EP1713955B1 - 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
EP1713955B1
EP1713955B1 EP05700867.4A EP05700867A EP1713955B1 EP 1713955 B1 EP1713955 B1 EP 1713955B1 EP 05700867 A EP05700867 A EP 05700867A EP 1713955 B1 EP1713955 B1 EP 1713955B1
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Prior art keywords
zinc
chromium
acid
solution
passivation
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EP05700867.4A
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German (de)
French (fr)
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EP1713955A1 (en
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Bertram Haag
Peter Herold
Rainer Dillinger
Sergej Vogelsang
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Schaeffler Technologies AG and Co KG
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Schaeffler Technologies AG and Co KG
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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 relates to associated methods for black passivation.
  • the black passivation of zinc surfaces is for example from the JP 2003 213446 A known.
  • the surface treatment is carried out here with acidic, aqueous solutions containing sulfur compounds.
  • 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 delayed even further than by galvanizing alone.
  • the corrosion protection by the layer system zinc / chromating is considerably higher than by an equal thickness zinc layer.
  • chromating also delays the optical impairment of a component due to environmental influences; even the corrosion products of zinc, the so-called white rust, have a disruptive effect on the appearance of a component.
  • the advantages An applied chromating is so great that almost every galvanized surface is additionally chromated.
  • the corrosion protection of undamaged black chromates based on chromium (VI) amounts to 50-150 hours in the salt spray test according to DIN 50021 SS.
  • a coated and passivated part is exposed to a 5% sodium chloride mist at 35 ° C. and 100% atmospheric humidity , The time taken to oxidize 5-10% of the area to white rust is measured.
  • the trivalent chromium is thereby 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 (III) is not complete, it is possible that chromium (VI) enters the passivation layer For example, chromium (VI) may be incorporated into the passivation layer, which is undesirable particularly when such coatings are used 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.
  • the EP 0 479 289 A1 describes a process in which phosphoric acid and hydrofluoric acid are in a certain proportion to the chromium (III) ions in the solution and result in a passivation surface of improved resistance.
  • the DE 38 12 076 A1 describes a process for blue-chromating using an acidic chromate-containing passivating solution containing 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.
  • the achieved with this bath corrosion protection is relatively weak and is about 44 - 50 hours according to DIN 50021 SS.
  • Chromium (III) based passivations are thus used in two ways.
  • thin-layer passivations with an additional post-treatment by sealing which is also referred to as top coat.
  • 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. Own such layers the thicknesses of common yellow or olive chromate layers and can be applied without sealing.
  • black chromating which is of particular importance in zinc alloys, there are particular problems, since these can be carried out with known solutions for other chromating, but offer unsatisfactory corrosion protection. This can only be improved by a Top Coat coating.
  • the object of the invention is therefore to provide an aqueous solution for the treatment of zinc or zinc alloy surfaces, which allows significantly improved black-passivation results in the formation of a chromium (VI) -free, homogeneous protective film of high corrosion resistance.
  • this object is achieved according to claim 1, characterized in that the solution contains sulfur compounds in the form of alkali metal sulfite and / or alkali metal disulfide, namely sodium sulfite and / or sodium disulfite.
  • the solution contains 2 - 10 g / l sodium sulfite and sodium disulfite, the two agents can be used in any mixing ratio.
  • the additive according to the invention makes it possible to substantially increase the anticorrosive effect of protective layers consisting of chromium (III) ions.
  • protective layers consisting of chromium (III) ions.
  • the black-color producing iron-sulfur pigments of the present invention improve the anticorrosive effect of the protective layer, while the prior art iron-phosphorus pigments deteriorate the anticorrosive effect.
  • the inorganic and / or organic sulfur compounds are handled as follows: The sulfur compounds of the invention are added to the passivation solution used, whereby the corrosion protection is substantially improved. The corresponding method is described in claim 6.
  • the solution 2 - contains 10 g / l, preferably 5 g / l sodium sulfite.
  • the solution 2 - 10 g / l preferably 6 g / l sodium disulfite.
  • the solution containing the inorganic and / or organic sulfur compounds is added to passivation solutions known per se, free from chromium (VI) ions, contains chromium (III) ions and works in the acidic range.
  • Such a passivation solution known per se contains, in addition to chromium (III) ions, acid and fluoride ions.
  • a steel component for a valve train of an internal combustion engine is provided with a corrosion protection layer of a ZnFe alloy.
  • the electroplated layer has an alloy content of Fe of 0.8% and has a layer thickness of 8 ⁇ m.
  • the thus coated steel component was exposed to a chromium (III) -containing passivation solution from COVENTYA GmbH, which is sold under the trade name LANTHANE 315. According to the safety data sheet, this contains among others chromium (III) nitrate and cobalt nitrate hexahydrate.
  • the solution is ready for use, with the operating temperature in the range of 40 to 70 °, preferably 60 °. 5 g / l of sodium sulfite were added to this passivation solution prepared in this way in accordance with the invention.
  • the steel component was immersed for about 60 seconds in the passivation solution 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 proved.
  • the passivated steel component was finally subjected to the corrosion test in accordance with DIN 50 021 SS, the corrosion protection effect being many times higher in comparison with commercially available black passivation layers.
  • the achieved corrosion protection performance amounted to> 1400 h.

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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)

Description

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. In addition, the invention relates to associated methods for black passivation.

Hintergrund der ErfindungBackground of the invention

Die Schwarzpassivierung von Zinkoberflächen ist beispielsweise aus der JP 2003 213446 A bekannt. Die Oberflächenbehandlung erfolgt hierbei mit sauren, wässrigen Lösungen, die Schwefelverbindungen enthalten.The black passivation of zinc surfaces is for example from the JP 2003 213446 A known. The surface treatment is carried out here with acidic, aqueous solutions containing sulfur compounds.

Weitere Verfahren der Schwarzpassivierung sind in der US 4,968,391 A offenbart. Hierbei kommen insbesondere Lösungen, die Chrom-(III)-Ionen enthalten, zum Einsatz.Other methods of black passivation are in the US 4,968,391 A disclosed. In particular, solutions containing chromium (III) ions are used here.

Die Verwendung von Chrom-(III)-Ionen enthaltenden Lösungen beim Schwarzpassivieren ist auch aus der DE 101 62 756 A1 bekannt. Als Aktivator wird in diesem Fall Phosphat zugegeben.The use of chromium (III) ion-containing solutions in black passivation is also known from the DE 101 62 756 A1 known. As activator in this case phosphate is added.

In einer zum Schwarzpassivieren vorgesehenen Behandlungslösung nach der WO 03/076686 A1 sind neben Chrom-(III)-Ionen unter anderem Kobaltsalze und Sulfationen enthalten.In a black passivation treatment solution after the WO 03/076686 A1 In addition to chromium (III) ions among other cobalt salts and sulfate ions are included.

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 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 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 corrosion protection of zinc It is based on the fact that it is even 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 respective galvanized component remains intact as long as 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 greater corrosion protection than thin coatings, as 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 erheblich 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 Vorteile 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 a chromating, and thus the base metal corrosion is delayed even further than by galvanizing alone. The corrosion protection by the layer system zinc / chromating is considerably higher than by an equal thickness zinc layer. Furthermore, chromating also delays the optical impairment of a component due to environmental influences; even the corrosion products of zinc, the so-called white rust, have a disruptive effect on the appearance of a component. The advantages An applied chromating is so great that almost every galvanized surface is additionally 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-, Eisen - oder Kobaltoxid bzw. Kobaltphosphat als Schwarzpigment in die Chromatschicht 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 or black surfaces are formed, which differ greatly both in their appearance and in their corrosion protection. For zinc alloys such as zinc / nickel, zinc / iron or zinc / cobalt, nickel, iron or cobalt oxide or cobalt phosphate as black pigment are incorporated in the chromate layer with suitable compositions of the chromating solution since the second metal contained in the zinc alloy is deposited on the chromate layer Metal surface is also converted by the acid effect in ionic form and thus involved in the formation of the metal oxide layer or the Matallphosphat layer. In the known processes of black chromating considerable amounts of chromium (VI) are incorporated into the chromate layer. The corrosion protection of undamaged black chromates based on chromium (VI) amounts to 50-150 hours in the salt spray test according to DIN 50021 SS. In this corrosion test, a coated and passivated part is exposed to a 5% sodium chloride mist at 35 ° C. and 100% atmospheric humidity , The time taken to oxidize 5-10% of the area 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 Blauchromatierungen 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 (III) 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 inhibitors based on less toxic chromium (III). In this process, processes for blue chromate formation based on chromium (III) have been developed, but they have disadvantages. For blue chromations are from the US 4,263,059 and the DE 30 38 699 A1 acidic passivation solutions containing chromium, 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. The trivalent chromium is thereby 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 (III) is not complete, it is possible that chromium (VI) enters the passivation layer For example, chromium (VI) may be incorporated into the passivation layer, which is undesirable particularly when such coatings are used in the food industry.

Auch wird seit längerem versucht, durch einen alternativen Ansatz Blaupassivierungen 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 ), Organophosphorverbindungen 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.It has also long been attempted, by an alternative approach, to produce blue passivations using only chromium (III). The acidic chromating solutions used for this purpose often additionally contain oxidizing agents ( US 4,171,231 ) and other additives such as silicates and / or other metal ions ( US 4,384,902 . US 4,359,347 . US 4,367,099 ), Organophosphorus compounds or carboxylic acids ( US 4,349,392 ). However, the addition of oxidants does not ensure that the layers produced are indeed 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 (III)-Ionen in der Lösung vorliegen und zu einer Passivierungsoberfläche von verbesserter Resistenz führen.The EP 0 479 289 A1 describes a process in which phosphoric acid and hydrofluoric acid are in a certain proportion to the chromium (III) ions in the solution and result in 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 gemäß DIN 50021 SS.The DE 38 12 076 A1 describes a process for blue-chromating using an acidic chromate-containing passivating solution containing 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. The achieved with this bath corrosion protection is relatively weak and is about 44 - 50 hours according to DIN 50021 SS.

Passivierungen auf Chrom (III)-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 Chromatierungsverfahren durchgeführt werden können, aber einen unbefriedigenden Korrosionsschutz bieten. Dieser kann nur durch eine Top Coat-Beschichtung verbessert werden.Chromium (III) based passivations are thus used in two ways. On the one hand as thin-layer passivations with an additional post-treatment by sealing, which is also referred to as 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. Own such layers the thicknesses of common yellow or olive chromate layers and can be applied without sealing. In the field of black chromating, which is of particular importance in zinc alloys, there are particular problems, since these can be carried out with known solutions for other chromating, but offer unsatisfactory corrosion protection. This can only be improved by a Top Coat coating.

Aus optischen Gründen spricht die Schwarzchromatierung in der Automobilindustrie eine besondere Rolle. Die bisherigen CrVI-freien Schwarzpassivierungen 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 betreffenden 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 offer, as already stated above, only a slight corrosion protection, which is improved by the Top Coat coating. In many cases, however, this additional coating after black passivation is undesirable, since under certain circumstances this may cause a functional failure of the relevant component. Because of their brittleness, coatings provided with Top Coat can not be rolled over and can not be used on 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 (VI)-freien, homogenen Schutzfilms von hoher Korrosionsresistenz ermöglicht.The object of the invention is therefore to provide an aqueous solution for the treatment of zinc or zinc alloy surfaces, which allows significantly improved black-passivation results in the formation of a chromium (VI) -free, homogeneous protective film of high corrosion resistance.

Erfindungsgemäß wird diese Aufgabe nach dem Anspruch 1 dadurch gelöst, dass die Lösung Schwefelverbindungen in Form von Alkalisulfit und/oder Alkalidisulfit, nämlich Natriumsulfit und/oder Natriumdisulfit, enthält.According to the invention this object is achieved according to claim 1, characterized in that the solution contains sulfur compounds in the form of alkali metal sulfite and / or alkali metal disulfide, namely sodium sulfite and / or sodium disulfite.

Die Lösung enthält 2 - 10 g/l Natriumsulfit und Natriumdisulfit, wobei die beiden Agenzien in jedem beliebigen Mischungsverhältnis einsetzbar sind.The solution contains 2 - 10 g / l sodium sulfite and sodium disulfite, the two agents can be used in any mixing ratio.

In überraschender Weise wurde gefunden, dass durch den erfindungsgemäßen Zusatz die Korrosionsschutzwirkung von aus Chrom-(III)-Ionen bestehenden Schutzschichten wesentlich gesteigert werden kann. Das ist darauf zurückzuführen, 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 werden die anorganischen und/oder organischen Schwefelverbindungen folgendermaßen gehandhabt: Die erfindungsgemäßen Schwefelverbindungen werden der verwendeten Passivierungslösung zugesetzt, womit der Korrosionsschutz wesentlich verbessert wird. Das entsprechende Verfahren ist in Anspruch 6 beschrieben.Surprisingly, it has been found that the additive according to the invention makes it possible to substantially increase the anticorrosive effect of protective layers consisting of chromium (III) ions. This is because the black-color producing iron-sulfur pigments of the present invention improve the anticorrosive effect of the protective layer, while the prior art iron-phosphorus pigments deteriorate the anticorrosive effect. In this case, the inorganic and / or organic sulfur compounds are handled as follows: The sulfur compounds of the invention are added to the passivation solution used, whereby the corrosion protection is substantially improved. The corresponding method is described in claim 6.

In Weiterbildung der Erfindung ist nach Anspruch 2 vorgesehen, dass die Lösung Salze oder Anhydride folgender Säuren enthält:

  • Hyposchwefelige Säure (H2SO2)
  • Schweflige Säure (H2SO3)
  • Schwefelwasserstoffsäure (H2S)
  • Thioschwefelsäure (H2S2O3)
  • Dischweflige Säure (H2S2O5)
In a further development of the invention, it is provided according to claim 2 that the solution contains salts or anhydrides of the following acids:
  • Hyposulphurous acid (H 2 SO 2 )
  • Sulfurous acid (H 2 SO 3 )
  • Hydrosilicic acid (H 2 S)
  • Thiosulphuric acid (H 2 S 2 O 3 )
  • Dischweflige acid (H 2 S 2 O 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 containing them.

Mögliche Dosierungen gehen aus den Ansprüchen 4 und 5 hervor. So ist nach Anspruch 4 vorgesehen, dass die Lösung 2 - 10 g/l, vorzugsweise 5 g/l Natriumsulfit enthält. Nach Anspruch 5 soll die Lösung 2 - 10 g/l, vorzugsweise 6 g/l Natriumdisulfit enthalten.Possible dosages are evident from the claims 4 and 5. Thus, it is provided according to claim 4, that the solution 2 - contains 10 g / l, preferably 5 g / l sodium sulfite. According to claim 5, the solution 2 - 10 g / l, preferably 6 g / l sodium disulfite.

Die Lösung mit den anorganischen und/oder organischen Schwefelverbindungen ist an sich bekannten Passivierungslösungen zugesetzt, frei von Chrom-(VI)-Ionen, enthält Chrom-(III)-Ionen und arbeitet im sauren Bereich.The solution containing the inorganic and / or organic sulfur compounds is added to passivation solutions known per se, free from chromium (VI) ions, contains chromium (III) ions and works in the acidic range.

Eine solche an sich bekannte Passivierungslösung enthält neben Chrom-(III)-Ionen Säure und Fluoridionen.Such a passivation solution known per se contains, in addition to chromium (III) ions, acid and fluoride ions.

Eine solche Lösung könnte beispielsweise folgende Zusammensetzung aufweisen:

  • 3 g/l KCr(SO4)2 ● 12H2O
  • 4 g/l HNO3
  • 2 g/l (NH4) HF2
Such a solution could, for example, have the following composition:
  • 3 g / l KCr (SO 4 ) 2 ● 12H 2 O
  • 4 g / l HNO 3
  • 2 g / l (NH 4 ) HF 2

Im Sinne der Erfindung sind damit die Grundbestandteile einer Passivierunglösung gemeint, zu denen in erfindungsgemäßer Weise die Agentien gemäß Hauptanspruch zugesetzt werden.For the purposes of the invention, this means the basic constituents of a passivation solution to which the agents according to the invention are added in accordance with the main claim.

Eine weitere an sich bekannte Passierungslösung enthält Chrom-(III)-Ionen und Kobaltsalze. Als Beispiel sei hierfür eine Chrom-(III)-Ionen, Kobaltnitrat, Natriumnitrat und Malonsäure enthaltende Lösung mit nachstehender Zusammensetzung aufgeführt:

  • 50 g/l CrCl3 ● 6H2O
  • 3 g/l Co (NO3)2
  • 100 g/l NaNO3
  • Figure imgb0001
Another known pass-through solution contains chromium (III) ions and cobalt salts. As an example, a chromium (III) ion, cobalt nitrate, sodium nitrate and malonic acid-containing solution having the following composition can be mentioned:
  • 50 g / l CrCl 3 ● 6H 2 O
  • 3 g / l Co (NO 3 ) 2
  • 100 g / l NaNO 3
  • Figure imgb0001

Die Erfindung wird an nachstehendem Ausführungsbeispiel näher erläutert:The invention is explained in more detail in 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 (III)-haltigen Passivierungslösung der Firma COVENTYA GmbH ausgesetzt, die unter dem Handelsnamen LANTHANE 315 vertrieben wird. Diese enthält nach dem Sicherheitsdatenblatt unter anderem Chrom -(III)-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 of a ZnFe alloy. The electroplated layer has an alloy content of Fe of 0.8% and has a layer thickness of 8 μm. The thus coated steel component was exposed to a chromium (III) -containing passivation solution from COVENTYA GmbH, which is sold under the trade name LANTHANE 315. According to the safety data sheet, this contains among others chromium (III) nitrate and cobalt nitrate hexahydrate. After setting a p H value in the range of 1.8 to 2.2, wherein the adjustment is to be carried out with nitric acid or sodium hydroxide solution, the solution is ready for use, with the operating temperature in the range of 40 to 70 °, preferably 60 °. 5 g / l of sodium sulfite were added to this passivation solution prepared in this way in accordance with the invention.

Das Stahlbauteil wurde etwa 60 sec in die Passivierungslösung eingetaucht und danach mehrfach in fließendem Wasser abgespült und schließlich getrocknet. 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 50 021 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 for about 60 seconds in the passivation solution 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 proved. The passivated steel component was finally subjected to the corrosion test in accordance with DIN 50 021 SS, the corrosion protection effect being many times higher in comparison with commercially available black passivation layers. The achieved corrosion protection performance amounted to> 1400 h.

Claims (6)

  1. Aqueous solution for improving the black passivation of zinc or zinc alloy surfaces, which contains inorganic and/or organic sulphur compounds, characterized in that it contains 2-10 g/l of sodium sulphite (Na2SO3) and sodium disulphite (Na2S2O5) in any mixing ratio and is added to a black passivation solution known per se which is free of chromium (VI) ions and contains chromium (III) ions, acid and fluoride ions.
  2. Solution according to Claim 1, characterized in that it contains salts or anhydrides of the following acids:
    - hyposulphurous acid (H2SO2)
    - sulphurous acid (H2SO3)
    - hydrogen sulphide (H2S) thiosulfuric acid (H2S2O3)
    - disulphurous acid (H2S2O5)
  3. Solution according to Claim 2, characterized in that it contains substances from which the compounds mentioned can be liberated.
  4. Solution according to Claim 1, characterized in that it contains 2-10 g/l, preferably 5 g/l, of sodium sulphite.
  5. Solution according to Claim 1, characterized in that it contains 2-10 g/l, preferably 6 g/l, of sodium disulphite.
  6. Process for black passivation, characterized by production of an aqueous solution according to Claim 1 and dipping of an object which has a zinc or zinc alloy surface and is to be treated into this solution.
EP05700867.4A 2004-01-14 2005-01-13 Black passivation of zinc or zinc alloy surfaces Expired - Fee Related EP1713955B1 (en)

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DE102009045569A1 (en) 2009-10-12 2011-04-14 Dr.-Ing. Max Schlötter GmbH & Co KG Black passivation of zinc and zinc iron layers
ES2765816T3 (en) 2017-07-14 2020-06-11 Doerken Ewald Ag Composition and procedure to passivate galvanized components

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US2302643A (en) * 1941-05-26 1942-11-17 Parker Rust Proof Co Method and composition for treating metals
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JPS6431982A (en) * 1987-07-29 1989-02-02 Nippon Steel Corp Black plated steel sheet and its production
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DE10162756A1 (en) * 2001-12-20 2003-07-10 Walter Hillebrand Gmbh & Co Schwarzpassivierungsverfahren
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