EP1816234A1 - Procédé et composition aqueuse pour la passivation du zinc ou des alliajes à base de zinc ainsi que l'utilisatiuon d'un composé sélecté d'un group contenant d'acide nicotinique, ses sels et ses derivés - Google Patents

Procédé et composition aqueuse pour la passivation du zinc ou des alliajes à base de zinc ainsi que l'utilisatiuon d'un composé sélecté d'un group contenant d'acide nicotinique, ses sels et ses derivés 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
European Patent Office
Prior art keywords
reaction solution
zinc
aqueous reaction
acid
workpieces
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP06001930A
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German (de)
English (en)
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EP1816234B1 (fr
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 AT06001930T priority Critical patent/ATE431442T1/de
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to EP06001930A priority patent/EP1816234B1/fr
Priority to DE502006003710T priority patent/DE502006003710D1/de
Priority to PL06001930T priority patent/PL1816234T3/pl
Priority to US12/086,796 priority patent/US8262811B2/en
Priority to PCT/EP2007/000805 priority patent/WO2007088030A1/fr
Priority to EP07703155A priority patent/EP1979507A1/fr
Priority to CN2007800013029A priority patent/CN101356301B/zh
Priority to JP2008551736A priority patent/JP5130226B2/ja
Priority to CA2624215A priority patent/CA2624215C/fr
Publication of EP1816234A1 publication Critical patent/EP1816234A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—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.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
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EP06001930A 2006-01-31 2006-01-31 Procédé et composition aqueuse pour la passivation du zinc ou des alliages à base de zinc Active EP1816234B1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
EP06001930A EP1816234B1 (fr) 2006-01-31 2006-01-31 Procédé et composition aqueuse pour la passivation du zinc ou des alliages à base de zinc
DE502006003710T DE502006003710D1 (de) 2006-01-31 2006-01-31 Wässrige Reaktionslösung und Verfahren zur Passivierung von Zink- und Zinklegierungen
PL06001930T PL1816234T3 (pl) 2006-01-31 2006-01-31 Reakcyjny roztwór wodny oraz metoda pasywacji cynku i stopów cynku
AT06001930T ATE431442T1 (de) 2006-01-31 2006-01-31 Wässrige reaktionslösung und verfahren zur passivierung von zink- und zinklegierungen
PCT/EP2007/000805 WO2007088030A1 (fr) 2006-01-31 2007-01-23 Solution de reaction aqueuse et procede de passivation de pieces travaillees comportant des surfaces en zinc ou en alliage de zinc
EP07703155A EP1979507A1 (fr) 2006-01-31 2007-01-23 Solution de reaction aqueuse et procede de passivation de pieces travaillees comportant des surfaces en zinc ou en alliage de zinc
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
CN2007800013029A CN101356301B (zh) 2006-01-31 2007-01-23 钝化具有锌或锌合金表面的加工件的含水反应溶液和方法
JP2008551736A JP5130226B2 (ja) 2006-01-31 2007-01-23 亜鉛または亜鉛合金表面を有する加工部品を不動態化するための水性反応溶液及び方法
CA2624215A CA2624215C (fr) 2006-01-31 2007-01-23 Solution de reaction aqueuse et procede de passivation de pieces travaillees comportant des surfaces en zinc ou en alliage de zinc

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06001930A EP1816234B1 (fr) 2006-01-31 2006-01-31 Procédé et composition aqueuse pour la passivation du zinc ou des alliages à base de zinc

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EP1816234A1 true EP1816234A1 (fr) 2007-08-08
EP1816234B1 EP1816234B1 (fr) 2009-05-13

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EP06001930A Active EP1816234B1 (fr) 2006-01-31 2006-01-31 Procédé et composition aqueuse pour la passivation du zinc ou des alliages à base de zinc
EP07703155A Withdrawn EP1979507A1 (fr) 2006-01-31 2007-01-23 Solution de reaction aqueuse et procede de passivation de pieces travaillees comportant des surfaces en zinc ou en alliage de zinc

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US (1) US8262811B2 (fr)
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DE102008044143A1 (de) * 2008-11-27 2010-06-02 Atotech Deutschland Gmbh Konversionsschichten für zinkhaltige Oberflächen
CN104141123A (zh) * 2014-07-24 2014-11-12 深圳市鑫明达环保科技有限公司 一种用于锌合金压铸件的高耐蚀钝化液及钝化方法
CN115516134A (zh) * 2020-04-03 2022-12-23 德国艾托特克有限两合公司 在锌铁合金上形成黑色钝化层的方法和黑色钝化组合物
RU2792999C1 (ru) * 2022-04-14 2023-03-28 Общество с ограниченной ответственностью "ЭКОТЕХ" Жидкость для химической конверсионной обработки и способ химической конверсионной обработки с ее использованием

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JP5155850B2 (ja) * 2006-03-03 2013-03-06 ディップソール株式会社 亜鉛又は亜鉛合金上に黒色の３価クロム化成皮膜を形成するための処理水溶液及び黒色３価クロム化成皮膜の形成方法
CN101665935B (zh) * 2009-09-27 2012-04-11 大连三达奥克化学股份有限公司 钢铁工件电泳涂装前常温皮膜钝化剂及其制备方法
DE102010001686A1 (de) * 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Zusammensetzung für die alkalische Passivierung von Zinkoberflächen
CN102560467A (zh) * 2012-02-14 2012-07-11 济南德锡科技有限公司 一种高耐蚀镀锌黑色钝化剂及其配制方法
WO2015029156A1 (fr) * 2013-08-28 2015-03-05 本田技研工業株式会社 Élément de véhicule et/ou élément de fixation filmogène de revêtement noir et procédé de fabrication s'y rapportant
CN103789758B (zh) * 2014-02-17 2016-09-07 默克新科技发展（天津）有限公司 一种镀锌层的金黄色钝化剂及其制备方法和钝化处理方法
CN103866307A (zh) * 2014-03-13 2014-06-18 沈阳市环东电镀厂 环保型一剂双色镀锌三价铬钝化剂及其制备和使用方法
CN104451645A (zh) * 2014-12-05 2015-03-25 上海奎鸣工程技术有限公司 一种三价铬钝化表面处理剂
US11008659B2 (en) * 2014-12-26 2021-05-18 Dipsol Chemicals Co., Ltd. Trivalent chromium chemical conversion liquid for zinc or zinc alloy bases and chemical conversion coating film
EP3771749A1 (fr) 2019-07-29 2021-02-03 Ewald Dörken Ag Procédé de passivation de substrats métalliques

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DE102008044143A1 (de) * 2008-11-27 2010-06-02 Atotech Deutschland Gmbh Konversionsschichten für zinkhaltige Oberflächen
DE102008044143B4 (de) * 2008-11-27 2011-01-13 Atotech Deutschland Gmbh Wässrige Behandlungslösung und Verfahren zur Erzeugung von Konversionsschichten für zinkhaltige Oberflächen
CN104141123A (zh) * 2014-07-24 2014-11-12 深圳市鑫明达环保科技有限公司 一种用于锌合金压铸件的高耐蚀钝化液及钝化方法
CN115516134A (zh) * 2020-04-03 2022-12-23 德国艾托特克有限两合公司 在锌铁合金上形成黑色钝化层的方法和黑色钝化组合物
CN115516134B (zh) * 2020-04-03 2024-02-09 德国艾托特克有限两合公司 在锌铁合金上形成黑色钝化层的方法和黑色钝化组合物
RU2792999C1 (ru) * 2022-04-14 2023-03-28 Общество с ограниченной ответственностью "ЭКОТЕХ" Жидкость для химической конверсионной обработки и способ химической конверсионной обработки с ее использованием

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CA2624215A1 (fr) 2007-08-09
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US8262811B2 (en) 2012-09-11
CN101356301A (zh) 2009-01-28
JP5130226B2 (ja) 2013-01-30
US20090032146A1 (en) 2009-02-05
PL1816234T3 (pl) 2009-10-30
DE502006003710D1 (de) 2009-06-25
ATE431442T1 (de) 2009-05-15
WO2007088030A1 (fr) 2007-08-09
CN101356301B (zh) 2011-12-28
CA2624215C (fr) 2013-07-02
EP1816234B1 (fr) 2009-05-13

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