EP1002143B1 - Alkaline strip passivation - Google Patents

Alkaline strip passivation Download PDF

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Publication number
EP1002143B1
EP1002143B1 EP98942626A EP98942626A EP1002143B1 EP 1002143 B1 EP1002143 B1 EP 1002143B1 EP 98942626 A EP98942626 A EP 98942626A EP 98942626 A EP98942626 A EP 98942626A EP 1002143 B1 EP1002143 B1 EP 1002143B1
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EP
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Prior art keywords
ions
free
passivation
alkaline
points
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EP98942626A
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German (de)
French (fr)
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EP1002143A1 (en
Inventor
Jörg Riesop
Heike Krautbauer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium 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
    • C23C22/73—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 characterised by the process
    • 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
    • C23C22/83—Chemical after-treatment

Definitions

  • the invention relates to a method for the alkaline passivation of galvanized and galvanized steel surfaces as well as aluminum and its Alloys in conveyor systems. This passivation creates a Corrosion protection layer, which is the basis for subsequent painting can serve.
  • Alkaline passivation processes are used to treat the above Metal surfaces have been known for a long time.
  • the treatment solutions usually toxic heavy metals such as nickel ions and / or Cobalt ions.
  • nickel ions and / or Cobalt ions By suitable complexing agents, these ions are among the alkaline conditions kept in solution. Examples of such Passivation solutions are given in EP-A-405 340.
  • the invention therefore has as its object a method for to provide alkaline passivation of suitable metal surfaces, which has a similar performance to processes containing nickel or cobalt has, but no toxic heavy metals used.
  • GB-A-1 042 108 describes an alkaline, chromate-free treatment bath for galvanized or coated with a zinc alloy surface, which preferably has a pH in the range from 12.6 to 13.3.
  • the bath contains 0.002 to 0.5% of a metal from the group Mg, Cd, Al, Sn, Ti, Sb, Mo, Cr, Ce, W, Mn, Co, Fe and Ni as well as an amount of an organic complexing agent to the metal to keep complex solutions.
  • the surfaces are treated for 20 to 60 seconds at a temperature of 90 to 200 ° F.
  • the bath contains 3% NaOH, 0.2% sodium hexahydroxyheptoate, 0.008% Fe 3+ and 0.042% Mg. Baths which hold two or more metals in solution in complex form are preferred; preferred metals are iron and cobalt.
  • Aluminum alloys which contain more than 50% by weight of aluminum.
  • Alkaline means that the treatment solutions have a pH from above 9.5, preferably in the range from 10 to 13. to In practice, the characterization of the treatment baths serves less the pH values, but the levels of free alkalinity and total alkalinity.
  • the free Alkalinity is determined by diluting 2 ml bath solution, preferably to 50 ml, with a 0.1 N acid such as hydrochloric acid or sulfuric acid titrated to a pH of 8.5. The consumption of acid solution in ml gives the Score of free alkalinity.
  • the overall alkalinity is determined accordingly, by adding 2 ml of treatment solution, diluted to 50 ml, with 0.1N acid up to titrated to a pH of 4.0. This inevitably means that the total alkalinity is higher than the free alkalinity.
  • the treatment solution can contain additional active substances that have a positive effect on the formation of layers and corrosion protection.
  • contents from about 0.001 to about 20 g / l of finely divided SiO 2 , for example pyrogenic silica, may be mentioned.
  • BET specific surface area
  • Aqueous suspensions of such silicas are commercially available.
  • Another optional component of the treatment solution is about 0.001 to about 10 g / l of monomeric or oligomeric acrylate and / or methacrylate ions.
  • This can be as soluble salts, for example sodium salts, or in the form of the free Acid can be added to the treatment solution.
  • Drying step at the latest when baking an applied lacquer, polymerize these ions and thereby improve the layer properties.
  • the amino or hydroxy carboxylate ions serve to prevent the precipitation of iron and magnesium compounds at the alkaline pH of the treatment solution to prevent.
  • all amino or hydroxy carboxylate ions are for this suitable that produce this effect. They can be in the form of soluble salts such as for example sodium salts or as free acids in the treatment solution be introduced.
  • Monobasic hydroxycarboxylic acids are preferred with at least 4 carbon atoms and at least 2 alcoholic hydroxyl groups.
  • Gluconate ions or those longer by one carbon atom are particularly preferred Glucoheptanationen.
  • the treatment solutions also contain the anions of the salts than that of the magnesium and iron (III) ions in the treatment solution have been introduced.
  • the nitrates are preferably used here, since Nitrate ions have no negative influence on corrosion protection.
  • the process is designed for the treatment of running metal strips, so that the treatment time depending on the belt speed and length of the Treatment zone is in the range of a few seconds.
  • the Treatment time is about 3 to about 30 seconds and is preferably in Range from 5 to 15 seconds.
  • aqueous treatment solution becomes the end of the desired exposure time rinsed.
  • the corrosion protection effect can be further improved if the undergoes post-passivation of alkaline passivated metal surfaces.
  • Post-passivation after an alkaline passivation is state of the art Processes containing chromium are widely used.
  • a post passivation containing chrome is also as an aftertreatment after the alkaline passivation according to the invention suitable.
  • chrome-free Post-passivation solutions are particularly suitable for aqueous solutions, the titanium and / or zirconium compounds, in particular complex fluorides thereof Contains items.
  • such a post-passivation solution a total of 0.4 to 10 g / l complex fluorides of titanium and / or zirconium contain.
  • the pH of this chrome-free post-passivation solution is preferably in the range of about 2 to about 4.
  • the alkaline passivation step according to the invention thus represents a Treatment stage of a multi-stage treatment chain, in which the metal strips are usually first degreased and rinsed. This is followed by the Alkaline passivation according to the invention, usually followed by the steps Rinsing, re-passivation, usually rinsing again, drying (at about 60 up to about 100 ° C object temperature), painting.
  • the procedure is preferably such that first magnesium and iron salts, preferably nitrates, until the required Dissolves the concentration in water, then adds the complexing carboxylic acid and only then by adding lye, for example sodium hydroxide solution, the alkaline pH established.
  • the following exemplary embodiments show that the alkaline passivation process according to the invention leads to similar corrosion protection results as comparison processes according to the prior art which contain toxic nickel and / or cobalt ions.
  • the galvanized and alloy-galvanized steel sheets listed in Table 2 were alkaline passivated according to Table 1, rinsed for 5 seconds with water, re-passivated with chrome-containing or chrome-free rinse solutions (treatment time: 5 seconds spraying), rinsed for 2 seconds with deionized water and in a circulating air Drying cabinet dried at a cabinet temperature of 70 ° C.
  • 5 ⁇ m primer and 18 ⁇ m top coat, each based on polyester, were applied and baked at 216 and 249 ° C, respectively.
  • test panels were then subjected to a 42-day salt spray test in accordance with the German standard DIN 50 021 SS.
  • the results (paint infiltration in mm at the cut or at the edge) are shown in Table 2.
  • the paint adhesion was examined after a T-Bend test. There were no significant differences between the method according to the invention and the nickel and / or cobalt-containing comparison methods.

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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)

Abstract

The invention relates to a method for the alkaline passivation of galvanised and alloy-galvanised steel surfaces and of aluminium in strip plants. According to the invention, the metal surfaces are brought into contact with an alkaline aqueous solution containing complexers and iron, said solution having a free alkalinity level of between 5 and 20 points and an overall alkalinity level of between 7 and 30 points and containing 0.1 to 1 g/l magnesium ions, 0.1 to 1 g/l iron (III) ions and 0.5 to 5 g/l amino or hydroxycarboxylate ions. A repassivation with or without chromium can then be carried out.

Description

Die Erfindung betrifft ein Verfahren zur alkalischen Passivierung von verzinkten und legierungsverzinkten Stahloberflächen sowie von Aluminium und dessen Legierungen in Bandanlagen. Durch diese Passivierung entsteht eine Korrosionsschutzschicht, die als Grundlage für eine nachfolgende Lackierung dienen kann.The invention relates to a method for the alkaline passivation of galvanized and galvanized steel surfaces as well as aluminum and its Alloys in conveyor systems. This passivation creates a Corrosion protection layer, which is the basis for subsequent painting can serve.

Alkalische Passivierverfahren sind zur Behandlung der genannten Metalloberflächen seit langem bekannt. Um einen ausreichenden Korrosionsschutz und die erforderliche Lackhaftung zu erzielen, enthalten die Behandlungslösungen in der Regel toxische Schwermetalle wie beispielsweise Nickelionen und/oder Cobaltionen. Durch geeignete Komplexbildner werden diese Ionen unter den alkalischen Bedingungen in Lösung gehalten. Beispiele derartiger Passivierungslösungen sind in der EP-A-405 340 angegeben.Alkaline passivation processes are used to treat the above Metal surfaces have been known for a long time. To provide adequate protection against corrosion and to achieve the required paint adhesion contain the treatment solutions usually toxic heavy metals such as nickel ions and / or Cobalt ions. By suitable complexing agents, these ions are among the alkaline conditions kept in solution. Examples of such Passivation solutions are given in EP-A-405 340.

Durch die Anwesenheit von Nickel- und/oder Cobaltionen in der alkalischen Passivierungslösung werden zufriedenstellende Ergebnisse hinsichtlich Korrosionsschutz und Lackhaftung erhalten. Wegen der hohen Toxizität, den erforderlichen Arbeitsschutzmaßnahmen und der aufwendigen Entsorgung bestehen jedoch Bedenken gegen den Einsatz toxischer Schwermetalle wie beispielsweise Nickel oder Cobalt. Die Erfindung stellt sich daher die Aufgabe, ein Verfahren zur alkalischen Passivierung geeigneter Metalloberflächen zur Verfügung zu stellen, das eine ähnliche Leistungsfähigkeit wie Nickel- oder Cobalt-haltige Verfahren aufweist, jedoch keine toxischen Schwermetalle verwendet. Due to the presence of nickel and / or cobalt ions in the alkaline Passivation solution will give satisfactory results in terms of corrosion protection and get paint adhesion. Because of the high toxicity, the required Occupational safety measures and elaborate disposal exist Concerns about the use of toxic heavy metals such as nickel or cobalt. The invention therefore has as its object a method for to provide alkaline passivation of suitable metal surfaces, which has a similar performance to processes containing nickel or cobalt has, but no toxic heavy metals used.

In der GB-A-1 042 108 wird ein alkalisches, Chromat-freies Behandlungsbad für verzinkte oder mit einer Zinklegierung beschichtete Oberfläche beschrieben, welches vorzugsweise einen pH-Wert im Bereich von 12,6 bis 13,3 aufweist. Das Bad enthält 0,002 bis 0,5 % eines Metalls aus der Gruppe Mg, Cd, Al, Sn, Ti, Sb, Mo, Cr, Ce, W, Mn, Co, Fe und Ni sowie soviel eines organischen Komplexierungsmittels, um das Metall komplexgebunden in Lösung zu halten. Die Behandlung der Oberflächen erfolgt für 20 bis 60 sec bei einer Temperatur von 90 bis 200 °F. In einem Beispiel enthält das Bad 3 % NaOH, 0,2 % Natrium-hexahydroxyheptoat, 0,008 % Fe3+ und 0,042 % Mg. Bevorzugt werden Bäder, die zwei oder mehrere Metalle komplexgebunden in Lösung halten; bevorzugte Metalle sind hierbei Eisen und Kobalt.GB-A-1 042 108 describes an alkaline, chromate-free treatment bath for galvanized or coated with a zinc alloy surface, which preferably has a pH in the range from 12.6 to 13.3. The bath contains 0.002 to 0.5% of a metal from the group Mg, Cd, Al, Sn, Ti, Sb, Mo, Cr, Ce, W, Mn, Co, Fe and Ni as well as an amount of an organic complexing agent to the metal to keep complex solutions. The surfaces are treated for 20 to 60 seconds at a temperature of 90 to 200 ° F. In one example, the bath contains 3% NaOH, 0.2% sodium hexahydroxyheptoate, 0.008% Fe 3+ and 0.042% Mg. Baths which hold two or more metals in solution in complex form are preferred; preferred metals are iron and cobalt.

Die vorstehend definierte Aufgabe wird gelöst durch ein Verfahren zur alkalischen Passivierung von verzinkten und legierungsverzinkten Stahloberflächen sowie von Aluminium oder Aluminiumlegierungen, die zu mehr als 50 Gew.-% Aluminium enthalten, in Bandanlagen, wobei man die Metalloberflächen mit einer alkalischen, komplexbildner- und eisenhaltigen wäßrigen Lösung in Kontakt bringt, die frei ist von zugesetzten Nickel- und Cobaltionen und die

  • eine freie Alkalität im Bereich von 5 bis 20 Punkten und
  • eine Gesamtalkalität im Bereich von 7 bis 30 Punkten aufweist und
  • 0,1 bis 1 g/l Magnesiumionen,
  • 0,1 bis 1 g/l Eisen(III)ionen und
  • 0,5 bis 5 g/l Amino- oder Hydroxycarboxylationen enthält.
    • The object defined above is achieved by a process for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminum or aluminum alloys which contain more than 50% by weight of aluminum in strip systems, the metal surfaces containing an alkaline, complexing agent and iron-containing brings into contact aqueous solution which is free of added nickel and cobalt ions and which
  • a free alkalinity in the range of 5 to 20 points and
  • has a total alkalinity in the range of 7 to 30 points and
  • 0.1 to 1 g / l magnesium ions,
  • 0.1 to 1 g / l iron (III) ions and
  • Contains 0.5 to 5 g / l amino or hydroxy carboxylate ions.

    • Wenn hierbei von "Aluminium" die Rede ist, so sind damit Aluminium und Aluminiumlegierungen gemeint, die zu mehr als 50 Gew.-% Aluminium enthalten.If we are talking about "aluminum", we are talking about aluminum and Aluminum alloys are meant which contain more than 50% by weight of aluminum.

    Unter "alkalisch" wird verstanden, daß die Behandlungslösungen einen pH-Wert von oberhalb 9,5, vorzugsweise im Bereich von 10 bis 13 aufweisen. Zur Charakterisierung der Behandlungsbäder dienen in der Praxis weniger die pH-Werte, sondern die Gehalte an freier Alkalität und Gesamtalkalität. Die freie Alkalität wird dadurch bestimmt, daß man 2 ml Badlösung, vorzugsweise verdünnt auf 50 ml, mit einer 0,1 n Säure wie beispielsweise Salzsäure oder Schwefelsäure bis zu einem pH-Wert von 8,5 titriert. Der Verbrauch an Säurelösung in ml gibt die Punktzahl der freien Alkalität an. Entsprechend bestimmt man die Gesamtalkalität, indem man 2 ml Behandlungslösung, verdünnt auf 50 ml, mit 0,1 n Säure bis zu einem pH-Wert von 4,0 titriert. Dies bedeutet zwangsläufig, daß die Gesamtalkalität höher ist als die freie Alkalität.“Alkaline” means that the treatment solutions have a pH from above 9.5, preferably in the range from 10 to 13. to In practice, the characterization of the treatment baths serves less the pH values, but the levels of free alkalinity and total alkalinity. The free Alkalinity is determined by diluting 2 ml bath solution, preferably to 50 ml, with a 0.1 N acid such as hydrochloric acid or sulfuric acid titrated to a pH of 8.5. The consumption of acid solution in ml gives the Score of free alkalinity. The overall alkalinity is determined accordingly, by adding 2 ml of treatment solution, diluted to 50 ml, with 0.1N acid up to titrated to a pH of 4.0. This inevitably means that the total alkalinity is higher than the free alkalinity.

    Die Behandlungslösung kann zusätzliche Wirkstoffe enthalten, die die Schichtausbildung und den Korrosionsschutz positiv beeinflussen. Beispielsweise genannt seien Gehalte von etwa 0,001 bis etwa 20 g/l feinteiliges SiO2, beispielsweise pyrogene Kieselsäure. Vorzugsweise verwendet man pyrogene Kieselsäure mit einer spezifischen Oberfläche (BET) im Bereich von etwa 150 bis etwa 300 m2/g, beispielsweise etwa 200 m2/g. Wäßrige Suspensionen derartiger Kieselsäuren sind im Handel erhältlich.The treatment solution can contain additional active substances that have a positive effect on the formation of layers and corrosion protection. For example, contents from about 0.001 to about 20 g / l of finely divided SiO 2 , for example pyrogenic silica, may be mentioned. Pyrogenic silica with a specific surface area (BET) in the range from about 150 to about 300 m 2 / g, for example about 200 m 2 / g, is preferably used. Aqueous suspensions of such silicas are commercially available.

    Ein weiterer fakultativer Bestandteil der Behandlungslösung sind etwa 0,001 bis etwa 10 g/l monomere oder oligomere Acrylat- und/oder Methacrylationen. Diese können als lösliche Salze, beispielsweise Natriumsalze, oder in Form der freien Säure der Behandlungslösung zugegeben werden. Bei dem nachfolgenden Trocknungsschritt, spätestens beim Einbrennen eines aufgebrachten Lacks, polymerisieren diese Ionen und verbessern hierdurch die Schichteigenschaften.Another optional component of the treatment solution is about 0.001 to about 10 g / l of monomeric or oligomeric acrylate and / or methacrylate ions. This can be as soluble salts, for example sodium salts, or in the form of the free Acid can be added to the treatment solution. In the following Drying step, at the latest when baking an applied lacquer, polymerize these ions and thereby improve the layer properties.

    Die Amino- oder Hydroxycarboxylationen dienen dazu, die Ausfällung von Eisen- und Magnesiumverbindungen bei dem alkalischen pH-Wert der Behandlungslösung zu verhindern. Prinzipiell sind hierfür alle Amino- oder Hydroxycarboxylationen geeignet, die diese Wirkung hervorrufen. Sie können in Form löslicher Salze wie beispielsweise Natriumsalze oder als freie Säuren in die Behandlungslösung eingebracht werden. Bevorzugt sind einbasische Hydroxycarbonsäuren mit mindestens 4 C-Atomen und mindestens 2 alkoholischen Hydroxylgruppen. Besonders bevorzugt sind Gluconationen oder die um ein C-Atom längeren Glucoheptanationen.The amino or hydroxy carboxylate ions serve to prevent the precipitation of iron and magnesium compounds at the alkaline pH of the treatment solution to prevent. In principle, all amino or hydroxy carboxylate ions are for this suitable that produce this effect. They can be in the form of soluble salts such as for example sodium salts or as free acids in the treatment solution be introduced. Monobasic hydroxycarboxylic acids are preferred with at least 4 carbon atoms and at least 2 alcoholic hydroxyl groups. Gluconate ions or those longer by one carbon atom are particularly preferred Glucoheptanationen.

    Außer diesen Komponenten enthalten die Behandlungslösungen noch die Anionen der Salze, als die die Magnesium- und Eisen(III)-Ionen in die Behandlungslösung eingebracht worden sind. Vorzugsweise setzt man hierbei die Nitrate ein, da Nitrationen keinen negativen Einfluß auf den Korrosionsschutz ausüben.In addition to these components, the treatment solutions also contain the anions of the salts than that of the magnesium and iron (III) ions in the treatment solution have been introduced. The nitrates are preferably used here, since Nitrate ions have no negative influence on corrosion protection.

    Das Verfahren ist für die Behandlung von laufenden Metallbändem konzipiert, so daß die Behandlungszeit je nach Bandgeschwindigkeit und Länge der Behandlungszone im Bereich weniger Sekunden liegt. Beispielsweise kann die Behandlungsdauer etwa 3 bis etwa 30 Sekunden betragen und liegt vorzugsweise im Bereich von 5 bis 15 Sekunden. Dabei bringt man die Metalloberflächen vorzugsweise mit einer wäßrigen Behandlungslösung in Kontakt, die eine Temperatur im Bereich von etwa 40 bis etwa 70 °C aufweist. Für das Inkontaktbringen sind Spritz-, Tauch- und Aufwalzverfahren geeignet. Üblich und im Rahmen des erfinderischen Verfahrens geeignet ist die Spritzapplikation. Nach Ende der erwünschten Einwirkungsdauer wird die wäßrige Behandlungslösung abgespült.The process is designed for the treatment of running metal strips, so that the treatment time depending on the belt speed and length of the Treatment zone is in the range of a few seconds. For example, the Treatment time is about 3 to about 30 seconds and is preferably in Range from 5 to 15 seconds. You bring the metal surfaces preferably in contact with an aqueous treatment solution, the one Has temperature in the range of about 40 to about 70 ° C. For the Spraying, dipping and rolling processes are suitable for contacting. Usual and Spray application is suitable within the scope of the inventive method. To The aqueous treatment solution becomes the end of the desired exposure time rinsed.

    Die Korrosionsschutzwirkung kann weiter verbessert werden, wenn man die alkalisch passivierten Metalloberflächen einer Nachpassivierung unterzieht. Zur Nachpassivierung nach einer alkalischen Passivierung sind im Stand der Technik chromhaltige Verfahren weit verbreitet. Eine chromhaltige Nachpassivierung ist auch als Nachbehandlung nach der erfindungsgemäßen alkalischen Passivierung geeignet. Ein besonderer Vorteil des erfindungsgemäßen Verfahrens liegt jedoch darin, daß auf eine ökologisch und toxikologisch problematische chromhaltige Nachbehandlung verzichtet werden und statt dessen eine chromfreie Nachpassivierung vorgenommen werden kann. Als chromfreie Nachpassivierungslösungen kommen insbesondere wäßrige Lösungen in Betracht, die Titan- und/oder Zirkonverbindungen, insbesondere komplexe Fluoride dieser Elemente enthält. Beispielsweise kann eine derartige Nachpassivierlösung insgesamt 0,4 bis 10 g/l komplexe Fluoride von Titan und/oder Zirkonium enthalten. Der pH-Wert dieser chromfreien Nachpassivierungslösung liegt vorzugsweise im Bereich von etwa 2 bis etwa 4.The corrosion protection effect can be further improved if the undergoes post-passivation of alkaline passivated metal surfaces. to Post-passivation after an alkaline passivation is state of the art Processes containing chromium are widely used. A post passivation containing chrome is also as an aftertreatment after the alkaline passivation according to the invention suitable. However, there is a particular advantage of the method according to the invention in that on an ecologically and toxicologically problematic chromium-containing After-treatment can be dispensed with and instead a chrome-free one Post passivation can be made. As chrome-free Post-passivation solutions are particularly suitable for aqueous solutions, the titanium and / or zirconium compounds, in particular complex fluorides thereof Contains items. For example, such a post-passivation solution a total of 0.4 to 10 g / l complex fluorides of titanium and / or zirconium contain. The pH of this chrome-free post-passivation solution is preferably in the range of about 2 to about 4.

    Der erfindungsgemäße alkalische Passivierungsschritt stellt damit eine Behandlungsstufe einer vielstufigen Behandlungskette dar, bei der die Metallbänder üblicherweise zunächst entfettet und gespült werden. Hierauf erfolgt die erfindungsgemäße alkalische Passivierung, üblicherweise gefolgt von den Schritten Spülen, Nachpassivieren, üblicherweise nochmaliges Spülen, Trocknen (bei etwa 60 bis etwa 100 °C Objekttemperatur), Lackieren.The alkaline passivation step according to the invention thus represents a Treatment stage of a multi-stage treatment chain, in which the metal strips are usually first degreased and rinsed. This is followed by the Alkaline passivation according to the invention, usually followed by the steps Rinsing, re-passivation, usually rinsing again, drying (at about 60 up to about 100 ° C object temperature), painting.

    Prinzipiell kann die alkalische Passivierungslösung vor Ort durch Auflösen der Einzelkomponenten in Wasser in der erforderlichen Einsatzkonzentration hergestellt werden. In der Praxis ist es jedoch üblich, Konzentrate zu fertigen und zur Behandlungsanlage zu transportieren, wo durch einfaches Verdünnen mit Wasser die anwendungsfertige Behandlungslösung zubereitet wird. Demgemäß umfaßt die Erfindung auch ein wäßriges Konzentrat, das beim Verdünnen mit Wasser um einen Faktor im Bereich von 7 bis 15 eine wäßrige Behandlungslösung zur alkalischen Passivierung von verzinkten und legierungsverzinkten Stahloberflächen sowie von Aluminium oder Aluminiumlegierungen, die zu mehr als 50 Gew.-% Aluminium enthalten, in Bandanlagen ergibt, die frei ist von zugesetzten Nickel- und Cobaltionen und die

  • eine freie Alkalität im Bereich von 5 bis 20 Punkten und
  • eine Gesamtalkalität im Bereich von 7 bis 30 Punkten aufweist und
  • 0,1 bis 1 g/l Magnesiumionen,
  • 0,1 bis 1 g/l Eisen(II)ionen und
  • 0,5 bis 5 g/l Amino- oder Hydroxycarboxylationen enthält.
    • In principle, the alkaline passivation solution can be prepared on site by dissolving the individual components in water in the required concentration. In practice, however, it is common to manufacture concentrates and transport them to the treatment plant, where the ready-to-use treatment solution is prepared by simply diluting with water. Accordingly, the invention also comprises an aqueous concentrate which, when diluted with water by a factor in the range from 7 to 15, contains an aqueous treatment solution for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminum or aluminum alloys which contain more than 50% by weight of aluminum contained in strip systems, which is free of added nickel and cobalt ions and which
  • a free alkalinity in the range of 5 to 20 points and
  • has a total alkalinity in the range of 7 to 30 points and
  • 0.1 to 1 g / l magnesium ions,
  • 0.1 to 1 g / l iron (II) ions and
  • Contains 0.5 to 5 g / l amino or hydroxy carboxylate ions.

    • Bei der Herstellung derartiger Konzentrate geht man vorzugsweise so vor, daß man zunächst Magnesium- und Eisensalze, vorzugsweise Nitrate, bis zur erforderlichen Konzentration in Wasser auflöst, anschließend die komplexierende Carbonsäure zugibt und erst dann durch Zugabe von Lauge, beispielsweise Natronlauge, den alkalischen pH-Wert einstellt. In the preparation of such concentrates, the procedure is preferably such that first magnesium and iron salts, preferably nitrates, until the required Dissolves the concentration in water, then adds the complexing carboxylic acid and only then by adding lye, for example sodium hydroxide solution, the alkaline pH established.

    Ausführungsbeispieleembodiments

    Die nachfolgenden Ausführungsbeispiele zeigen, daß das erfindungsgemäße alkalische Passivierverfahren zu ähnlichen Korrosionsschutzergebnissen führt wie Vergleichsverfahren nach dem Stand der Technik, die toxische Nickel- und/oder Cobaltionen enthalten. Dabei wurden die in Tabelle 2 genannten verzinkten und legierungsverzinkten Stahlbleche gemäß Tabelle 1 alkalisch passiviert, für 5 Sekunden mit Wasser gespült, mit chromhaltigen oder chromfreien Nachspüllösungen nachpassiviert (Behandlungszeit: 5 Sekunden Spritzen), für 2 Sekunden mit vollentsalztem Wasser gespült und in einem Umluft-Trockenschrank bei einer Schranktemperatur von 70 °C getrocknet. Zur Lackierung wurden 5 µm Primer und 18 um Decklack, jeweils auf Polyesterbasis, aufgebracht und bei 216 bzw. 249 °C eingebrannt. Danach wurden die Probebleche einem 42-tägigen Salzsprühtest gemäß deutscher Norm DIN 50 021 SS unterzogen. Die Ergebnisse (Lackunterwanderung in mm am Schnitt bzw. an der Kante) sind in Tabelle 2 wiedergegeben. Zusätzlich wurde die Lackhaftung nach einem T-Bend-Test untersucht. Hierbei zeigten sich keine signifikanten Unterschiede zwischen dem erfindungsgemäßen Verfahren und den Nickel- und/oder Cobalt-haltigen Vergleichsverfahren.

    Figure 00090001
    Figure 00100001
    Figure 00110001
    Figure 00120001
    The following exemplary embodiments show that the alkaline passivation process according to the invention leads to similar corrosion protection results as comparison processes according to the prior art which contain toxic nickel and / or cobalt ions. The galvanized and alloy-galvanized steel sheets listed in Table 2 were alkaline passivated according to Table 1, rinsed for 5 seconds with water, re-passivated with chrome-containing or chrome-free rinse solutions (treatment time: 5 seconds spraying), rinsed for 2 seconds with deionized water and in a circulating air Drying cabinet dried at a cabinet temperature of 70 ° C. For the coating, 5 µm primer and 18 µm top coat, each based on polyester, were applied and baked at 216 and 249 ° C, respectively. The test panels were then subjected to a 42-day salt spray test in accordance with the German standard DIN 50 021 SS. The results (paint infiltration in mm at the cut or at the edge) are shown in Table 2. In addition, the paint adhesion was examined after a T-Bend test. There were no significant differences between the method according to the invention and the nickel and / or cobalt-containing comparison methods.
    Figure 00090001
    Figure 00100001
    Figure 00110001
    Figure 00120001

    Claims (7)

    1. A process for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminium or aluminium alloys containing more than 50% by weight aluminium in strip lines, the metal surfaces being contacted with an alkaline aqueous solution which contains complexing agents and iron, is free from added nickel and cobalt ions, has a free alkalinity of 5 to 20 points and a total alkalinity of 7 to 30 points and contains
      0.1 to 1 g/l magnesium ions,
      0.1 to 1 g/l iron(II) ions and
      0.5 to 5 g/l amino- or hydroxycarboxylate ions.
    2. A process as claimed in claim 1, characterized in that the aqueous solution additionally contains 0.001 to 20 g/l pyrogenic silica.
    3. A process as claimed in one or both of claims 1 and 2, characterized in that the aqueous solution additionally contains a total of 0.001 to 10 g/l acrylate and/or methacrylate ions.
    4. A process as claimed in one or more of claims 1 to 3, characterized in that the hydroxycarboxylate ions are selected from gluconate ions and glucoheptanoate ions.
    5. A process as claimed in one of more claims 1 to 4, characterized in that the metal surfaces are contacted with the aqueous treatment solution, which has a temperature of 40 to 70°C, for 3 to 30 seconds.
    6. A process as claimed in one or more of claims 1 to 5, characterized in that, after contact with the aqueous treatment solution, the metal surfaces are rinsed with water and then treated with a chromium-free secondary passivation solution containing a total of 0.4 to 10 g/l complex fluorides of titanium and/or zirconium.
    7. A water-based concentrate which, on dilution with water by a factor of 7 to 15, gives an aqueous treatment solution for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminium or aluminium alloys containing more than 50% by weight aluminium in strip lines which is free from added nickel and cobalt ions, has a free alkalinity of 5 to 20 points and a total alkalinity of 7 to 30 points and contains
      0.1 to 1 g/l magnesium ions,
      0.1 to 1 g/l iron(II) ions and
      0.5 to 5 g/l amino- or hydroxycarboxylate ions.
    EP98942626A 1997-08-06 1998-07-25 Alkaline strip passivation Expired - Fee Related EP1002143B1 (en)

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    DE19733972A DE19733972A1 (en) 1997-08-06 1997-08-06 Alkaline band passivation
    DE19733972 1997-08-06
    PCT/EP1998/004670 WO1999007917A1 (en) 1997-08-06 1998-07-25 Alkaline strip passivation

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