WO2005068684A1 - Black passivation of zinc or zinc alloy surfaces - Google Patents

Black passivation of zinc or zinc alloy surfaces Download PDF

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Publication number
WO2005068684A1
WO2005068684A1 PCT/EP2005/000250 EP2005000250W WO2005068684A1 WO 2005068684 A1 WO2005068684 A1 WO 2005068684A1 EP 2005000250 W EP2005000250 W EP 2005000250W WO 2005068684 A1 WO2005068684 A1 WO 2005068684A1
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solution
solution according
passivation
chromium
zinc
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PCT/EP2005/000250
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German (de)
French (fr)
Inventor
Bertram Haag
Peter Herold
Rainer Dillinger
Sergej Vogelsang
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Schaeffler Kg
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Priority to EP05700867.4A priority Critical patent/EP1713955B1/en
Publication of WO2005068684A1 publication Critical patent/WO2005068684A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • 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
    • 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 invention relates to an aqueous solution for improving the black passivation of zinc or zinc alloy surfaces.
  • the invention also relates to associated methods for black passivation.
  • Metallic materials are galvanized to protect them from corrosive environmental influences.
  • the protection against corrosion of the zinc is based on the fact that it is even less noble than the base metal and therefore initially only attracts the corrosive attack, it acts as a sacrificial layer.
  • the base metal of the galvanized component in question remains intact as long as it is continuously covered with zinc and the mechanical functionality is retained over longer periods than with non-galvanized parts. Thick layers of zinc provide greater protection against corrosion than thin layers because the corrosive removal of thick layers takes longer.
  • the corrosive attack on the zinc layer in turn, can be greatly delayed by the application of chromate, and thus the base metal corrosion is also delayed further than by galvanizing alone.
  • the corrosion protection provided by the zinc / chromating layer system is considerably higher than that of a zinc layer of the same thickness. Chromating also delays the visual impairment of a component due to environmental influences, and the corrosion products of zinc, the so-called white rust, also have a disruptive effect on the appearance of a component.
  • the advantage The chromate applied is so large that almost every galvanized surface is also chromated.
  • the corrosion protection of undamaged black chromations based on chromium (VI) amounts to 50-150 hours in the salt spray test according to DIN 50021 SS. This corrosion test exposes a coated and passivated part to a 5% sodium chloride mist at 35 ° C and 100% humidity , The time required to oxidize 5 - 10% of the surface to white rust is measured.
  • the trivalent chromium is formed from hexavalent chromium by the addition of a reducing agent such as an aldehyde or alcohol, an alkali metal sulfite, bisulfite, iodide, hydrogen peroxide, sulfur dioxide or an iron salt. Since the conversion to chromium (IM) is not complete, it is possible that chromium (VI) in the passivation layer it is possible for chromium (VI) to be incorporated into the passivation layer, which is not particularly desirable when using such coatings in the food industry.
  • a reducing agent such as an aldehyde or alcohol, an alkali metal sulfite, bisulfite, iodide, hydrogen peroxide, sulfur dioxide or an iron salt.
  • EP 0 479 289 A1 describes a process in which phosphoric acid and hydrofluoric acid are present in the solution in a specific ratio to the chromium (III) ions and lead to a passivation surface of improved resistance.
  • Passivations based on chrome (Ill) are therefore used in two ways.
  • thin-film passivation with an additional post-treatment by sealing which is also referred to as a top coat.
  • This is to be understood as aftertreatment with wax-based, silicate or polymer-based agents.
  • thick film passivation which work with higher chromium concentrations and special stabilizers at higher temperatures and require longer exposure times.
  • Such layers have the thicknesses of common yellow or olive chromate layers and can be applied without sealing.
  • black chromating which is of particular importance for zinc alloys, there are particular problems since, although these can be carried out using known solutions for other chromating processes, they offer unsatisfactory corrosion protection. This can only be improved by a top coat coating.
  • top-coat covers cannot be rolled over and cannot be used for press and joint seats.
  • the object of the invention is therefore to provide an aqueous solution for the treatment of zinc or zinc alloy surfaces which, in the case of black passivation, enables substantially improved results in the formation of a chromium (VI) -free, homogeneous protective film of high corrosion resistance.
  • this object is achieved according to the characterizing part of claim 1 in that the solution contains inorganic and / or organic sulfur compounds.
  • the corrosion protection effect of protective layers consisting of chromium (III) ions can be significantly increased by the addition according to the invention. That's because to be attributed to the fact that the iron-sulfur pigments according to the invention which produce the black color improve the anti-corrosion effect of the protective layer, while the iron-phosphor pigments according to the prior art impair the anti-corrosion effect.
  • the inorganic and / or organic sulfur compounds can be handled in different ways. On the one hand, the aqueous solution with the sulfur compounds can be prepared as a separate solution and used immediately before or after the actual passivation of the surfaces, this being possible, for example, by a simple immersion process. On the other hand, it is also possible that the sulfur compounds according to the invention are added to the passivation solution used and in this way significantly improve the corrosion protection.
  • the associated different methods are described in claims 12, 13 and 14.
  • the solution contains salts or anhydrides of the following acids:
  • Hydrogen sulfide H 2 S
  • Thiosulfuric acid H 2 S 2 0 3
  • Disulphurous acid H 2 S 2 0 5
  • the solution should contain sulfur compounds in the form of alkali sulfite and / or alkali disulfite, especially sodium sulfite and / or sodium disulfite.
  • the dosage is evident from claims 6, 7 and 8. It is provided according to claim 6 that the solution contains 2-10 g / l, preferably 5 g / l sodium sulfite. According to claim 7, the solution should contain 2-10 g / l, preferably 6 g / l sodium disulfite. It is apparent from claim 8 that the solution should contain 2-10 g / l sodium sulfite and sodium disulfite, the two agents being usable in any mixing ratio.
  • the solution and thus the inorganic and / or organic sulfur compounds should be added to known passivation solutions, be free of chromium (VI) ions, contain chromium (III) ions and work in the acidic range.
  • Such a passivation solution known per se is derived from claim 10. Thereafter, it should contain chromium (III) ions acid and fluoride ions.
  • Such a solution could have the following composition, for example:
  • a steel component for a valve train of an internal combustion engine is provided with a corrosion protection layer made of a ZnFe alloy.
  • the electroplated layer has an alloying content of Fe of 0.8% and a layer thickness of 8 ⁇ m.
  • the steel component coated in this way was exposed to a chromium (III) -containing passivation solution from COVENTYA GmbH, which is sold under the trade name LANTHANE 315. This includes in accordance with the safety data among others chromium - (HO- nitrate and cobalt nitrate hexahydrate After setting a p H -value in the range of 1, 8 -.
  • the solution is ready for use, wherein the operating temperature is in the range from 40 to 70 °, preferably at 60 ° C. 5 g / l sodium sulfite were added to this passivation solution prepared in this way.
  • the steel component was immersed in the passivation solution for about 60 seconds and then rinsed several times in running water and finally dried.
  • the applied passivation layer showed a deep black color and was free of Cr (VI), as a corresponding test showed.
  • the passivated steel component was then subjected to the corrosion test according to DIN 50021 SS, the corrosion protection effect being many times higher than that of commercially available black passivation layers.
  • the corrosion protection performance achieved was> 1400 h.

Abstract

The invention relates to an aqueous solution which is used to improve black passivation of zinc or zinc alloy surfaces. Said solution is characterised in that it contains inorganic and/or organic sulphur compounds. As a result, protection against corrosion is essentially improved.

Description

Schwarzpassivierung von Zink- oder Zinklegierungsoberflächen Black passivation of zinc or zinc alloy surfaces
Anwendungsgebiet der ErfindungField of application of the invention
Die Erfindung betrifft eine wässrige Lösung zur Verbesserung der Schwarzpassivierung von Zink- oder Zinklegierungsoberflächen. Außerdem betrifft die Erfindung zugehörige Verfahren zur Schwarzpassivierung.The invention relates to an aqueous solution for improving the black passivation of zinc or zinc alloy surfaces. The invention also relates to associated methods for black passivation.
Hintergrund der ErfindungBackground of the Invention
Metallische Werkstoffe, insbesondere Eisen und Stahl, werden verzinkt, 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 Opfer- schicht. 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 einen höheren Korrosionsschutz als dünne Schichten, da der korrosive Abtrag von dicken Schichten länger dauert.Metallic materials, especially iron and steel, are galvanized to protect them from corrosive environmental influences. The protection against corrosion of the zinc is based on the fact that it is even less noble than the base metal and therefore initially only attracts the corrosive attack, it acts as a sacrificial layer. The base metal of the galvanized component in question remains intact as long as it is continuously covered with zinc and the mechanical functionality is retained over longer periods than with non-galvanized parts. Thick layers of zinc provide greater protection against corrosion than thin layers because the corrosive removal of thick layers takes 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 hinaus gezögert als durch eine Verzinkung allein. Der Korrosionsschutz durch das Schichtsystem Zink/Chromatierung ist erheb- lieh höher als durch eine gleichdicke Zinkschicht. Ferner wird durch die Chromatierung auch die optische Beeinträchtigung eines Bauteils durch Umwelteinflüsse hinausgezögert, auch die Korrosionsprodukte von Zink, der sogenannte Weißrost, wirken sich störend auf das Aussehen eines Bauteils aus. Die Vortei- le einer aufgebrachten Chromatierung sind so groß, dass fast jede galvanisch verzinkte Oberfläche zusätzlich auch chromatiert wird.The corrosive attack on the zinc layer, in turn, can be greatly delayed by the application of chromate, and thus the base metal corrosion is also delayed further than by galvanizing alone. The corrosion protection provided by the zinc / chromating layer system is considerably higher than that of a zinc layer of the same thickness. Chromating also delays the visual impairment of a component due to environmental influences, and the corrosion products of zinc, the so-called white rust, also have a disruptive effect on the appearance of a component. The advantage The chromate applied is so large that almost every galvanized surface is also chromated.
Je nach Zusammensetzung dieser Chromatierungslösungen entstehen dabei blaue, gelbe, olivfarbene oder schwarze Oberflächen, die sich sowohl im optischen Eindruck als auch in ihrem Korrosionsschutz stark unterscheiden. Bei Zinklegierungen wie Zink/Nickel, Zink/Eisen oder Zink/Kobalt lagern sich bei geeigneter Zusammensetzungen der Chromatierungslösung Nickel-, Eisenoder Kobaltoxid bzw. Kobaltphosphat als Schwarzpigment in die Chromat- schicht ein, da das in der Zink-Legierung enthaltene zweite Metall an der Metalloberfläche durch die Säurewirkung ebenfalls in ionische Form überführt und somit an der Ausbildung der Metalloxid-Schicht bzw. der Matallphosphat- Schicht beteiligt ist. Bei den bekannten Verfahren der Schwarzchromatierung werden erhebliche Mengen an Chrom (VI) in die Chromatschicht eingebaut. Der Korrosionsschutz von unverletzten Schwarzchromatierungen auf Basis von Chrom (VI) beläuft sich dabei auf 50-150 Stunden im Salzsprühtest gemäß DIN 50021 SS. Bei diesem Korrosionstest wird ein beschichtetes und passiviertes Teil bei 35 ° C und 100 % Luftfeuchtigkeit einem 5% igen Natriumchloridnebel ausgesetzt. Gemessen wird die Zeit, die benötigt wird, 5 - 10 % der Fläche zu Weißrost zu oxidieren.Depending on the composition of these chromating solutions, blue, yellow, olive-colored or black surfaces are created, which differ greatly in terms of both their visual impression and their corrosion protection. In the case of zinc alloys such as zinc / nickel, zinc / iron or zinc / cobalt, with suitable compositions of the chromating solution, nickel, iron or cobalt oxide or cobalt phosphate is deposited as a black pigment in the chromate layer, since the second metal contained in the zinc alloy binds to the Metal surface is also converted into ionic form by the acid action and is therefore involved in the formation of the metal oxide layer or the metal phosphate layer. In the known processes of black chromating, considerable amounts of chromium (VI) are built into the chromate layer. The corrosion protection of undamaged black chromations based on chromium (VI) amounts to 50-150 hours in the salt spray test according to DIN 50021 SS. This corrosion test exposes a coated and passivated part to a 5% sodium chloride mist at 35 ° C and 100% humidity , The time required to oxidize 5 - 10% of the surface to white rust is measured.
Aufgrund der Giftigkeit und krebserregenden Wirkung von Chrom (VI) wird seit Jahren versucht, Korrosionsschutzmittel auf Basis des weniger giftigen Chrom (III) zu etablieren. Dabei wurden Verfahren zur Blauchromatierung auf Basis von Chrom (III) entwickelt, die jedoch mit Nachteilen behaftet sind. Für Blau- chromatierungen sind aus der US 4,263,059 und der DE 30 38 699 A1 saure chromhaltige Passivierungslösungen bekannt, die aus einer blauen Lösung von dreiwertigem Chrom, einer Säure wie Ameisen-, Essig- oder Phosphorsäure, Salpeter-, Schwefel-, Salz- oder Fluorwasserstoffsäure sowie Fluoridionen bestehen. Das dreiwertige Chrom wird dabei aus sechswertigem Chrom durch die Zugabe eines Reduktionsmittels, wie etwa einem Aldehyd oder Alkohol, einem Alkalimetallsulfit, -bisulfit, -jodid Wasserstoffperoxid, Schwefeldioxid oder einem Eisensalz gebildet. Da die Umsetzung zu Chrom (IM) nicht vollständig ist, ist es möglich, daß Chrom (VI) in die Passivierungsschicht ist es möglich, daß Chrom (VI) in die Passivierungsschicht eingebaut wird, was insbesondere bei Verwendung solcher Beschichtungen in der Lebensmittelindustrie nicht erwünscht ist.Due to the toxicity and carcinogenic effects of chromium (VI), attempts have been made for years to establish corrosion protection agents based on the less toxic chromium (III). Processes for blue chromating based on chromium (III) were developed, but they have disadvantages. Acidic chromium-containing passivation solutions are known for blue chromating from US Pat. No. 4,263,059 and DE 30 38 699 A1 which consist of a blue solution of trivalent chromium, an acid such as formic, acetic or phosphoric acid, nitric, sulfuric, hydrochloric or Hydrofluoric acid and fluoride ions exist. The trivalent chromium is formed from hexavalent chromium by the addition of a reducing agent such as an aldehyde or alcohol, an alkali metal sulfite, bisulfite, iodide, hydrogen peroxide, sulfur dioxide or an iron salt. Since the conversion to chromium (IM) is not complete, it is possible that chromium (VI) in the passivation layer it is possible for chromium (VI) to be incorporated into the passivation layer, which is not particularly desirable when using such coatings in the food industry.
Auch wird seit längerem versucht, durch einen alternativen Ansatz Blaupassi- vierungen unter ausschließlicher Verwendung von Chrom (III) herzustellen. Die dazu eingesetzten sauren Chromatierungslösungen enthalten oft zusätzlich Oxidationsmittel (US 4,171 ,231) und weitere Zusätze wie Silikate und/oder andere Metallionen (US 4,384,902, US 4,359,347, US 4,367,099), Orga- nophosphorverbindungen oder Karbonsäuren (US 4,349,392). Durch den Zusatz von Oxidationsmitteln ist aber wiederum nicht sichergestellt, dass die erzeugten Schichten tatsächlich frei von Chrom (VI) sind.For some time now, attempts have been made to produce blue passages using only chromium (III) using an alternative approach. The acidic chromating solutions used for this often contain additional oxidizing agents (US Pat. No. 4,171, 231) and other additives such as silicates and / or other metal ions (US Pat. No. 4,384,902, US 4,359,347, US 4,367,099), organophosphorus compounds or carboxylic acids (US 4,349,392). However, the addition of oxidizing agents in turn does not ensure that the layers produced are actually free of chromium (VI).
Die EP 0 479 289 A1 beschreibt ein Verfahren, bei dem Phosphorsäure und Flusssäure in einem bestimmten Verhältnis zu den Chrom (lll)-lonen in der Lösung vorliegen und zu einer Passivierungsoberfläche von verbesserter Resistenz führen.EP 0 479 289 A1 describes a process in which phosphoric acid and hydrofluoric acid are present in the solution in a specific ratio to the chromium (III) ions and lead to a passivation surface of improved resistance.
Die DE 38 12 076 A1 beschreibt ein Verfahren zur Blauchromatierung unter Verwendung einer sauren chromathaltigen Passivierungslösung, die nur Chrom (III), aber keine Oxidationsmittel oder starken Komplexbildner enthält. Die verwendete Reaktionslösung enthält außerdem Nitrationen, Fluorid und Salz- oder Salpetersäure zur Einstellung des pH-Wertes. Der mit diesem Bad erzielte Korrosionsschutz ist aber relativ schwach und liegt bei etwa 44 - 50 Stunden ge- maß DIN 50021 SS.DE 38 12 076 A1 describes a process for blue chromating using an acidic chromate-containing passivation solution which contains only chromium (III) but no oxidizing agents or strong complexing agents. The reaction solution used also contains nitrate ions, fluoride, and hydrochloric or nitric acid to adjust the p H -value. However, the corrosion protection achieved with this bath is relatively weak and is around 44 - 50 hours according to DIN 50021 SS.
Passivierungen auf Chrom (Ill)-Basis werden demnach auf zwei Arten genutzt. Zum einen als Dünnschichtpassivierungen mit einer zusätzlichen Nachbehandlung durch Versiegeln, das auch als Top Coat bezeichnet wird. Darunter ist ein Nachbehandeln mit Mitteln auf Wachsbasis, silikatischer oder Polymerbasis zu verstehen. Zum anderen als Dickschichtpassivierung, die mit höheren Chrom - Konzentrationen und speziellen Stabilisatoren bei höheren Temperaturen arbeiten und längere Expositionszeiten benötigen. Derartige Schichten besitzen die Dicken von üblichen Gelb- oder Olivchromatschichten und können ohne Versiegelung angewendet werden. Im Bereich der Schwarzchromatierung, die bei Zinklegierungen von besonderer Bedeutung ist, ergeben sich besondere Probleme, da diese zwar mit bekannten Lösungen für andere Chromatierungs- verfahren durchgeführt werden können, aber einen unbefriedigenden Korrosionsschutz bieten. Dieser kann nur durch eine Top Coat-Beschichtung verbessert werden.Passivations based on chrome (Ill) are therefore used in two ways. On the one hand as thin-film passivation with an additional post-treatment by sealing, which is also referred to as a top coat. This is to be understood as aftertreatment with wax-based, silicate or polymer-based agents. On the other hand as thick film passivation, which work with higher chromium concentrations and special stabilizers at higher temperatures and require longer exposure times. Such layers have the thicknesses of common yellow or olive chromate layers and can be applied without sealing. In the area of black chromating, which is of particular importance for zinc alloys, there are particular problems since, although these can be carried out using known solutions for other chromating processes, they offer unsatisfactory corrosion protection. This can only be improved by a top coat coating.
Aus optischen Gründen spricht die Schwarzchromatierung in der Automobilin- dustrie eine besondere Rolle. Die bisherigen CrVI-freien Schwarzpassivierun- gen bieten jedoch, wie vorstehend bereits ausgeführt, nur einen geringen Korrosionsschutz, der durch die Top Coat-Beschichtung verbessert wird. In vielen Fällen ist diese zusätzliche Beschichtung nach der Schwarzpassivierung aber unerwünscht, da diese unter Umständen einen funktionellen Ausfall des betref- fenden Bauteils bewirken kann. So sind mit Top Coat versehene Überzüge aufgrund ihrer Sprödigkeit nicht überrollfähig und auch für Press- und Fügesitze nicht verwendbar.For optical reasons, black chromating plays a special role in the automotive industry. However, the previous CrVI-free black passivations, as already explained above, offer only a low level of corrosion protection, which is improved by the top coat coating. In many cases, this additional coating after the black passivation is undesirable, since under certain circumstances this can cause the component in question to fail. Because of their brittleness, top-coat covers cannot be rolled over and cannot be used for press and joint seats.
Zusammenfassung der ErfindungSummary of the invention
Aufgabe der Erfindung ist es daher, eine wässrige Lösung zur Behandlung von Zink- oder Zinklegierungsoberflächen bereitzustellen, die beim Schwarz- passivieren wesentlich verbesserte Ergebnisse bei der Ausbildung eines Chrom (Vl)-freien, homogenen Schutzfilms von hoher Korrosionsresistenz er- möglicht.The object of the invention is therefore to provide an aqueous solution for the treatment of zinc or zinc alloy surfaces which, in the case of black passivation, enables substantially improved results in the formation of a chromium (VI) -free, homogeneous protective film of high corrosion resistance.
Erfindungsgemäß wird diese Aufgabe nach dem kennzeichnenden Teil von Anspruch 1 dadurch gelöst, dass die Lösung anorganische und/oder organische Schwefelverbindungen enthält.According to the invention, this object is achieved according to the characterizing part of claim 1 in that the solution contains inorganic and / or organic sulfur compounds.
In überraschender Weise wurde gefunden, dass durch den erfindungsgemäßen Zusatz die Korrosionsschutzwirkung von aus Chrom-(lll)-lonen bestehenden Schutzschichten wesentlich gesteigert werden kann. Das ist darauf zu- rückzuführen, dass die die schwarze Farbe erzeugenden erfindungsgemäßen Eisen-Schwefel-Pigmente die Korrosionsschutzwirkung der Schutzschicht verbessern, während die Eisen-Phosphor-Pigmente nach dem Stand der Technik die Korrosionsschutzwirkung verschlechtern. Dabei können die anorgani- sehen und/oder organischen Schwefelverbindungen auf unterschiedliche Weise gehandhabt werden. Zum einen kann die wässrige Lösung mit den Schwefelverbindungen als getrennte Lösung angesetzt und unmittelbar vor oder auch nach der eigentlichen Passivierung der Oberflächen verwendet werden, wobei dies beispielsweise durch einen einfachen Tauchvorgang geschehen kann. Zum anderen ist es auch möglich, dass die erfindungsgemäßen Schwefelverbindungen der verwendeten Passivierungslösung zugesetzt werden und auf diese Weise den Korrosionsschutz wesentlich verbessern. Die zugehörigen unterschiedlichen Verfahren sind in den Ansprüchen 12, 13 und 14 beschrieben.Surprisingly, it was found that the corrosion protection effect of protective layers consisting of chromium (III) ions can be significantly increased by the addition according to the invention. That's because to be attributed to the fact that the iron-sulfur pigments according to the invention which produce the black color improve the anti-corrosion effect of the protective layer, while the iron-phosphor pigments according to the prior art impair the anti-corrosion effect. The inorganic and / or organic sulfur compounds can be handled in different ways. On the one hand, the aqueous solution with the sulfur compounds can be prepared as a separate solution and used immediately before or after the actual passivation of the surfaces, this being possible, for example, by a simple immersion process. On the other hand, it is also possible that the sulfur compounds according to the invention are added to the passivation solution used and in this way significantly improve the corrosion protection. The associated different methods are described in claims 12, 13 and 14.
In Weiterbildung der Erfindung ist nach Anspruch 2 vorgesehen, dass die Lösung Salze oder Anhydride folgender Säuren enthält:According to a further development of the invention, the solution contains salts or anhydrides of the following acids:
Hyposchwefelige Säure (H2S02) - Schweflige Säure (H2S03)Hyposulphurous acid (H 2 S0 2 ) - Sulphurous acid (H 2 S0 3 )
Schwefelwasserstoffsäure (H2S) Thioschwefelsäure (H2S203) Dischweflige Säure (H2S205)Hydrogen sulfide (H 2 S) Thiosulfuric acid (H 2 S 2 0 3 ) Disulphurous acid (H 2 S 2 0 5 )
Nach einem weiteren Merkmal der Erfindung gemäß Anspruch 3 ist vorgesehen, dass sich die in Anspruch 2 genannten Verbindungen auch aus Substanzen freisetzen lassen, die diese enthalten.According to a further feature of the invention according to claim 3 it is provided that the compounds mentioned in claim 2 can also be released from substances which contain them.
Nach weiteren Merkmalen gemäß den Ansprüchen 4 und 5 soll die Lösung Schwefelverbindungen in Form von Alkalisulfit und/oder Alkalidisulfit, speziell Natriumsulfit und/oder Natriumdisulfit enthalten. Die Dosierung geht aus den Ansprüchen 6, 7 und 8 hervor. So ist nach Anspruch 6 vorgesehen, dass die Lösung 2 - 10 g/l, vorzugsweise 5 g/l Natriumsulfit enthält. Nach Anspruch 7 soll die Lösung 2 - 10 g/l, vorzugsweise 6 g/l Natriumdisulfit enthalten. Aus Anspruch 8 geht hervor, dass die Lösung 2 - 10 g/l Natriumsulfit und Natriumdisulfit enthalten soll, wobei die beiden Agenzien in jedem beliebigen Mischungsverhältnis einsetzbar sind.According to further features according to claims 4 and 5, the solution should contain sulfur compounds in the form of alkali sulfite and / or alkali disulfite, especially sodium sulfite and / or sodium disulfite. The dosage is evident from claims 6, 7 and 8. It is provided according to claim 6 that the solution contains 2-10 g / l, preferably 5 g / l sodium sulfite. According to claim 7, the solution should contain 2-10 g / l, preferably 6 g / l sodium disulfite. It is apparent from claim 8 that the solution should contain 2-10 g / l sodium sulfite and sodium disulfite, the two agents being usable in any mixing ratio.
Nach Anspruch 9 soll die Lösung und damit die anorganisch und/oder organi- sehen Schwefelverbindungen an sich bekannten Passivierungslösungen zugesetzt sein, frei von Chrom-(VI)-lonen sein, Chrom-(lll)-lonen enthalten und im sauren Bereich arbeiten.According to claim 9, the solution and thus the inorganic and / or organic sulfur compounds should be added to known passivation solutions, be free of chromium (VI) ions, contain chromium (III) ions and work in the acidic range.
Eine solche an sich bekannte Passivierungslösung geht aus Anspruch 10 her- vor. Danach soll diese Chrom-(lll)-lonen Säure und Fluoridionen enthalten.Such a passivation solution known per se is derived from claim 10. Thereafter, it should contain chromium (III) ions acid and fluoride ions.
Eine solche Lösung könnte beispielsweise folgende Zusammensetzung aufweisen:Such a solution could have the following composition, for example:
3 g/I KCr(S04)2 » 12H203 g / l KCr (S0 4 ) 2 »12H 2 0
4 g/I HN03 2 g/l (NH4) HF2 4 g / l HN0 3 2 g / l (NH 4 ) HF 2
Im Sinne der Erfindung sind damit die Grundbestandteile einer Passivierunglö- sung gemeint, zu denen in erfindungsgemäßer Weise die Agentien gemäß Hauptanspruch zugesetzt werden.For the purposes of the invention, this means the basic components of a passivation solution, to which the agents according to the main claim are added in the manner according to the invention.
Eine weitere an sich bekannte Passierungslösung ist in Anspruch 11 beschrieben. Danach soll diese Chrom-(lll)-lonen und Kobaltsalze enthalten. Als Bei- spiel sei hierfür eine Chrom-(lll)-Ionen, Kobaltnitrat, Natriumnitrat und Malon- säure enthaltende Lösung mit nachstehender Zusammensetzung aufgeführt: 50 g/l CrCI3 • 6H20Another known pass solution is described in claim 11. Thereafter, it should contain chromium (III) ions and cobalt salts. An example of this is a solution containing chromium (III) ions, cobalt nitrate, sodium nitrate and malonic acid with the following composition: 50 g / l CrCI 3 • 6H 2 0
3 g/l Co (N03)2 3 g / l Co (N0 3 ) 2
100 g/I NaNO3 100 g / l NaNO 3
31 g/l CH2^ C00H N C00H31 g / l CH 2 ^ C00H N C00H
Die Erfindung wird an nachstehendem Ausführungsbeispiel näher erläutert:The invention is explained in more detail using the following exemplary embodiment:
Ein Stahlbauteil für einen Ventiltrieb einer Brennkraftmaschine ist mit einer Korrosionsschutzschicht aus einer ZnFe-Legierung versehen. Die galvanisch aufgebrachte Schicht hat einen Legierungsanteil an Fe von 0,8 % und weist eine Schichtstärke von 8 μm auf. Das derart beschichtete Stahlbauteil wurde einer Chrom (lll)-haltigen Passivierungslösung der Firma COVENTYA GmbH ausgesetzt, die unter dem Handelsnamen LANTHANE 315 vertrieben wird. Diese enthält nach dem Sicherheitsdatenblatt unter anderem Chrom -(HO- Nitrat und Kobaltnitrathexahydrat. Nach Einstellung eines pH-Wertes im Bereich von 1 ,8 - 2,2, wobei die Einstellung mit Salpetersäure oder Natronlauge vorzunehmen ist, ist die Lösung betriebsbereit, wobei die Betriebstemperatur im Bereich von 40 - 70 °, vorzugsweise bei 60 ° liegt. Dieser so vorbereiteten Passivierungslösung wurden in erfindungsgemäßer Weise 5 g/l Natriumsulfit zugesetzt.A steel component for a valve train of an internal combustion engine is provided with a corrosion protection layer made of a ZnFe alloy. The electroplated layer has an alloying content of Fe of 0.8% and a layer thickness of 8 μm. The steel component coated in this way was exposed to a chromium (III) -containing passivation solution from COVENTYA GmbH, which is sold under the trade name LANTHANE 315. This includes in accordance with the safety data among others chromium - (HO- nitrate and cobalt nitrate hexahydrate After setting a p H -value in the range of 1, 8 -. 2.2, wherein the adjustment is to be made with nitric acid or sodium hydroxide solution, the solution is ready for use, wherein the operating temperature is in the range from 40 to 70 °, preferably at 60 ° C. 5 g / l sodium sulfite were added to this passivation solution prepared in this way.
Das Stahlbauteil wurde etwa 60 sec in die Passivierungslösung eingetaucht und danach mehrfach in fließendem Wasser abgespült und schließlich ge- trocknet. Die aufgebrachte Passivierungsschicht zeigte eine tiefschwarze Färbung und war frei von Cr (VI), wie ein entsprechender Test belegte. Das so passivierte Stahlbauteil wurde abschließend dem Korrosionstest nach DIN 50021 SS unterzogen, wobei die Korrosionsschutzwirkung im Vergleich zu kommerziell erhältlichen Schwarzpassivierungsschichten um ein Vielfaches höher lag. Die erreichte Korrosionsschutzleistung belief sich auf > 1400 h. The steel component was immersed in the passivation solution for about 60 seconds and then rinsed several times in running water and finally dried. The applied passivation layer showed a deep black color and was free of Cr (VI), as a corresponding test showed. The passivated steel component was then subjected to the corrosion test according to DIN 50021 SS, the corrosion protection effect being many times higher than that of commercially available black passivation layers. The corrosion protection performance achieved was> 1400 h.

Claims

Patentansprüche claims
1. Wässrige Lösung zur Verbesserung der Schwarzpassivierung von Zinkoder Zinklegierungsoberflächen, dadurch gekennzeichnet, dass sie anorganische und/oder organische Schwefelverbindungen enthält.1. Aqueous solution to improve the black passivation of zinc or zinc alloy surfaces, characterized in that it contains inorganic and / or organic sulfur compounds.
2. Lösung nach Anspruch 1 , dadurch gekennzeichnet, dass sie Salze oder Anhydride folgender Säuren enthält:2. Solution according to claim 1, characterized in that it contains salts or anhydrides of the following acids:
- Hyposchwefelige Säure (H2S02)- Hyposulphurous acid (H 2 S0 2 )
- Schweflige Säure (H2S03)- Sulphurous acid (H 2 S0 3 )
- Schwefelwasserstoffsäure (H2S) - Thioschwefelsäure (H2S203)- Hydrogen sulfide (H 2 S) - Thiosulfuric acid (H 2 S 2 0 3 )
- Dischweflige Säure (H2S205)- Sulfuric acid (H 2 S 2 0 5 )
3. Lösung nach Anspruch 2, dadurch gekennzeichnet, dass sie Substanzen enthält, aus denen sich die genannten Verbindungen freisetzen lassen.3. Solution according to claim 2, characterized in that it contains substances from which the said compounds can be released.
4. Lösung nach Anspruch 1 , dadurch gekennzeichnet, dass sie Alkalisulfit und/oder Alkalidisulfit enthält.4. Solution according to claim 1, characterized in that it contains alkali sulfite and / or alkali disulfite.
5. Lösung nach Anspruch 4, dadurch gekennzeichnet, dass sie Natriumsulfit (Na2S03) und/oder Natriumdisulfit (Na2S205) enthält.5. Solution according to claim 4, characterized in that it contains sodium sulfite (Na 2 S0 3 ) and / or sodium disulfite (Na 2 S 2 0 5 ).
6. Lösung nach Anspruch s, dadurch gekennzeichnet, dass sie 2 - 10 g/l, vorzugsweise 5 g/l Natriumsulfit enthält.6. Solution according to claim s, characterized in that it contains 2-10 g / l, preferably 5 g / l sodium sulfite.
7. Lösung nach Anspruch s, dadurch gekennzeichnet, dass sie 2 - 10 g/l, vorzugsweise 6 g/l Natriumdisulfit enthält. 7. Solution according to claim s, characterized in that it contains 2-10 g / l, preferably 6 g / l sodium disulfite.
8. Lösung nach Anspruch 5, dadurch gekennzeichnet, dass sie 2 - 10 g/l Natriumsulfit und Natriumdisulfit in einem beliebigen Mischungsverhältnis enthält.8. Solution according to claim 5, characterized in that it contains 2-10 g / l sodium sulfite and sodium disulfite in any mixing ratio.
9. Lösung nach Anspruch 1 , dadurch gekennzeichnet, dass sie an sich bekannten Schwarzpassivierungslösungen zugesetzt ist, frei von Chrom-(VI)- lonen ist, Chrom - (III) - Ionen enthält und im sauren Bereich arbeitet.9. Solution according to claim 1, characterized in that it is added to known black passivation solutions, is free of chromium (VI) ions, contains chromium (III) ions and works in the acidic range.
10. Lösung nach Anspruch 9, dadurch gekennzeichnet, dass sie Chrom-(lll)- Ionen, Säure und Fluoridionen enthält.10. Solution according to claim 9, characterized in that it contains chromium (III) ions, acid and fluoride ions.
11. Lösung nach Anspruch 9, dadurch gekennzeichnet, dass sie Chrom-(lll)- lonen und Kobaltsalze enthält.11. Solution according to claim 9, characterized in that it contains chromium (III) ions and cobalt salts.
12. Verfahren zur Schwarzpassivierung, gekennzeichnet durch die Herstellung einer wässrigen Lösung nach Anspruch 1 , Eintauchen eines zu behandeln den Gegenstandes in diese Lösung, Eintauchen dieses Gegenstandes in eine an sich bekannte Passivierungslösung.12. A method for black passivation, characterized by the preparation of an aqueous solution according to claim 1, immersing an object to be treated in this solution, immersing this object in a passivation solution known per se.
13. Verfahren zur Schwarzpassivierung, gekennzeichnet durch Eintauchen eines zu behandelnden Gegenstandes in eine an sich bekannte Passivierungslösung, Herstellung einer wässrigen Lösung nach Anspruch 1 und Eintauchen dieses Gegenstandes in diese Lösung.13. A method for black passivation, characterized by immersing an object to be treated in a passivation solution known per se, producing an aqueous solution according to claim 1 and immersing this object in this solution.
14. Verfahren zur Schwarzpassivierung, gekennzeichnet durch die Herstellung einer wässrigen Lösung nach Anspruch 1 , Zugabe dieser Lösung in eine an sich bekannte Passivierungslösung und Eintauchen eines zu behandelnden Gegenstandes in eine derart hergestellte Lösung. 14. A method for black passivation, characterized by the preparation of an aqueous solution according to claim 1, adding this solution in a passivation solution known per se and immersing an object to be treated in a solution prepared in this way.
PCT/EP2005/000250 2004-01-14 2005-01-13 Black passivation of zinc or zinc alloy surfaces WO2005068684A1 (en)

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