EP0209143A2 - Surface treatment process for a sheet iron zinc-aluminium alloy coating - Google Patents

Surface treatment process for a sheet iron zinc-aluminium alloy coating Download PDF

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Publication number
EP0209143A2
EP0209143A2 EP86109842A EP86109842A EP0209143A2 EP 0209143 A2 EP0209143 A2 EP 0209143A2 EP 86109842 A EP86109842 A EP 86109842A EP 86109842 A EP86109842 A EP 86109842A EP 0209143 A2 EP0209143 A2 EP 0209143A2
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Prior art keywords
solution
chromium
process step
zinc
brought
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EP86109842A
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German (de)
French (fr)
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EP0209143A3 (en
EP0209143B1 (en
Inventor
Akimitsu Fukuda
Yutaka Tsuchiya
Kazuyuki Oyama
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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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
    • C23C22/60—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
    • C23C22/73—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 object of the invention is to provide a method by means of which the corrosion resistance and the adhesion of a lacquer applied in a later phase to steel sheets which are provided with a zinc / aluminum alloy can be improved without thereby having to accept a complex method to have to.
  • the object is achieved by the method of the type mentioned in the introduction according to the invention is designed in such a way that the metal surface in process step b) is brought into contact with a solution which additionally contains silica.
  • the metal ions contained in the alkaline solution according to stage a) are usually used as inorganic salts, for example nitrates, sulfates, carbonates, chlorides and the like. the like. However, other compounds are also suitable as long as they are soluble in the alkaline medium.
  • the concentration of the metal ions is generally 0.01 to 10 g / l, preferably 0.05 to 5 g / 1. These metal ions must be bound by a sufficient amount of complexing agent to ensure that they are and remain in the dissolved state. The amount of complexing agent is therefore about 0.1 to 20 g / l.
  • the complexing agents can be inorganic or organic in nature.
  • Suitable inorganic complexing agents are, for example, condensed phosphates, ammonia or amine compounds.
  • Suitable organic complexing agents are, for example, dicarboxylic acids, in particular malonic acid, fumaric acid, amino acids, such as glycine, hydroxycarboxylic acids, such as citric acid, gluconic acid and lactic acid, polyhydroxyaliphatic compounds, such as sorbitol or 1,2-ethanediol, phenylcarboxylic acids, such as salicylic acid and phthalic acid, aminocarboxylic acids, such as ethylenedic acid, Polyamino acids such as diethanolamine methane phosphonate, lignin sulfonate and the like.
  • Particularly preferred complexing agents are hexahydroxyheptanoic acid, sodium gluconate and sodium ethylenediaminetetraacetate.
  • the treatment solution according to stage a) is applied at a temperature between room temperature and the boiling point of the solution in spraying or dipping for a time sufficient to selectively dissolve aluminum out of the alloy layer.
  • Treatment at a temperature of 50 to 80 ° C. for a period of 4 to 10 seconds with a continuously operating belt system is particularly expedient. If necessary, shorter treatment times can also be used, in which case solutions of higher concentration and higher temperature should be used.
  • the treatment solution according to process stage b) is obtained in the simplest way by dissolving chromic acid and incorporating colloidal silica.
  • the layer formed with this solution should - after Drying on - have a layer weight of 10 to 400 mg / m 2 .
  • the purpose pursued by the invention is only incompletely achieved, with higher layer weights there is a risk that the paint adhesion will decrease.
  • Preferred refinements of the invention envisage using a treatment solution in process stage b) which additionally contains chromium III ions and / or phosphate ions.
  • the chromium III ion content is created in the simplest manner by adding a reducing agent, such as starch, oxalic acid, tannin or alcohol, to the aqueous solution of chromate in certain amounts.
  • the metal surfaces in process step b) into contact with a solution in which the weight ratio of SiO 2 : chromium VI is in the range from 0.6 to 15.
  • the weight ratio chromium III: chromium VI should be 0.2 to 1. If the solution contains phosphate, it is recommended to set the weight ratio of P0 4 : Chrom-VI to a value in the range of 0.6 to 3.
  • the method according to the invention is intended for the treatment of steel sheets provided with zinc / aluminum alloys, in which the aluminum content in the alloy layer is generally 1 to 70% by weight.
  • the adhesion to organic coatings mediated by the layer formed is particularly high if an epoxy lacquer is applied in step d).
  • at least the base lacquer should be an epoxy lacquer.
  • Steel sheets of the nature mentioned in the test example were at 57 to 63 ° C. for 10 seconds with an alkaline solution containing 0.17 g / l Fe (III) and 0.24 g / 1 Ni ions (each introduced as nitrate) as well as 1.7 g / 1 sodium hexahydroxy heptonate and 22 g / l sodium hydroxide and had a pH of 13.6, treated by spraying, rinsed with water and with an aqueous solution containing provided by roll order. It was then dried. The layer weight was 190 mg / m 2 .
  • the solution for producing the chromate coating used in comparative experiment la of table 2 had the same nature as the aforementioned solution.
  • test sheets which were again the same, were pretreated with an alkaline solution at 55 to 60 ° C. and for 6 seconds in spraying, the 0.17 g / 1 Fe (III) -, 0.24 g / 1 Co ions (in each case as nitrate introduced), 1.7 g / 1 Contained sodium hexahydroxy heptonate and 22 g / 1 sodium hydroxide.
  • the pH of the solution was 13.6. Then it was rinsed with water and a solution was applied by roller application contained and had a pH of 1.5. After drying, the layer weight was 280 mg / m2.
  • the chromium-containing solution used in Table 2 in Comparative Example 2 had the same nature as the last-mentioned solution.
  • the sheets treated as in Examples 1 and 2 above were subjected to two different coatings.
  • it was a two-layer coating system with a Epoxy as a base paint was applied with a layer thickness of 5 / um and then baked at 190 ° C.
  • a polyester paint which was applied with a layer thickness of 13 / um and baked at 200 ° C was used.
  • the other painting consisted of a single-layer paint structure, for which a polyester top coat had been used. There were carried out the deposition with a layer thickness of 14 / um, and the baking at 210 ° C.
  • a device from Du Pont was used to carry out the impact test. It works with a beater bar with a diameter of 12.7 mm, which is loaded with 1 kg and hits the painted sheet metal surface from a height of 50 cm. The paint adhesion is again determined using adhesive tape, as stated above.
  • the evaluation is as follows.
  • a cut was made with a knife to determine corrosion resistance and paint infiltration down to the metal surface.
  • Such scored sheets and sheets deformed in accordance with the bending test were subjected to the salt spray test, which works with a 5% saline solution, for 500 hours (with a single-layer paint structure) or for 1000 hours (with a two-layer paint structure) in accordance with JIS-Z-2371. The evaluation takes place at the interfaces, on the edges and at the bending point.
  • the treated sheets were exposed to the weather for a period of 3 years.
  • the evaluation was carried out according to the following standards:

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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)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A steel sheet carrying a coating of an alloy of zinc and aluminium is pretreated with an aqueous alkaline solution containing polyvalent metal ions held in solution by a sequestering agent and is then coated with an aqueous chromate solution that contains silica and that is dried on to the surface.

Description

Die Erfindung berifft ein Verfahren zur Oberflächenbehandlung von mit einer Zink/Aluminium-Legierung versehenem Stahlblech gemäß der Verfahrensfolge

  • a) In-Kontakt-Bringen mit einer Ionen eines oder mehrerer der Metalle Nickel, Eisen, Kobalt oder Mangan sowie Komplexbildner enthaltenden Lösung, deren pH-Wert 11 oder mehr beträgt,
  • b) In-Kontakt-Bringen mit einer wäßrigen, Chrom-VI-Ionen enthaltenden Lösung,
  • c) Auftrocknen der Lösung gemäß Stufe b),
  • d) Aufbringen eines organischen Überzuges,

sowie dessen Anwendung auf die Behandlung von Stahlblech, das mit einer 90 bis 96,5 Gew.-% Zink sowie 3,5 bis 10 new.-% Aluminium enthaltenden Legierung beschichtet ist.The invention relates to a process for the surface treatment of steel sheet provided with a zinc / aluminum alloy according to the process sequence
  • a) contacting an ion containing one or more of the metals nickel, iron, cobalt or manganese and complexing agent solution, the pH of which is 11 or more,
  • b) contacting with an aqueous solution containing chromium VI ions,
  • c) drying the solution according to stage b),
  • d) applying an organic coating,

and its application to the treatment of steel sheet which is coated with an alloy containing 90 to 96.5% by weight zinc and 3.5 to 10 new% aluminum.

Es ist bekannt, mit Zink beschichtete Stahlbleche mit einer wäßrigen Chromatierungslösung zu behandeln, die Chrom-VI-Ionen als Hauptkomponente enthält, um dadurch das Verhalten des anschließend aufgebrachten Lackes zu verbessern. Auch ist es bekannt, zuvor eine Behandlung mit einer alkalischen Lösung, die Ionen eines oder mehrerer Metalle sowie Komplexbildner enthält, vorzusehen (DE-PS 15 21 854). Hierdurch sollen Korrosionswiderstand und Lackhaftung gegenüber reinen Chromatierverfahren verbessert werden.It is known to treat steel sheets coated with zinc with an aqueous chromating solution which contains chromium VI ions as the main component, in order thereby to improve the behavior of the lacquer which is subsequently applied. It is also known to provide a treatment beforehand with an alkaline solution which contains ions of one or more metals and complexing agents (DE-PS 15 21 854). This is intended to prevent corrosion and Paint adhesion compared to pure chromating processes can be improved.

In jüngerer Zeit sind vielfältige legierungsbeschichtete Stahlbleche entwickelt worden mit dem Ziel, deren Korrosionswiderstand zu verstärken. Dabei erlangen mit Zink/Aluminium-Legierungen beschichtete Stahlbleche zunehmend an Bedeutung. Derartige Zink/Aluminium-Legierungen enthalten etwa 1 bis 70 Gew.-% Aluminium. Die mit derartigen Legierungen beschichteten Stahlbleche besitzen bereits als solche gegenüber herkömmlichen feuerverzinkten Stahlblechen einen deutlich verbesserten Korrosionswiderstand. Jedoch ist die Wirkung gegenüber dem Verhalten der Lackschicht auch bei Auftrocknung einer Chromatierungslösung praktisch unverändert. Ebenso ist eine Verbesserung hinsichtlich der Blasenbildung an den Schnittkanten der lackierten Bleche bei dreijähriger Einwirkung von Witterungseinflüssen praktisch nicht erkennbar, gleichgültig ob die Bleche vor der Lackierung einer Chromatierbehandlung unterworfen worden sind oder nicht.A variety of alloy-coated steel sheets have recently been developed with the aim of increasing their corrosion resistance. Steel sheets coated with zinc / aluminum alloys are becoming increasingly important. Such zinc / aluminum alloys contain about 1 to 70 wt .-% aluminum. The steel sheets coated with such alloys already have a significantly improved corrosion resistance as such compared to conventional hot-dip galvanized steel sheets. However, the effect on the behavior of the lacquer layer is practically unchanged even when a chromating solution dries on. Likewise, there is practically no improvement in the formation of blisters on the cut edges of the coated sheets after three years of exposure to weathering, regardless of whether the sheets have been subjected to a chromating treatment or not before painting.

Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, mit dessen Hilfe der Korrosionswiderstand und die Haftung eines in einer späteren Phase aufgebrachten Lackes bei Stahlblechen, die mit einer Zink/Aluminium-Legierung versehen sind, zu verbessern, ohne dadurch ein aufwendiges Verfahren in Kauf nehmen zu müssen.The object of the invention is to provide a method by means of which the corrosion resistance and the adhesion of a lacquer applied in a later phase to steel sheets which are provided with a zinc / aluminum alloy can be improved without thereby having to accept a complex method to have to.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberfläche in der Verfahrensstufe b) mit einer Lösung in Kontakt bringt, die zusätzlich Kieselsäure enthält.The object is achieved by the method of the type mentioned in the introduction according to the invention is designed in such a way that the metal surface in process step b) is brought into contact with a solution which additionally contains silica.

Zwar ist bei der Darstellung des Standes der Technik und dementsprechend bei der Fassung des Oberbegriffs von Anspruch 1 zum Ausdruck gebracht, daß ein Verfahren mit der Abfolge gemäß den Stufen a) bis d) unter alleiniger Beachtung formeller Gesichtspunkte bekannt ist. Jedoch ist dabei zu berücksichtigen, daß dieses bekannte Verfahren als geeignet bezeichnet ist zum Aufbringen von Überzügen auf unterschiedlichste Metalloberflächen, nämlich von z.B. reinem Zink, elektroplattiertem Zink, feuerverzinkten Oberflächen, einschließlich solchen, die geringe Mengen legierende Bestandteile, wie z.B. Aluminium usw., enthalten, und auf Zinklegierungen als solche etc. Es ist also nicht erkannt worden, daß diese Verfahrensabfolge gerade bei der Behandlung von mit Zink/Aluminium-Legierungen versehenen Stahlblechen von beträchtlichem Vorteil ist.It is indeed expressed in the representation of the prior art and accordingly in the wording of the preamble of claim 1 that a method with the sequence according to steps a) to d) is known with only formal considerations. However, it should be taken into account that this known method is designated as being suitable for applying coatings to a wide variety of metal surfaces, namely e.g. pure zinc, electroplated zinc, hot-dip galvanized surfaces, including those containing small amounts of alloying components, e.g. Aluminum, etc., and on zinc alloys as such, etc. It has not been recognized that this sequence of processes is of considerable advantage particularly in the treatment of steel sheets provided with zinc / aluminum alloys.

Die in der alkalischen Lösung gemäß Stufe a) enthaltenen Metallionen werden üblicherweise als anorganische Salze, z.B. Nitrate, Sulfate, Carbonate, Chloride u. dergl., eingebracht. Es sind jedoch auch andere Verbindungen geeignet, soweit sie im alkalischen Medium löslich sind. Die Konzentration der Metallionen beträgt im allgemeinen 0,01 bis 10 g/l, vorzugsweise 0,05 bis 5 g/1. Diese Metallionen müssen durch eine ausreichende Komplexbildnermenge gebunden sein, damit sichergestellt ist, daß sie in gelöstem Zustand sind und verbleiben. Die Komplexbildnermenge beträgt daher etwa 0,1 bis 20 g/l. Die Komplexbildner können anorganischer oder organischer Natur sein. Geeignete anorganische Komplexbildner sind beispielsweise kondensierte Phosphate, Ammoniak oder Aminverbindungen. Geeignete organische Komplexbildner sind beispielsweise Dicarbonsäuren, insbesondere Malonsäure, Fumarsäure, Aminosäuren, wie Glycin, Hydroxycarbonsäuren, wie Zitronensäure, Gluconsäure und Milchsäure, polyhydroxyaliphatische Verbindungen, wie Sorbitol oder 1,2-Ethandiol, Phenylcarbonsäuren, wie Salicylsäure und Phthalsäure, Amincarbonsäuren, wie Ethylendiamintetraessigsäure, Polyaminosäuren, wie Diethanolaminmethanphosphonat, Ligninsulfonat und dergl. Besonders bevorzugte Komplexbildner sind Hexahydroxyheptansäure, Natriumgluconat und Natriumethylendiamintetraacetat.The metal ions contained in the alkaline solution according to stage a) are usually used as inorganic salts, for example nitrates, sulfates, carbonates, chlorides and the like. the like. However, other compounds are also suitable as long as they are soluble in the alkaline medium. The concentration of the metal ions is generally 0.01 to 10 g / l, preferably 0.05 to 5 g / 1. These metal ions must be bound by a sufficient amount of complexing agent to ensure that they are and remain in the dissolved state. The amount of complexing agent is therefore about 0.1 to 20 g / l. The complexing agents can be inorganic or organic in nature. Suitable inorganic complexing agents are, for example, condensed phosphates, ammonia or amine compounds. Suitable organic complexing agents are, for example, dicarboxylic acids, in particular malonic acid, fumaric acid, amino acids, such as glycine, hydroxycarboxylic acids, such as citric acid, gluconic acid and lactic acid, polyhydroxyaliphatic compounds, such as sorbitol or 1,2-ethanediol, phenylcarboxylic acids, such as salicylic acid and phthalic acid, aminocarboxylic acids, such as ethylenedic acid, Polyamino acids such as diethanolamine methane phosphonate, lignin sulfonate and the like. Particularly preferred complexing agents are hexahydroxyheptanoic acid, sodium gluconate and sodium ethylenediaminetetraacetate.

Die Behandlungslösung gemäß Stufe a) wird bei einer Temperatur zwischen Raumtemperatur und dem Siedepunkt der Lösung im Spritzen oder Tauchen während einer Zeit, die ausreicht, selektiv Aluminium aus der Legierungsschicht herauszulösen, appliziert. Besonders zweckmäßig ist eine Behandlung bei einer Temperatur von 50 bis 80°C während einer Zeitdauer von 4 bis 10 sec. mit einer kontinuierlich arbeitenden Bandanlage. Im Bedarfsfall sind auch kürzere Behandlungszeiten anwendbar, wobei dann Lösungen höherer Konzentration und höherer Temperatur eingesetzt werden sollten.The treatment solution according to stage a) is applied at a temperature between room temperature and the boiling point of the solution in spraying or dipping for a time sufficient to selectively dissolve aluminum out of the alloy layer. Treatment at a temperature of 50 to 80 ° C. for a period of 4 to 10 seconds with a continuously operating belt system is particularly expedient. If necessary, shorter treatment times can also be used, in which case solutions of higher concentration and higher temperature should be used.

Im allgemeinen ist es üblich, nach der Applikation der Lösung gemäß Stufe a) mit Wasser zwischenzuspülen.In general, it is customary to rinse with water after application of the solution in step a).

Die Behandlungslösung gemäß der Verfahrensstufe b) wird in einfachster Weise durch Auflösen von Chromsäure und Einarbeiten von kolloidaler Kieselsäure erhalten. Die mit dieser Lösung gebildete Schicht sollte - nach dem Auftrocknen - ein Schichtgewicht von 10 bis 400 mg/m2 aufweisen. Bei geringerem Schichtgewicht wird der mit der Erfindung verfolgte Zweck nur unvollkommen erreicht, bei höheren Schichtgewichten besteht die Gefahr, daß die Lackhaftung nachläßt.The treatment solution according to process stage b) is obtained in the simplest way by dissolving chromic acid and incorporating colloidal silica. The layer formed with this solution should - after Drying on - have a layer weight of 10 to 400 mg / m 2 . With a lower layer weight, the purpose pursued by the invention is only incompletely achieved, with higher layer weights there is a risk that the paint adhesion will decrease.

Bevorzugte Ausgestaltungen der Erfindung sehen vor, in der Verfahrensstufe b) eine Behandlungslösung einzusetzen, die zusätzlich Chrom-III-Ionen und/oder Phosphationen enthält. Der Gehalt an Chrom-III-Ionen wird in einfachster Weise geschaffen, indem der wäßrigen Lösung von Chromat ein Reduktionsmittel, wie Stärke, Oxalsäure, Tannin oder Alkohol, in bestimmten Mengen zugesetzt wird.Preferred refinements of the invention envisage using a treatment solution in process stage b) which additionally contains chromium III ions and / or phosphate ions. The chromium III ion content is created in the simplest manner by adding a reducing agent, such as starch, oxalic acid, tannin or alcohol, to the aqueous solution of chromate in certain amounts.

Im übrigen ist es vorteilhaft, die Metalloberflächen in der Verfahrensstufe b) mit einer Lösung in Kontakt zu bringen, in der das Gewichtsverhältnis von SiO2 : Chrom-VI im Bereich von 0,6 bis 15 liegt. Für den Fall eines Chrom-III-Gehaltes sollte das Gewicht,sverhältnis Chrom-III : Chrom-VI 0,2 bis 1 betragen. Sofern die Lösung Phosphat enthält, empfiehlt es sich, das Gewichtsverhältnis von P04 : Chrom-VI auf einen Wert im Bereich von 0,6 bis 3 einzustellen.In addition, it is advantageous to bring the metal surfaces in process step b) into contact with a solution in which the weight ratio of SiO 2 : chromium VI is in the range from 0.6 to 15. In the case of a chromium III content, the weight ratio chromium III: chromium VI should be 0.2 to 1. If the solution contains phosphate, it is recommended to set the weight ratio of P0 4 : Chrom-VI to a value in the range of 0.6 to 3.

Das erfindungsgemäße Verfahren ist zur Behandlung von mit Zink/Aluminium-Legierungen versehenen Stahlblechen bestimmt, bei denen in der Regel der Aluminiumanteil in der Legierungsschicht 1 bis 70 Gew.-% beträgt. Die durch die gebildete Schicht vermittelte Haftung gegenüber organischen Überzügen ist besonders hoch, wenn in der Stufe d) ein Epoxylack aufgebracht wird. Bei einem mehrschichtigen Lackaufbau sollte mindestens der Grundlack ein Epoxylack sein.The method according to the invention is intended for the treatment of steel sheets provided with zinc / aluminum alloys, in which the aluminum content in the alloy layer is generally 1 to 70% by weight. The adhesion to organic coatings mediated by the layer formed is particularly high if an epoxy lacquer is applied in step d). In the case of a multi-layer lacquer structure, at least the base lacquer should be an epoxy lacquer.

Mit dem erfindungsgemäßen Verfahren werden besonders große Vorteile erzielt, wenn es zur Behandlung von Stahlblech, das mit einer 90 bis 96,5 Gew.-% sowie 3,5 bis 10 Gew.-% Aluminium enthaltenden Legierung beschichtet ist, angewendet wird.Particularly great advantages are achieved with the method according to the invention if it is used for the treatment of steel sheet which is coated with an alloy containing 90 to 96.5% by weight and 3.5 to 10% by weight aluminum.

Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.

TestbeispielTest example

Im Handel erhältliche, mit einer Zink/Aluminium-Legierung überzogene Stahlbleche (Zn 90 bis 96,5 Gew.-%, Al 3,5 bis 10 Gew.-%; Handelsbezeichnung "Superzinc") wurden bei 57 bis 63 °C 5 sec. mit verschiedenen alkalischen Lösungen, deren Gehalt an wirksamen Bestandteilen in Tabelle 1 angegeben ist und die einen pH-Wert von 13,5 bis 13,7 aufwiesen, im Spritzen behandelt. Die Eisen-(Fe3+),Nickel- und Kobaltionen wurden über die Nitrate eingebracht.Commercially available steel sheets coated with a zinc / aluminum alloy (Zn 90 to 96.5 wt .-%, Al 3.5 to 10 wt .-%; trade name "Superzinc") were at 57 to 63 ° C for 5 sec sprayed with various alkaline solutions, the active ingredient content of which is given in Table 1 and which had a pH of 13.5 to 13.7. The iron (Fe 3+ ), nickel and cobalt ions were introduced via the nitrates.

Zur Ermittlung der Zn/Al-Anteile in der Legierungsoberfläche wurden die so behandelten Bleche einer Röntgenfluoreszenz-Analyse unterworfen und durch Auszählung der Zn- bzw. Al-K-alpha-Werte das Verhältnis Al/Zn bestimmt. Die Ergebnisse sind in Tabelle 1 enthalten.

Figure imgb0001
To determine the Zn / Al fractions in the alloy surface, the sheets treated in this way were subjected to an X-ray fluorescence analysis and the ratio Al / Zn was determined by counting the Zn or Al-K-alpha values. The results are shown in Table 1.
Figure imgb0001

Aus der vorstehenden Tabelle ergibt sich, daß die Al-Menge in der Legierungsschicht der Stahlbleche, die mit den alkalischen Lösungen 1 bis 3 behandelt worden sind, gegenüber denen, die mit andersartigen Lösungen (Beispiel 4 und 5) oder ohne eine alkalische Lösung (Beispiel 6) in Kontakt gebracht worden sind, erniedrigt worden ist.From the table above it follows that the amount of Al in the alloy layer of the steel sheets which have been treated with alkaline solutions 1 to 3 compared to those with other types of solutions (examples 4 and 5) or without an alkaline solution (example 6) have been brought into contact, has been degraded.

Beispiel 1example 1

Stahlbleche der im Testbeispiel genannten Beschaffenheit wurden bei 57 bis 63°C während 10 sec. mit einer alkalischen Lösung, die 0,17 g/l Fe(III)- und 0,24 g/1 Ni-Ionen (jeweils als Nitrat eingebracht) sowie 1,7 g/1 Natriumhexahydroxiheptonat und 22 g/l Natriumhydroxid enthielt und einen pH-Wert von 13,6 aufwies, im Spritzen behandelt, mit Wasser gespült und mit einer wäßrigen Lösung mit einem Gehalt an

Figure imgb0002
durch Rollenauftrag versehen. Anschließend wurde getrocknet. Das Schichtgewicht betrug 190 mg/m2.Steel sheets of the nature mentioned in the test example were at 57 to 63 ° C. for 10 seconds with an alkaline solution containing 0.17 g / l Fe (III) and 0.24 g / 1 Ni ions (each introduced as nitrate) as well as 1.7 g / 1 sodium hexahydroxy heptonate and 22 g / l sodium hydroxide and had a pH of 13.6, treated by spraying, rinsed with water and with an aqueous solution containing
Figure imgb0002
 provided by roll order. It was then dried. The layer weight was 190 mg / m 2 .

Die im Vergleichsversuch la der Tabelle 2 eingesetzte Lösung zur Erzeugung des Chromatüberzuges besaß die gleiche Beschaffenheit wie die vorgenannte Lösung.The solution for producing the chromate coating used in comparative experiment la of table 2 had the same nature as the aforementioned solution.

Beispiel 2Example 2

Die wiederum gleichen Testbleche wurden mit einer alkalischen Lösung bei 55 bis 60°C und während 6 sec. im Spritzen vorbehandelt, die 0,17 g/1 Fe(III)-, 0,24 g/1 Co-Ionen (jeweils als Nitrat eingebracht), 1,7 g/1 Natriumhexahydroxiheptonat und 22 g/1 Natriumhydroxid enthielt. Der pH-Wert der Lösung war 13,6. Anschließend wurde mit Wasser gespült und durch Rollenauftrag eine Lösung appliziert, die

Figure imgb0003
enthielt und einen pH-Wert von 1,5 aufwies. Nach der Trocknung betrug das Schichtgewicht 280 mg/m2.The test sheets, which were again the same, were pretreated with an alkaline solution at 55 to 60 ° C. and for 6 seconds in spraying, the 0.17 g / 1 Fe (III) -, 0.24 g / 1 Co ions (in each case as nitrate introduced), 1.7 g / 1 Contained sodium hexahydroxy heptonate and 22 g / 1 sodium hydroxide. The pH of the solution was 13.6. Then it was rinsed with water and a solution was applied by roller application
Figure imgb0003
 contained and had a pH of 1.5. After drying, the layer weight was 280 mg / m2.

Die in Tabelle 2 im Vergleichsbeispiel 2 eingesetzte chromhaltige Lösung hatte die gleiche Beschaffenheit wie die zuletzt erwähnte Lösung.The chromium-containing solution used in Table 2 in Comparative Example 2 had the same nature as the last-mentioned solution.

Die wie vorstehend in Beispiel 1 und 2 behandelten Bleche wurden zwei unterschiedlichen Lackierungen unterworfen. In einem Fall handelte es sich um einen zweischichtigen Lackaufbau mit einem Epoxylack als Grundlack, der mit einer Schichtdicke von 5 /um aufgebracht und dann bei 190°C eingebrannt wurde. Als Decklack diente ein Polyesterlack, der mit einer Schichtdicke von 13 /um aufgebracht und bei 200°C eingebrannt wurde.The sheets treated as in Examples 1 and 2 above were subjected to two different coatings. In one case, it was a two-layer coating system with a Epoxy as a base paint was applied with a layer thickness of 5 / um and then baked at 190 ° C. As a top coat, a polyester paint, which was applied with a layer thickness of 13 / um and baked at 200 ° C was used.

Die andere Lackierung bestand aus einem einschichtigen Lackaufbau, für den ein Polyesterdecklack eingesetzt worden war. Es erfolgten die Aufbringung mit einer Schichtdicke von 14 /um und das Einbrennen bei 210°C.The other painting consisted of a single-layer paint structure, for which a polyester top coat had been used. There were carried out the deposition with a layer thickness of 14 / um, and the baking at 210 ° C.

Beide Blechserien wurden unterschiedlichen Tests unterworfen, die der Ermittlung des Korrosionswiderstandes und der Lackhaftung dienten. Die Ergebnisse sind in der Tabelle 2 zusammengestellt.Both sheet series were subjected to different tests subjected to the determination of corrosion resistance and paint adhesion. The results are summarized in Table 2.

Die Tests wurden wie folgt durchgeführt:The tests were carried out as follows:

1. Biege- und Schlagtest1. Bending and impact test

Beim Biegetest wurden die behandelten Bleche von Hand über einen aus zwei unbehandelten Blechen gebildeten Kern gebogen. Die Biegestelle wurde dann mit Klebeband versehen, das anschließend schnell wieder entfernt wurde. Nach dem Test wurde das Ausmaß der Lackentfernung an der Biegestelle bewertet.In the bending test, the treated sheets were bent by hand over a core formed from two untreated sheets. The bending point was then provided with adhesive tape, which was then quickly removed again. After the test, the extent of paint removal at the bend was evaluated.

Zur Durchführung des Schlagtestes diente ein Gerät der Firma Du Pont. Es arbeitet mit einer Schlagstange von 12,7 mm Durchmesser, die mit 1 kg belastet ist und aus 50 cm Höhe auf die lackierte Blechoberfläche auftrifft. Die Lackhaftung wird wiederum mit Klebeband, wie vorstehend angegeben, ermittelt.A device from Du Pont was used to carry out the impact test. It works with a beater bar with a diameter of 12.7 mm, which is loaded with 1 kg and hits the painted sheet metal surface from a height of 50 cm. The paint adhesion is again determined using adhesive tape, as stated above.

Die Bewertung bei beiden Tests geschieht wie folgt:

Figure imgb0004
Both tests are rated as follows:
Figure imgb0004

2. Münzenkratztest2nd coin scratch test

Hierbei wird mit einer Münze über die lackierte Oberfläche gestrichen (gekratzt) und danach der Grad der Lackentfernung ermittelt.Here, a coin is brushed over the painted surface and then the degree of paint removal is determined.

Die Bewertung erfolgt wie nachstehend aufgeführt.

Figure imgb0005
The evaluation is as follows.
Figure imgb0005

3. Korrosionstest3. Corrosion test a) Salzsprühtesta) Salt spray test

Zur Ermittlung von Korrosionswiderstand und Lackunterwanderung wurde mit einem Messer ein Schnitt bis auf die Metalloberfläche durchgeführt. Derartig angeritzte Bleche sowie entsprechend dem Biegetest verformte Bleche wurden dem Salzsprühtest, der mit einer 5%igen Kochsalzlösung arbeitet, 500 Stunden lang (bei einschichtigem Lackaufbau) bzw. 1000 Stunden lang (bei zweischichtigem Lackaufbau) gemäß JIS-Z-2371 unterworfen. Die Bewertung erfolgt an den Schnittstellen, an den Kanten und an der Biegestelle.A cut was made with a knife to determine corrosion resistance and paint infiltration down to the metal surface. Such scored sheets and sheets deformed in accordance with the bending test were subjected to the salt spray test, which works with a 5% saline solution, for 500 hours (with a single-layer paint structure) or for 1000 hours (with a two-layer paint structure) in accordance with JIS-Z-2371. The evaluation takes place at the interfaces, on the edges and at the bending point.

b) Bewitterungstestb) Weathering test

Hierzu wurden die behandelten Bleche für die Dauer von 3 Jahren dem Wetter ausgesetzt. Die Bewertung erfolgte nach folgenden Maßstäben:

Figure imgb0006
Figure imgb0007
 For this purpose, the treated sheets were exposed to the weather for a period of 3 years. The evaluation was carried out according to the following standards:
Figure imgb0006
Figure imgb0007

Ein Vergleich der in Tabelle 2 zusammengestellten Testergebnisse zeigt, daß der Korrosionswiderstand der mit einer Zn/Al-Legierung versehenen Stahlbleche verstärkt ist, wenn die Behandlung vor der Lackierung nach dem erfindungsgemäßen Verfahren anstelle von bekannten Verfahren erfolgte.

Figure imgb0008
Figure imgb0009
 A comparison of the test results summarized in Table 2 shows that the corrosion resistance of the steel sheets provided with a Zn / Al alloy is increased if the treatment before painting was carried out by the process according to the invention instead of known processes.
Figure imgb0008
Figure imgb0009

Claims (7)

1. Verfahren zur Oberflächenbehandlung von mit einer Zink/Aluminium-Legierung versehenem Stahlblech gemäß der Verfahrensfolge a) In-Kontakt-Bringen mit einer Ionen eines oder mehrerer der Metalle Nickel, Eisen, Kobalt oder Mangan sowie Komplexbildner enthaltenden Lösung, deren pH-Wert 11 oder mehr beträgt, b) In-Kontakt-Bringen mit einer wäßrigen, Chrom-VI-Ionen enthaltenden Lösung, c) Auftrocknen der Lösung gemäß Stufe b), d) Aufbringen eines organischen Überzuges,
dadurch gekennzeichnet, daß man die Metalloberfläche in der Verfahrensstufe b) mit einer Lösung in Kontakt bringt, die zusätzlich Kieselsäure enthält.1. Method for the surface treatment of a steel sheet provided with a zinc / aluminum alloy according to the sequence of processes a) contacting an ion containing one or more of the metals nickel, iron, cobalt or manganese and complexing agent solution, the pH of which is 11 or more, b) contacting with an aqueous solution containing chromium VI ions, c) drying the solution according to stage b), d) applying an organic coating,
characterized in that the metal surface in process step b) is brought into contact with a solution which additionally contains silica. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Metalloberfläche in der Verfahrensstufe b) mit einer Lösung derart in Kontakt bringt, daß nach dem Auftrocknen ein Schichtgewicht von 10 bis 400 mg/m2 resultiert.2. The method according to claim 1, characterized in that the metal surface in process step b) is brought into contact with a solution such that a layer weight of 10 to 400 mg / m 2 results after drying. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß man die Metalloberfläche in der Verfahrensstufe b) mit einer Lösung in Kontakt bringt, die zusätzlich Chrom-III-Ionen und/oder Phosphationen enthält.3. The method according to claim 1 and 2, characterized in that the metal surface in process step b) is brought into contact with a solution which additionally contains chromium-III ions and / or phosphate ions. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Metalloberfläche in der Verfahrensstufe b) mit einer Lösung in Kontakt bringt, in der das Gewichtsverhältnis Si02 : Chrom-VI im Bereich von 0,6 bis 15 und das Gewichtsverhältnis von Chrom-III : Chrom-VI im Bereich von 0,2 bis 1 liegt.4. The method according to claim 1, 2 or 3, characterized in that the metal surface in process step b) is brought into contact with a solution in which the weight ratio Si0 2 : chromium VI in the range from 0.6 to 15 and that Chromium III: Chromium VI weight ratio is in the range of 0.2 to 1. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Metalloberoberfläche in der Verfahrensstufe b) mit einer Lösung in Kontakt bringt, in der das Gewichtsverhältnis Po4 : Chrom-VI im Bereich von 0,6 bis 3 liegt.5. The method according to one or more of claims 1 to 4, characterized in that the metal surface in process step b) is brought into contact with a solution in which the weight ratio Po 4: chromium-VI is in the range from 0.6 to 3 lies. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man in der Verfahrensstufe d) einen Epoxylack aufbringt.6. The method according to one or more of claims 1 to 5, characterized in that one applies an epoxy paint in process step d). 7. Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 6 auf die Oberflächenbehandlung von Stahlblech, das mit einer 90 bis 96,5 Gew.-% Zink sowie 3,5 bis 10 Gew.-% Aluminium enthaltenden Legierung versehen ist.7. Application of the method according to one or more of claims 1 to 6 to the surface treatment of steel sheet which is provided with an alloy containing 90 to 96.5% by weight of zinc and 3.5 to 10% by weight of aluminum.
EP19860109842 1985-07-19 1986-07-17 Surface treatment process for a sheet iron zinc-aluminium alloy coating Expired - Lifetime EP0209143B1 (en)

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JP15801685A JPS6220880A (en) 1985-07-19 1985-07-19 Surface treatment of zinc-aluminum alloy plated steel sheet
JP158016/85 1985-07-19

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WO1991011542A2 (en) * 1990-01-30 1991-08-08 Henkel Corporation Surface treatment method and composition for zinc coated steel sheet
FR2701754A1 (en) * 1993-02-18 1994-08-26 Pont A Mousson Piping element for buried pipe, corresponding underground pipe, and method of protecting such pipe element.
EP1314796A3 (en) * 2001-11-21 2004-04-14 Chiyoda Chemical Co. Ltd Surface treatment method of metal member, and metal goods

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JPH08983B2 (en) * 1987-03-05 1996-01-10 新日本製鐵株式会社 Chromate treatment method with excellent corrosion resistance
JP2697485B2 (en) * 1992-05-27 1998-01-14 住友金属工業株式会社 Manufacturing method of high corrosion resistant galvannealed steel sheet
LT3218B (en) 1993-03-27 1995-04-25 Chemijos Inst Method for coating zinc alloy by chromium plating
JP3983386B2 (en) 1998-04-03 2007-09-26 日本ペイント株式会社 Chromate antirust treatment agent
PL2503025T3 (en) 2011-03-22 2013-12-31 Henkel Ag & Co Kgaa Multi-step corrosion-resistant treatment of metallic workpieces having at least partially zinc or zinc alloy surfaces
EP2631333A1 (en) * 2012-02-24 2013-08-28 Henkel AG & Co. KGaA Pre-treatment of zinc surfaces before passivation

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WO1991011542A2 (en) * 1990-01-30 1991-08-08 Henkel Corporation Surface treatment method and composition for zinc coated steel sheet
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FR2701754A1 (en) * 1993-02-18 1994-08-26 Pont A Mousson Piping element for buried pipe, corresponding underground pipe, and method of protecting such pipe element.
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EP1314796A3 (en) * 2001-11-21 2004-04-14 Chiyoda Chemical Co. Ltd Surface treatment method of metal member, and metal goods
US7381281B2 (en) 2001-11-21 2008-06-03 Chiyoda Chemical Co., Ltd Surface treatment method of metal member, and metal goods

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EP0209143A3 (en) 1988-10-26
EP0209143B1 (en) 1991-06-19
DE3679866D1 (en) 1991-07-25
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DE3624101A1 (en) 1987-01-22
JPS6220880A (en) 1987-01-29

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