chromium. Workpieces provided with such layers have a very high corrosion resistance which is comparable or even better than that of galvanized surfaces provided with yellow chromating.

Der zur Durchführung verwendete pH-Wert der Reaktionslösung kann beispielsweise mindestens etwa 1,5 betragen, vorzugsweise mindestens etwa 1,8. Die obere pH-Grenze kann bei 3,0, vorzugsweise bei 2,2, liegen. Dabei kann der gewünschte pH-Wert durch Zugabe von Wasserstoffionen, d.h. durch Zugabe der mindestens einen Säure, vorzugsweise Salpetersäure oder einer anderen Mineral- oder Carbonsäure, erzeugt und anschließend mit Natronlauge exakt eingestellt werden.The pH of the reaction solution used for carrying out may be, for example, at least about 1.5, preferably at least about 1.8. The upper pH limit may be 3.0, preferably 2.2. In this case, the desired pH value can be generated by adding hydrogen ions, ie by adding at least one acid, preferably nitric acid or another mineral or carboxylic acid, and then adjusted exactly with sodium hydroxide solution.

Die Konzentration der gelösten Chrom(III)-lonen kann mindestens 0,2 g/l, vorzugsweise mindestens 1 g/l, betragen. Sie kann in einem Bereich bis maximal 30 g/l, vorzugsweise bis maximal 5 g/l, liegen. Grundsätzlich können die Chrom(III)-Verbindungen auch in einer Konzentration bis zur Sättigungsgrenze in der Reaktionslösung enthalten sein. Als Quelle für die Chrom(III)-lonen kann Chromchlorid (CrCl3), Chromnitrat (Cr(NO3)3), Chromsulfat (Cr2(SO4)3) oder ein anderes wasserlösliches Chrom(III)-Salz verwendet werden.The concentration of the dissolved chromium (III) ions may be at least 0.2 g / l, preferably at least 1 g / l. It can be in a range up to a maximum of 30 g / l, preferably up to a maximum of 5 g / l. In principle, the chromium (III) compounds can also be present in the reaction solution in a concentration up to the saturation limit. Chromium chloride (CrCl 3 ), chromium nitrate (Cr (NO 3 ) 3 ), chromium sulfate (Cr 2 (SO 4 ) 3 ) or another water-soluble chromium (III) salt may be used as the source of the chromium (III) ions.

Als Katalysatoren können 2- bis 6-wertige Metallionen mindestens eines Elements, wie von Aluminium, Cobalt, Nickel, Eisen, Gallium, Indium, den Lanthaniden, Zirkonium, Scandium, Titan, Vanadium, Chrom, Mangan, Kupfer, Zink, Yttrium, Niob, Molybdän, Hafnium, Tantal und Wolfram, in der Reaktionslösung enthalten sein. Diese Metallionen können der Reaktionslösung als lösliche Salze zugegeben werden, vorzugsweise als Nitrate, Sulfate oder Halogenide. In einer bevorzugten Ausführungsform sind Cobalt(II)-lonen in einer Konzentration von mindestens etwa 0,1 g/l enthalten. Deren Konzentration kann vorzugsweise bis zu 5 g/l reichen. Dabei stellen wasserhaltige oder wasserfreie Cobaltnitrate (Co(NO3)2), Cobaltsulfate (CoSO4) oder Cobaltchlorid (CoCl2) Beispiele für geeignete Cobalt(II)-Quellen dar.As catalysts, 2- to 6-valent metal ions of at least one element such as aluminum, cobalt, nickel, iron, gallium, indium, the lanthanides, zirconium, scandium, titanium, vanadium, chromium, manganese, copper, zinc, yttrium, niobium , Molybdenum, hafnium, tantalum and tungsten, to be contained in the reaction solution. These metal ions may be added to the reaction solution as soluble salts, preferably as nitrates, sulfates or halides. In a preferred embodiment, cobalt (II) ions are contained in a concentration of at least about 0.1 g / L. Their concentration may preferably reach up to 5 g / l. Water-containing or anhydrous cobalt nitrates (Co (NO 3 ) 2 ), cobalt sulfates (CoSO 4 ) or cobalt chloride (CoCl 2 ) are examples of suitable cobalt (II) sources.

Weiterhin kann die chemische Zusammensetzung mindestens ein säurestabiles wasserlösliches Silikat enthalten, um die passivierenden Eigenschaften zu verbessern und der Passivierungsschicht eine höhere Härte zu verleihen. Die Konzentration beträgt bevorzugt mindestens 0,5 g/l. Die obere Konzentrationsgrenze liegt vorzugsweise bei 10 g/l. Diese Konzentrationswerte beziehen sich jeweils auf SiO2. Verwendbare Silikate können sowohl anorganisch als auch organisch sein, sofern sie in der Reaktionslösung löslich sind. Organische Silikate sind wegen deren stabilisierender Eigenschaft hinsichtlich der Badstandzeit vorzuziehen. Verwendbare anorganische Silikate können säurestabile kolloidale Lösungen von Siliziumdioxid sein. Organische Silikate können ebenfalls eingesetzt werden. Derartige Silikate können insbesondere Tetramethylammoniumsilikat, Phenyltrimethylammoniumsilikat, -disilikat und -trisilikat sowie Benzyltrimethylammoniumsilikat und -disilikat sein. Geeignet sind organische Silikate mit der allgemeinen chemischen Formel ROR':xSiO2:yH2O, wobei R ein quarternäres Ammoniumradikal ist, das mit vier organischen Resten substituiert ist, die ausgewählt sind aus der Gruppe, umfassend Alkyl-, Alkylen-, Alkanol-, Aryl-, Aralkyl-Reste und deren Mischungen, wobei R' entweder R oder Wasserstoff ist und wobei x=1-3 und y=0-15. Derartige organische Silikate können mit üblichen chemischen Methoden synthetisiert werden. Beispielsweise sind Synthesemethoden von Merrill und Spencer, "Some Quaternary Ammonium Silicates", Journal of Physical and Colloid Chemistry, 55, 187 (1951) sowie in US-Patent 3,993,548 beschrieben.Furthermore, the chemical composition may contain at least one acid-stable water-soluble silicate in order to improve the passivating properties and to impart a higher hardness to the passivation layer. The concentration is preferably at least 0.5 g / l. The upper concentration limit is preferably 10 g / l. These concentration values relate in each case to SiO 2 . Usable silicates may be both inorganic and organic, as long as they are soluble in the reaction solution. Organic silicates are preferable because of their stabilizing property in terms of bath life. Useful inorganic silicates may be acid stable colloidal solutions of silica. Organic silicates can also be used. Such silicates may in particular be tetramethylammonium silicate, phenyltrimethylammonium silicate, disilicate and trisilicate and also benzyltrimethylammonium silicate and disilicate. Suitable organic silicates with the general chemical formula ROR ': xSiO 2 : yH 2 O, where R is a quaternary ammonium radical substituted with four organic radicals selected from the group comprising alkyl, alkylene, alkanol, aryl, aralkyl Radicals and mixtures thereof, wherein R 'is either R or hydrogen and where x = 1-3 and y = 0-15. Such organic silicates can be synthesized by conventional chemical methods. For example, methods of synthesis by Merrill and Spencer, "Some Quaternary Ammonium Silicates", Journal of Physical and Colloid Chemistry, 55, 187 (1951) and in U.S. Patent 3,993,548 described.

Als weitere Komponenten bzw. Leitionen kann die Reaktionslösung Halogenide, insbesondere Chlorid und Fluorid, Sulfationen, Nitrationen, Phosphorsäure, Phosphorsäureester oder Phosphationen, Silikationen, Kieselsäuren, Aminosäuren, Amine und Tenside enthalten. Geeignete Tenside sind beispielsweise aliphatische Fluorcarbonsulfonate, wie etwa die Produkte Fluorad® von 3M Comp., US, etwa Fluorad FC 98. Zusätzlich können Komplexbildner für Chrom(III)-lonen, wie Malonsäure und Oxalsäure, vorhanden sein.As further components or conductive ions, the reaction solution may contain halides, in particular chloride and fluoride, sulfate ions, nitrate ions, phosphoric acid, phosphoric acid esters or phosphate ions, silicates, silicic acids, amino acids, amines and surfactants. Suitable surfactants are, for example, aliphatic fluorocarbonsulfonates, such as the Fluorad® products from 3M Comp., US, such as Fluorad FC 98. In addition, chelating agents may be present for chromium (III) ions, such as malonic acid and oxalic acid.

Mit der erfindungsgemäßen Reaktionslösung können vorzugsweise Werkstücke mit Oberflächen aus Zink- oder Zinklegierungen mit einer Passivierungsschicht versehen werden. Dabei sind sowohl Werkstücke passivierbar, die mit einem durch alkalische cyanidische oder durch saure nicht-cyanidische elektrolytische Zinkabscheidung erzeugten Zinküberzug versehen sind, als auch Werkstücke, die mittels einer Schmelze verzinkt sind oder die überhaupt aus Zink oder aus einer Zinklegierung bestehen. Zinklegierungen an den Werkstückoberflächen können beispielsweise Zn/Fe-, Zn/Ni- und Zn/Co-Legierungen sein. Weiterhin können mit der Reaktionslösung auch Werkstücke in erfindungsgemäßer Weise behandelt werden, an denen zusätzlich zu den Zink- oder Zinklegierungsoberflächen auch Oberflächen frei liegen, die nicht aus Zink oder einer Zinklegierung bestehen, beispielsweise Eisen enthaltende Oberflächen wie Stahloberflächen. Diese weiteren Oberflächen können zusammen mit den Zink- oder Zinklegierungsoberflächen passiviert werden. Grundsätzlich besteht auch die Möglichkeit, dass die erfindungsgemäße Reaktionslösung auch zur Passierung von Aluminium-, Aluminiumlegierungsoberflächen sowie Oberflächen, die aus Cadmium bestehen, zu verwenden.The reaction solution according to the invention can preferably be used to provide workpieces with surfaces of zinc or zinc alloys with a passivation layer. In this case, both workpieces are passivated, which are provided with a generated by alkaline cyanide or acidic non-cyanide zinc electroplating zinc coating, as well as workpieces that are galvanized by means of a melt or even made of zinc or of a zinc alloy. Zinc alloys on the workpiece surfaces may be, for example, Zn / Fe, Zn / Ni and Zn / Co alloys. Furthermore, the reaction solution can also be used to treat workpieces in accordance with the invention in which, in addition to the zinc or zinc alloy surfaces, surfaces which are not zinc or a zinc alloy, for example iron-containing surfaces such as steel surfaces, are also exposed. These other surfaces can be passivated together with the zinc or zinc alloy surfaces. In principle, it is also possible that the reaction solution according to the invention also for the passage of aluminum, aluminum alloy surfaces and surfaces made of cadmium.

Das Passivierungsverfahren umfasst das In-Kontakt-Bringen der Oberflächen aus Zink- oder Zinklegierungen aufweisenden Werkstücke mit der Reaktionslösung. Die Reaktion erfolgt bevorzugt ab einer Mindestbadtemperatur von ca. 10°C. Die obere Badtemperatur kann beispielsweise 80°C betragen. Besonders bevorzugte Badtemperaturen liegen im Bereich von 30°C bis 50°C.The passivation process involves contacting the surfaces of zinc or zinc alloyed workpieces with the reaction solution. The reaction is preferably carried out from a minimum bath temperature of about 10 ° C. The upper bath temperature may be, for example, 80 ° C. Particularly preferred bath temperatures are in the range from 30 ° C to 50 ° C.

Die Werkstücke können mit der Reaktionslösung bevorzugt durch Tauchen in Kontakt gebracht werden, d.h. die Werkstücke werden in die in einem Behälter befindliche Reaktionslösung eingetaucht. Hierzu können die Werkstücke entweder an Gestellen gehalten werden und mit den Gestellen in die Reaktionslösung eintauchen oder sich in einer Trommel oder auf einer Horde befinden und mit der Trommel oder der Horde in die Reaktionslösung eintauchen. In einer alternativen Verfahrensweise werden die Werkstücke auch durch Spritztauchen mit der Reaktionslösung in Kontakt gebracht. In einer weiteren Verfahrensweise werden die Werkstücke auch durch Sprühen mit der Reaktionslösung in Kontakt gebracht. Ferner können die Werkstücken auch mit der Reaktionslösung beschwallt werden, etwa mittels einer Düse, aus der ein Schwall der Reaktionslösung austritt. Eine noch andere Behandlungsweise besteht darin, die Reaktionslösung durch Pinseln, Rollen oder eine andere Auftragstechnik auf die Werkstückoberflächen aufzubringen. Die Behandlung kann in herkömmlichen Anlagen stattfinden, in denen die Werkstücke chargenweise behandelt werden, oder in Durchlaufanlagen, durch die die Werkstücke kontinuierlich hindurchgeführt und dabei behandelt werden.The workpieces may be contacted with the reaction solution preferably by dipping, i. the workpieces are immersed in the reaction solution contained in a container. For this purpose, the workpieces can either be held on racks and immersed with the racks in the reaction solution or are in a drum or on a horde and immerse with the drum or the Horde in the reaction solution. In an alternative procedure, the workpieces are also contacted by spray dipping with the reaction solution. In a further procedure, the workpieces are also brought into contact by spraying with the reaction solution. Furthermore, the workpieces can also be walled with the reaction solution, for example by means of a nozzle, from which a surge of the reaction solution emerges. Yet another method of treatment is to apply the reaction solution to the workpiece surfaces by brushing, rolling or another application technique. The treatment can take place in conventional plants, in which the workpieces are treated batchwise, or in continuous plants, through which the workpieces are continuously passed and treated.

Werden die Werkstücke durch Tauchen in der Reaktionslösung behandelt, kann die Behandlungszeit in einem Bereich von 20 bis 200 s liegen; in einer bevorzugten Ausführungsform liegt sie in einem Bereich von etwa 30 s bis etwa 90 s. Je nach der Technik, mit der die Werkstücke mit der Reaktionslösung in Kontakt gebracht werden, können auch längere oder kürzere Behandlungszeiten erforderlich werden.If the workpieces are treated by immersion in the reaction solution, the treatment time may be in a range of 20 to 200 s; in a preferred embodiment, it is in the range of about 30 seconds to about 90 seconds. Depending on the technology with which the workpieces are brought into contact with the reaction solution, longer or shorter treatment times may be required.

Zur Durchführung der erfindungsgemäßen Passivierung werden die Werkstücke vor dem In-Kontakt-Bringen mit der Reaktionslösung gegebenenfalls zunächst gereinigt. Dies kann allerdings dann entfallen, wenn die Werkstücke unmittelbar nach dem elektrolytischen Verzinken und anschließenden Abspülen der Verzinkungslösung mit der Reaktionslösung in Kontakt gebracht werden. Nach Abschluss des erfindungsgemäßen Passivierungsverfahrens werden die Werkstücke vorzugsweise getrocknet, beispielsweise mit warmer Luft. Zusätzlich können die Werkstücke vor dem Trocknen auch gespült werden, um überschüssige Reaktionslösung von der Oberfläche zu entfernen.To carry out the passivation according to the invention, the workpieces are optionally first cleaned before being brought into contact with the reaction solution. However, this can be omitted if the workpieces are brought into contact with the reaction solution immediately after the electrolytic galvanizing and subsequent rinsing of the galvanizing solution. After completion of the passivation process according to the invention, the workpieces are preferably dried, for example with warm air. In addition, the workpieces may also be rinsed before drying to remove excess reaction solution from the surface.

Die nachstehenden Beispiele dienen zur näheren Erläuterung der Erfindung:The following examples serve to illustrate the invention:

Beispiel 1:Example 1:

Es wurde eine Reaktionslösung mit folgender Zusammensetzung hergestellt:

  • 2 g/l Cr(III) als Chromnitrat
  • 1,5 g/l Ammoniumhydrogenfluorid
  • 1 ml/l Salpetersäure (konz.)
  • 10 g/l Nicotinsäure als Natriumsalz
  • in Wasser
A reaction solution with the following composition was prepared:
  • 2 g / l Cr (III) as chromium nitrate
  • 1.5 g / l ammonium hydrogen fluoride
  • 1 ml / l nitric acid (conc.)
  • 10 g / l nicotinic acid as sodium salt
  • in water

Der pH-Wert der Reaktionslösung wurde mit Salpetersäure oder Natronlauge auf pH 2,0 eingestellt. Die Lösung wurde auf 45°C erwärmt. Verzinkte Teile wurden an einem Gestell gehalten für 60 Sekunden in die Reaktionslösung eingetaucht, anschließend abgespült und getrocknet. Die resultierende Passivierungsschicht wies eine einheitliche gelb-grün irisierende Farbgebung auf. Ihre Korrosionsbeständigkeit nach DIN 50021 SS wurde zu ca. 72 h bis zum ersten Auftreten von Weißkorrosion bestimmt.The pH of the reaction solution was adjusted to pH 2.0 with nitric acid or sodium hydroxide solution. The solution was heated to 45 ° C. Galvanized parts were held on a rack for 60 seconds immersed in the reaction solution, then rinsed and dried. The resulting passivation layer had a uniform yellow-green iridescent color. Their corrosion resistance in accordance with DIN 50021 SS was determined to be approx. 72 h until the first occurrence of white corrosion.

Beispiel 2:Example 2:

Der Versuch gemäß der Beschreibung von Beispiel 1 wurde wiederholt, wobei der Lösung zusätzlich 0,5 g/l Cobalt(II)-Nitrat zugesetzt wurden. Die Korrosionsbeständigkeit der Schicht nach DIN 50021 SS wurde zu 96 h bis zum Auftreten von Weißkorrosionen bestimmt.The experiment according to the description of Example 1 was repeated, wherein the solution was additionally added 0.5 g / l cobalt (II) nitrate. The corrosion resistance The layer according to DIN 50021 SS was determined to 96 h until the occurrence of white corrosion.

Beispiel 3:Example 3:

Der Versuch gemäß der Beschreibung von Beispiel 1 wurde wiederholt, wobei die Zusammensetzung wie folgt verändert wurde:

  • 3 g/l Cr(III) als Chromnitrat
  • 2 g/l Natriumfluorid
  • 1 ml/l Salpetersäure (konz.)
  • 1 g/l Malonsäure
  • 5 g/l Nicotinsäure als Natriumsalz
  • in Wasser
The experiment according to the description of Example 1 was repeated, the composition being changed as follows:
  • 3 g / l Cr (III) as chromium nitrate
  • 2 g / l sodium fluoride
  • 1 ml / l nitric acid (conc.)
  • 1 g / l malonic acid
  • 5 g / l nicotinic acid as sodium salt
  • in water

Die resultierende Passivierungsschicht wies eine einheitliche gelb-grün irisierende Farbgebung auf. Ihre Korrosionsbeständigkeit nach DIN 50021 SS wurde zu ca. 96h bis zum ersten Auftreten von Weißkorrosion bestimmt.The resulting passivation layer had a uniform yellow-green iridescent color. Their corrosion resistance according to DIN 50021 SS was determined to approx. 96 h until the first appearance of white corrosion.

Claims (18)

Wässrige Reaktionslösung zur Passivierung von Zink- und Zinklegierungen, enthaltend dreiwertige Chromionen sowie mindestens eine Säure,
dadurch gekennzeichnet, dass die Reaktionslösung mindestens eine Verbindung, ausgewählt aus der Gruppe, umfassend Nicotinsäure, deren Salze und deren Derivate, enthält.Aqueous reaction solution for the passivation of zinc and zinc alloys containing trivalent chromium ions and at least one acid,
characterized in that the reaction solution contains at least one compound selected from the group comprising nicotinic acid, its salts and their derivatives. Wässrige Reaktionslösung nach Anspruch 1, dadurch gekennzeichnet, dass das Salz der Nicotinsäure das Natriumsalz ist.Aqueous reaction solution according to claim 1, characterized in that the salt of nicotinic acid is the sodium salt. Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass Nicotinsäure in einer Konzentration von 0,5 - 30 g/l enthalten ist.Aqueous reaction solution according to one of the preceding claims, characterized in that nicotinic acid is present in a concentration of 0.5-30 g / l. Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass Nicotinsäure in einer Konzentration von 10 - 20 g/l enthalten ist.Aqueous reaction solution according to any one of the preceding claims, characterized in that nicotinic acid is contained in a concentration of 10 - 20 g / l. Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die dreiwertigen Chromionen in einer Konzentration von 0,2 - 30 g/l enthalten sind.Aqueous reaction solution according to any one of the preceding claims, characterized in that the trivalent chromium ions are contained in a concentration of 0.2 to 30 g / l. Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die dreiwertigen Chromionen in einer Konzentration von 1 - 5 g/l enthalten sind.Aqueous reaction solution according to any one of the preceding claims, characterized in that the trivalent chromium ions are contained in a concentration of 1-5 g / l. Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass 2 - 6-wertige Metallionen von mindestens einem Element, ausgewählt aus der Gruppe, umfassend Al, Co, Ni, Fe, Ga, In, Lanthanide, Zr, Sc, Ti, V, Cr, Mn, Cu, Zn, Y, Nb, Mo, Hf, Ta und W, enthalten sind.Aqueous reaction solution according to any one of the preceding claims, characterized in that 2- to 6-valent metal ions of at least one element, selected from the group comprising Al, Co, Ni, Fe, Ga, In, lanthanides, Zr, Sc, Ti, V, Cr, Mn, Cu, Zn, Y, Nb, Mo, Hf, Ta and W. , Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass Cobalt(II)-lonen in einer Konzentration von etwa 0,1 bis etwa 5 g/l enthalten sind.Aqueous reaction solution according to any one of the preceding claims, characterized in that cobalt (II) ions are present in a concentration of about 0.1 to about 5 g / l. Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die mindestens eine Säure ausgewählt ist aus der Gruppe, umfassend Salpetersäure, Salzsäure und Schwefelsäure.Aqueous reaction solution according to any one of the preceding claims, characterized in that the at least one acid is selected from the group comprising nitric acid, hydrochloric acid and sulfuric acid. Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass mindestens ein säurestabiles wasserlösliches Silikat enthalten ist.Aqueous reaction solution according to any one of the preceding claims, characterized in that at least one acid-stable water-soluble silicate is contained. Wässrige Reaktionslösung nach Anspruch 8, dadurch gekennzeichnet, dass mindestens eine Halogenidionenquelle enthalten ist.Aqueous reaction solution according to claim 8, characterized in that at least one halide ion source is contained. Wässrige Reaktionslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass mindestens eine Fluoridionenquelle enthalten ist.Aqueous reaction solution according to any one of the preceding claims, characterized in that at least one fluoride ion source is contained. Verfahren zur Passivierung von Oberflächen aus Zink- und Zinklegierungen aufweisenden Werkstücken, umfassend In-Kontakt-Bringen der Werkstücke mit einer wässrigen Reaktionslösung, die dreiwertige Chromionen sowie mindestens eine Säure enthält,
dadurch gekennzeichnet, dass die Reaktionslösung mindestens eine Verbindung, ausgewählt aus der Gruppe, umfassend Nicotinsäure, deren Salze und deren Derivate, enthält.A process for passivating surfaces of zinc and zinc alloyed workpieces, comprising contacting the workpieces with an aqueous reaction solution containing trivalent chromium ions and at least one acid,
characterized in that the reaction solution contains at least one compound selected from the group comprising nicotinic acid, its salts and their derivatives. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass die Werkstücke mit der wässrigen Reaktionslösung bei einer Reaktionstemperatur von etwa 10°C bis etwa 80°C in Kontakt gebracht werden.A method according to claim 13, characterized in that the workpieces are brought into contact with the aqueous reaction solution at a reaction temperature of about 10 ° C to about 80 ° C. Verfahren nach einem der Ansprüche 13 und 14, dadurch gekennzeichnet, dass die Werkstücke mit der wässrigen Reaktionslösung bei einer Reaktionstemperatur von etwa 30°C bis etwa 50°C in Kontakt gebracht werden.Method according to one of claims 13 and 14, characterized in that the workpieces are brought into contact with the aqueous reaction solution at a reaction temperature of about 30 ° C to about 50 ° C. Verfahren nach einem der Ansprüche 13 - 15, dadurch gekennzeichnet, dass die Werkstücke durch Tauchen mit der wässrigen Reaktionslösung während einer Tauchzeit von etwa 20 Sekunden bis etwa 200 Sekunden in Kontakt gebracht werden.Method according to one of claims 13-15, characterized in that the workpieces are brought by dipping with the aqueous reaction solution during a dipping time of about 20 seconds to about 200 seconds in contact. Verfahren nach einem der Ansprüche 13 - 15, dadurch gekennzeichnet, dass die Werkstücke durch Tauchen mit der wässrigen Reaktionslösung während einer Tauchzeit von etwa 30 bis etwa 90 Sekunden in Kontakt gebracht werden.Method according to one of claims 13-15, characterized in that the workpieces are brought by dipping with the aqueous reaction solution during a dipping time of about 30 to about 90 seconds in contact. Verwendung einer Verbindung, ausgewählt aus der Gruppe, umfassend Nicotinsäure, deren Salze und deren Derivate, zur Erzeugung farbiger Passivierungsschichten auf Zink- und Zinklegierungen.Use of a compound selected from the group comprising nicotinic acid, its salts and their derivatives, for producing colored passivation layers on zinc and zinc alloys.
EP06001930A 2006-01-31 2006-01-31 Aqueous passivating coating composition for zinc or zinc alloys and method for using same Active EP1816234B1 (en)

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PL06001930T PL1816234T3 (en) 2006-01-31 2006-01-31 Aqueous passivating coating composition for zinc or zinc alloys and method for using same
EP06001930A EP1816234B1 (en) 2006-01-31 2006-01-31 Aqueous passivating coating composition for zinc or zinc alloys and method for using same
AT06001930T ATE431442T1 (en) 2006-01-31 2006-01-31 AQUEOUS REACTION SOLUTION AND METHOD FOR PASSIVATION OF ZINC AND ZINC ALLOYS
DE502006003710T DE502006003710D1 (en) 2006-01-31 2006-01-31 Aqueous reaction solution and process for the passivation of zinc and zinc alloys
CN2007800013029A CN101356301B (en) 2006-01-31 2007-01-23 Aqueous reaction solution and method of passivating workpieces having zinc or zinc alloy surfaces
JP2008551736A JP5130226B2 (en) 2006-01-31 2007-01-23 Aqueous reaction solution and method for passivating workpieces with zinc or zinc alloy surfaces
US12/086,796 US8262811B2 (en) 2006-01-31 2007-01-23 Aqueous reaction solution and method of passivating workpieces having zinc or zinc alloy surfaces and use of a heteroaromatic compound
CA2624215A CA2624215C (en) 2006-01-31 2007-01-23 Aqueous reaction solution and method of passivating workpieces having zinc or zinc alloy surfaces
EP07703155A EP1979507A1 (en) 2006-01-31 2007-01-23 Aqueous reaction solution and method of passivating workpieces having zinc or zinc alloy surfaces
PCT/EP2007/000805 WO2007088030A1 (en) 2006-01-31 2007-01-23 Aqueous reaction solution and method of passivating workpieces having zinc or zinc alloy surfaces

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CN104141123A (en) * 2014-07-24 2014-11-12 深圳市鑫明达环保科技有限公司 High corrosion resistance passivation solution for zinc alloy die castings and passivation method
CN115516134A (en) * 2020-04-03 2022-12-23 德国艾托特克有限两合公司 Method for forming black passivation layer on zinc-iron alloy and black passivation composition
RU2792999C1 (en) * 2022-04-14 2023-03-28 Общество с ограниченной ответственностью "ЭКОТЕХ" Chemical conversion treatment liquid and chemical conversion treatment method using the liquid

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DE102010001686A1 (en) * 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Composition for the alkaline passivation of zinc surfaces
CN102560467A (en) * 2012-02-14 2012-07-11 济南德锡科技有限公司 Highly corrosion-resistant galvanized black passivating agent and preparation method thereof
US10005104B2 (en) * 2013-08-28 2018-06-26 Honda Motor Co., Ltd. Black coating film-forming vehicle component and/or fastening component, and manufacturing method thereof
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CN103866307A (en) * 2014-03-13 2014-06-18 沈阳市环东电镀厂 Environment-friendly single-dose and double-color galvanized trivalent chromium passivation agent and preparation and application methods thereof
CN104451645A (en) * 2014-12-05 2015-03-25 上海奎鸣工程技术有限公司 Trivalent chromium passivation surface treating agent,
CN107109659B (en) * 2014-12-26 2020-05-05 迪普索股份公司 3-valent chromium chemical conversion treatment liquid and chemical conversion coating for zinc or zinc alloy substrate

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CN104141123A (en) * 2014-07-24 2014-11-12 深圳市鑫明达环保科技有限公司 High corrosion resistance passivation solution for zinc alloy die castings and passivation method
CN115516134A (en) * 2020-04-03 2022-12-23 德国艾托特克有限两合公司 Method for forming black passivation layer on zinc-iron alloy and black passivation composition
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US8262811B2 (en) 2012-09-11
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CN101356301A (en) 2009-01-28
CA2624215A1 (en) 2007-08-09
WO2007088030A1 (en) 2007-08-09
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JP2009525398A (en) 2009-07-09
CA2624215C (en) 2013-07-02
US20090032146A1 (en) 2009-02-05
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DE502006003710D1 (en) 2009-06-25
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