EP1002143A1 - Alkaline strip passivation - Google Patents

Alkaline strip passivation

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Publication number
EP1002143A1
EP1002143A1 EP98942626A EP98942626A EP1002143A1 EP 1002143 A1 EP1002143 A1 EP 1002143A1 EP 98942626 A EP98942626 A EP 98942626A EP 98942626 A EP98942626 A EP 98942626A EP 1002143 A1 EP1002143 A1 EP 1002143A1
Authority
EP
European Patent Office
Prior art keywords
ions
range
passivation
alkaline
points
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98942626A
Other languages
German (de)
French (fr)
Other versions
EP1002143B1 (en
Inventor
Jörg Riesop
Heike Krautbauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1002143A1 publication Critical patent/EP1002143A1/en
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Anticipated expiration legal-status Critical
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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 alloy-galvanized steel surfaces and of aluminum and its alloys in belt systems. This passivation creates a corrosion protection layer that can serve as the basis for subsequent painting.
  • Alkaline passivation processes have long been known for the treatment of the metal surfaces mentioned.
  • the treatment solutions usually contain toxic heavy metals such as nickel ions and / or cobalt ions. These ions are kept in solution under the alkaline conditions by means of suitable complexing agents. Examples of such passivation solutions are given in EP-A-405 340.
  • the object of the invention is therefore to provide a process for the alkaline passivation of suitable metal surfaces which has a performance similar to that of processes containing nickel or cobalt, but does not use any toxic heavy metals.
  • This object is achieved by a process for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminum in strip plants, the metal surfaces being brought into contact with an alkaline, complexing agent and iron-containing aqueous solution, characterized in that the aqueous solution
  • aluminum when used here, it means aluminum and aluminum alloys which contain more than 50% by weight of aluminum.
  • Alkaline is understood to mean that the treatment solutions have a pH of above 9.5, preferably in the range from 10 to 13.
  • the pH values are used less for the characterization of the treatment baths, but for the contents of free alkalinity and
  • the free alkalinity is determined by titrating 2 ml bath solution, preferably diluted to 50 ml, with a 0.1 N acid such as hydrochloric acid or sulfuric acid up to a pH of 8.5 ml indicates the number of free alkalinity and the total alkalinity is determined accordingly by titrating 2 ml of treatment solution, diluted to 50 ml, with 0.1 N acid to a pH of 4.0, which 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.
  • additional active substances that have a positive effect on the formation of layers and corrosion protection.
  • contents of about 0.001 to about 20 g / 1 of finely divided SiO 2 may be mentioned , for example fumed silica. Pyrogens are preferably used
  • BET specific surface area
  • Silicas are commercially available.
  • Another optional component of the treatment solution are about 0.001 to about 10 g / 1 monomeric or oligomeric acrylate and / or methacrylate ions. These can be added to the treatment solution as soluble salts, for example sodium salts, or in the form of the free acid. In the subsequent drying step, at the latest when baking an applied lacquer, these ions polymerize 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.
  • all amino or hydroxy carboxylate ions which produce this effect are suitable. They can be introduced into the treatment solution in the form of soluble salts such as sodium salts or as free acids. Preference is given to monobasic hydroxy carboxylic acids with at least 4 carbon atoms and at least 2 alcoholic hydroxyl groups. Gluconate ions or the glucoheptanate ions which are one carbon atom longer are particularly preferred.
  • the treatment solutions also contain the anions of the salts when the magnesium and iron (III) ions were introduced into the treatment solution.
  • the nitrates are preferably used here, since nitrate ions have no negative influence on the corrosion protection.
  • the process is designed for the treatment of running metal belts, so that the treatment time is in the range of a few seconds depending on the belt speed and the length of the treatment zone.
  • the Treatment time is about 3 to about 30 seconds and is preferably in the range of 5 to 15 seconds.
  • the metal surfaces are preferably brought into contact with an aqueous treatment solution which has a temperature in the range from about 40 to about 70 ° C. Spraying, dipping and rolling processes are suitable for contacting. Spray application is customary and suitable in the context of the inventive method. After the desired exposure time, the aqueous treatment solution is rinsed off.
  • the corrosion protection effect can be further improved if the alkaline passivated metal surfaces are re-passivated.
  • Processes containing chromium are widely used in the prior art for post-passivation after an alkaline passivation.
  • a post-passivation containing chromium is also suitable as post-treatment after the alkaline passivation according to the invention.
  • a particular advantage of the method according to the invention is that there is no need for an ecologically and toxicologically problematic chromium-containing aftertreatment and instead a chromium-free postpassivation can be carried out.
  • a chromium-free post-passivation solutions are in particular aqueous solutions which contain titanium and / or zirconium compounds, in particular complex fluorides of these elements.
  • such a post-passivation solution can contain a total of 0.4 to 10 g / l of complex fluorides of titanium and / or zirconium.
  • the pH of this chromium-free post-passivation solution is preferably in the range from 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 repeated rinsing, drying (at about 60 to about 100 ° C object temperature), painting.
  • the alkaline passivation solution can be removed from Ott by
  • Invention also an aqueous concentrate that when diluted with water by one
  • Aluminum in conveyor systems results in a free alkalinity in the range of 5 to 20 points and a total alkalinity in the range of 7 to 30 points and
  • the preparation of such concentrates is preferably carried out by first dissolving magnesium and iron salts, preferably nitrates, in water to the required concentration, then adding the complexing carboxylic acid and only then adding the alkaline pH by adding alkali, for example sodium hydroxide solution. Value.
  • the following exemplary embodiments show that the alkaline passivation process according to the invention leads to corrosion protection results similar to those of 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.
  • Chromium-containing post-passivation solution (1.5 g / 1 Cr (VI); pH 3.2)

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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

"Alkalische Bandpassivierung""Alkaline band passivation"
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 alloy-galvanized steel surfaces and of aluminum and its alloys in belt systems. This passivation creates a corrosion protection layer that can serve as the basis for subsequent painting.
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 have long been known for the treatment of the metal surfaces mentioned. In order to achieve adequate corrosion protection and the required paint adhesion, the treatment solutions usually contain toxic heavy metals such as nickel ions and / or cobalt ions. These ions are kept in solution under the alkaline conditions by means of suitable complexing agents. 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. Diese Aufgabe wird gelöst durch ein Verfahren zur alkalischen Passivierung von verzinkten und legierungsverzinkten Stahloberflächen sowie von Aluminium in Bandanlagen, wobei man die Metalloberflächen mit einer alkalischen, komplexbildner- und eisenhaltigen wäßrigen Lösung in Kontakt bringt, dadurch gekennzeichnet, daß die wäßrige LösungThe presence of nickel and / or cobalt ions in the alkaline passivation solution gives satisfactory results in terms of corrosion protection and paint adhesion. Because of the high toxicity, the necessary occupational safety measures and the elaborate disposal, there are concerns about the use of toxic heavy metals such as nickel or cobalt. The object of the invention is therefore to provide a process for the alkaline passivation of suitable metal surfaces which has a performance similar to that of processes containing nickel or cobalt, but does not use any toxic heavy metals. This object is achieved by a process for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminum in strip plants, the metal surfaces being brought into contact with an alkaline, complexing agent and iron-containing aqueous solution, characterized in that the aqueous solution
eine freie Alkalität im Bereich von 5 bis 20 Punkten und eine Gesamtalkalität im Bereich von 7 bis 30 Punkten aufweist undhas a free alkalinity in the range from 5 to 20 points and a total alkalinity in the range from 7 to 30 points and
0,1 bis 1 g/1 Magnesiumionen,0.1 to 1 g / 1 magnesium ions,
0,1 bis 1 g/1 Eisen(III)ionen und0.1 to 1 g / 1 iron (III) ions and
0,5 bis 5 g/1 Amino- oder Hydroxycarboxylationen enthält.Contains 0.5 to 5 g / 1 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.When "aluminum" is used here, it means aluminum and aluminum alloys 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” is understood to mean that the treatment solutions have a pH of above 9.5, preferably in the range from 10 to 13. In practice, the pH values are used less for the characterization of the treatment baths, but for the contents of free alkalinity and The free alkalinity is determined by titrating 2 ml bath solution, preferably diluted to 50 ml, with a 0.1 N acid such as hydrochloric acid or sulfuric acid up to a pH of 8.5 ml indicates the number of free alkalinity and the total alkalinity is determined accordingly by titrating 2 ml of treatment solution, diluted to 50 ml, with 0.1 N acid to a pH of 4.0, which 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/1 feinteiliges Si02, beispielsweise pyrogene Kieselsäure. Vorzugsweise verwendet man pyrogeneThe treatment solution can contain additional active substances that have a positive effect on the formation of layers and corrosion protection. For example, contents of about 0.001 to about 20 g / 1 of finely divided SiO 2 may be mentioned , for example fumed silica. Pyrogens are preferably used
Kieselsäure mit einer spezifischen Oberfläche (BET) im Bereich von etwa 150 bis etwa 300 m Ig, beispielsweise etwa 200 m"/g. Wäßrige Suspensionen derartigerSilica with a specific surface area (BET) in the range from about 150 to about 300 m Ig, for example about 200 m " / g. Aqueous suspensions of such
Kieselsäuren sind im Handel erhältlich.Silicas are commercially available.
Ein weiterer fakultativer Bestandteil der Behandlungslösung sind etwa 0,001 bis etwa 10 g/1 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 are about 0.001 to about 10 g / 1 monomeric or oligomeric acrylate and / or methacrylate ions. These can be added to the treatment solution as soluble salts, for example sodium salts, or in the form of the free acid. In the subsequent drying step, at the latest when baking an applied lacquer, these ions polymerize 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 Hydroxy carbonsäuren 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. In principle, all amino or hydroxy carboxylate ions which produce this effect are suitable. They can be introduced into the treatment solution in the form of soluble salts such as sodium salts or as free acids. Preference is given to monobasic hydroxy carboxylic acids with at least 4 carbon atoms and at least 2 alcoholic hydroxyl groups. Gluconate ions or the glucoheptanate ions which are one carbon atom longer are particularly preferred.
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 when the magnesium and iron (III) ions were introduced into the treatment solution. The nitrates are preferably used here, since nitrate ions have no negative influence on the corrosion protection.
Das Verfahren ist für die Behandlung von laufenden Metallbändern 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 belts, so that the treatment time is in the range of a few seconds depending on the belt speed and the length of the treatment zone. For example, the Treatment time is about 3 to about 30 seconds and is preferably in the range of 5 to 15 seconds. The metal surfaces are preferably brought into contact with an aqueous treatment solution which has a temperature in the range from about 40 to about 70 ° C. Spraying, dipping and rolling processes are suitable for contacting. Spray application is customary and suitable in the context of the inventive method. After the desired exposure time, the aqueous treatment solution is rinsed off.
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/1 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 alkaline passivated metal surfaces are re-passivated. Processes containing chromium are widely used in the prior art for post-passivation after an alkaline passivation. A post-passivation containing chromium is also suitable as post-treatment after the alkaline passivation according to the invention. A particular advantage of the method according to the invention, however, is that there is no need for an ecologically and toxicologically problematic chromium-containing aftertreatment and instead a chromium-free postpassivation can be carried out. A chromium-free post-passivation solutions are in particular aqueous solutions which contain titanium and / or zirconium compounds, in particular complex fluorides of these elements. For example, such a post-passivation solution can contain a total of 0.4 to 10 g / l of complex fluorides of titanium and / or zirconium. The pH of this chromium-free post-passivation solution is preferably in the range from 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 repeated rinsing, drying (at about 60 to about 100 ° C object temperature), painting.
Prinzipiell kann die alkalische Passivierungslösung vor Ott durch Auflösen derIn principle, the alkaline passivation solution can be removed from Ott by
Einzelkomponenten in Wasser in der erforderlichen Einsatzkonzentration hergestellt werden. In der Praxis ist es jedoch üblich, Konzentrate zu fertigen und zurIndividual components can be produced in water in the required concentration. In practice, however, it is common to manufacture and use concentrates
Behandlungsanlage zu transportieren, wo durch einfaches Verdünnen mit Wasser die anwendungsfertige Behandlungslösung zubereitet wird. Demgemäß umfaßt dieTransport treatment system where the ready-to-use treatment solution is prepared by simply diluting it with water. Accordingly, the
Erfindung auch ein wäßriges Konzentrat, das beim Verdünnen mit Wasser um einenInvention also an aqueous concentrate that when diluted with water by one
Faktor im Bereich von 7 bis 15 eine wäßrige Behandlungslösung zur alkalischenFactor in the range of 7 to 15 an aqueous treatment solution for alkaline
Passivierung von verzinkten und legierungsverzinkten Stahloberflächen sowie vonPassivation of galvanized and alloy galvanized steel surfaces as well as of
Aluminium in Bandanlagen ergibt, die eine freie Alkalität im Bereich von 5 bis 20 Punkten und eine Gesamtalkalität im Bereich von 7 bis 30 Punkten aufweist undAluminum in conveyor systems results in a free alkalinity in the range of 5 to 20 points and a total alkalinity in the range of 7 to 30 points and
0,1 bis 1 g/1 Magnesiumionen,0.1 to 1 g / 1 magnesium ions,
0,1 bis 1 g/1 Eisen(III)ionen und0.1 to 1 g / 1 iron (III) ions and
0,5 bis 5 g/1 Amino- oder Hydroxycarboxylationen enthält.Contains 0.5 to 5 g / 1 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. The preparation of such concentrates is preferably carried out by first dissolving magnesium and iron salts, preferably nitrates, in water to the required concentration, then adding the complexing carboxylic acid and only then adding the alkaline pH by adding alkali, for example sodium hydroxide solution. Value.
Ausführungsbeispieleembodiments
Die nachfolgenden Ausführungsbeispiele zeigen, daß das erfindungs gemäße alkalische Passivierverfahren zu ähnlichen Korrosionsschutzergebnissen fuhrt 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 μm 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. The following exemplary embodiments show that the alkaline passivation process according to the invention leads to corrosion protection results similar to those of 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.
Tabelle 1: Alkalische Passivierungslösungen und BehandlungsbedingungenTable 1: Alkaline passivation solutions and treatment conditions
1) Freie Alkalität (vergl. Text)1) Free alkalinity (see text)
2) Gesamtalkalität (vergl. Text)2) Overall alkalinity (see text)
3) Komplexbildner: Glucoheptanat3) Complexing agent: glucoheptanate
4) Pyrogene Kieselsäure; spezifische Oberfläche 200 m Ig4) fumed silica; specific surface 200 m Ig
5) chromhaltige Nachpassivierlösung (1,5 g/1 Cr(VI); pH 3,2)5) Chromium-containing post-passivation solution (1.5 g / 1 Cr (VI); pH 3.2)
6) chromfreie Nachpassivierlösung auf Basis TiF6 2" (0,5 g/1, pH 3,4)6) Chrome-free post-passivation solution based on TiF 6 2 " (0.5 g / 1, pH 3.4)
Tabelle 2: Korrosionstestergebnisse (42 Tage Salzsprühtest)Table 2: Corrosion test results (42 days salt spray test)
1) Schmelztauchverzinkter Stahl1) Hot-dip galvanized steel
2) legierungsverzinkter Stahl mit 95 % Zn, 5 % AI (GalfanR)2) Alloy galvanized steel with 95% Zn, 5% AI (Galfan R )
3) legierungsverzinkter Stahl mit 45 % Zn, 55 % AI (GalvalumeR) 3) Alloy galvanized steel with 45% Zn, 55% AI (Galvalume R )

Claims

Patentansprüche claims
1. Verfahren zur alkalischen Passivierung von verzinkten und legierungsverzinkten Stahloberflächen sowie von Aluminium in Bandanlagen, wobei man die Metalloberflächen mit einer alkalischen, komplexbildner- und eisenhaltigen wäßrigen Lösung in Kontakt bringt, dadurch gekennzeichnet, daß die wäßrige Lösung1. A process for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminum in strip plants, the metal surfaces being brought into contact with an alkaline, complexing agent and iron-containing aqueous solution, characterized in that the aqueous solution
eine freie Alkalität im Bereich von 5 bis 20 Punkten und eine Gesamtalkalität im Bereich von 7 bis 30 Punkten aufweist undhas a free alkalinity in the range from 5 to 20 points and a total alkalinity in the range from 7 to 30 points and
0,1 bis 1 g/1 Magnesiumionen,0.1 to 1 g / 1 magnesium ions,
0,1 bis 1 g/1 Eisen(III)ionen und0.1 to 1 g / 1 iron (III) ions and
0,5 bis 5 g/1 Amino- oder Hydroxycarboxylationen enthält.Contains 0.5 to 5 g / 1 amino or hydroxy carboxylate ions.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die wäßrige Lösung zusätzlich 0,001 bis 20 g/1 pyrogene Kieselsäure enthält.2. The method according to claim 1, characterized in that the aqueous solution additionally contains 0.001 to 20 g / 1 fumed silica.
3. Verfahren nach einem oder beiden der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die wäßrige Lösung zusätzlich insgesamt 0,001 bis 10 g/1 Acrylat- und/oder Methacrylationen enthält.3. The method according to one or both of claims 1 and 2, characterized in that the aqueous solution additionally contains a total of 0.001 to 10 g / 1 acrylate and / or methacrylate ions.
4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Hydroxycarboxylationen ausgewählt sind aus Gluconationen und Glucoheptanationen.4. The method according to one or more of claims 1 to 3, characterized in that the hydroxycarboxylate ions are selected from gluconate ions and glucoheptanate ions.
5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Metalloberflächen für eine Zeitdauer im Bereich von 3 bis 30 Sekunden mit der wäßrigen Behandlungslösung in Kontakt gebracht werden, die eine Temperatur im Bereich von 40 bis 70 °C aufweist. 5. The method according to one or more of claims 1 to 4, characterized in that the metal surfaces are brought into contact with the aqueous treatment solution which has a temperature in the range from 40 to 70 ° C for a period in the range from 3 to 30 seconds .
6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, man die Metalloberflächen nach dem Kontakt mit der wäßrigen Behandlungslösung mit Wasser abspült und anschließend mit einer chromfreien Nachpassivierungslösung behandelt, die insgesamt 0,4 bis 10 g/1 komplexe Fluoride von Titan und/oder Zirkonium enthält.6. The method according to one or more of claims 1 to 5, characterized in that the metal surfaces are rinsed with water after contact with the aqueous treatment solution and then treated with a chromium-free post-passivation solution containing a total of 0.4 to 10 g / 1 of complex fluorides Contains titanium and / or zirconium.
7. 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 in Bandanlagen ergibt, die7. Aqueous concentrate which, when diluted with water by a factor in the range from 7 to 15, results in an aqueous treatment solution for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminum in belt systems
eine freie Alkalität im Bereich von 5 bis 20 Punkten und eine Gesamtalkalität im Bereich von 7 bis 30 Punkten aufweist undhas a free alkalinity in the range from 5 to 20 points and a total alkalinity in the range from 7 to 30 points and
0,1 bis 1 g/1 Magnesiumionen,0.1 to 1 g / 1 magnesium ions,
0,1 bis 1 g/1 Eisen(III)ionen und0.1 to 1 g / 1 iron (III) ions and
0,5 bis 5 g/1 Amino- oder Hydroxycarboxylationen enthält. Contains 0.5 to 5 g / 1 amino or hydroxy carboxylate ions.
EP98942626A 1997-08-06 1998-07-25 Alkaline strip passivation Expired - Lifetime EP1002143B1 (en)

Applications Claiming Priority (3)

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

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WO1999007917A1 (en) 1999-02-18
DE59803640D1 (en) 2002-05-08
AU730256B2 (en) 2001-03-01
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DE19733972A1 (en) 1999-02-11
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