EP0240943A2 - Process for applying conversion coatings to zinc or zinc alloy surfaces - Google Patents
Process for applying conversion coatings to zinc or zinc alloy surfaces Download PDFInfo
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- EP0240943A2 EP0240943A2 EP87104930A EP87104930A EP0240943A2 EP 0240943 A2 EP0240943 A2 EP 0240943A2 EP 87104930 A EP87104930 A EP 87104930A EP 87104930 A EP87104930 A EP 87104930A EP 0240943 A2 EP0240943 A2 EP 0240943A2
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- polyvalent metals
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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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
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Definitions
- the invention relates to a process for producing conversion coatings on zinc or zinc alloy surfaces by means of aqueous solutions which contain ions of polyvalent metals and complexing agents in sufficient amounts to keep the ions of polyvalent metals in solution and their pH is greater than ll is.
- the object of the invention is to improve these properties of the conversion coatings produced and at the same time to reduce the concentration of the treatment solution and / or its application temperature.
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surface is brought into contact with a solution, the chromium III ions and ions contains at least two other polyvalent metals.
- the cations of polyvalent metals that are also used in the aqueous solution in addition to chromium III ions can be of the aforementioned type.
- a particularly advantageous embodiment of the invention provides for the surfaces to be brought into contact with a solution which contains iron III ions and cobalt and / or nickel ions as further ions of polyvalent metals.
- Complexing agents suitable for the process according to the invention are organic chelating agents from a wide variety of groups, such as, for example, dicarboxylic acids (malonic acid, fumaric acid, etc.); Amino acids (eg glycine); Hydroxy carboxylic acids (citric acid, gluconic acid, lactic acid, etc.); Hydroxy aldehydes (e.g.
- acetylacetone aliphatic polyalcohols (eg sorbitol, 1,2-ethanediol); aromatic carboxylic acids (eg salicylic acid, phthalic acid); Aminocarboxylic acids (eg ethylenediaminetetraacetic acid); other compounds, such as, for example, methanephosphonic acid diethanolamide or salts of low molecular weight lignosulphonic acids which are obtained in the production of cellulose, can also be used.
- the amount of complexing agent that must be present is the amount that is at least sufficient to fully complex bind the existing ions of polyvalent metals. Thus, if the polyvalent metal ion content in the solution increases, the complexing agent content must also be increased.
- complexing agents which are acidic in nature, can reduce the effective alkalinity of the solution
- complexing agents in the form of the neutral salts, in particular the alkali metal salts are preferably used. It was found that excess complexing agents beyond the amounts required for complex formation have no advantage.
- gluconic acid but especially hexahydroxy heptanoic acid or its salts, are used as complexing agents.
- the most advantageous embodiment of the invention consists in adding chromium as chromium acetate and the ions of the other polyvalent metals as nitrates or other inorganic salts.
- the aqueous solution must have a pH above II. Best results are achieved in the pH range from l2.2 to l3.3.
- the adjustment of the pH value can e.g. by triethanolamine, alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, alkali metal borates, alkali metal silicates, alkali metal polyphosphates, alkali metal pyrophosphates or mixtures thereof.
- alkali hydroxides especially sodium hydroxide.
- the amount required to adjust the pH is usually between 5 and 35 g / l.
- the metal surfaces are brought into contact with a solution which contains ions of the polyvalent metals in a total amount of 0.3 to 3 g / l, preferably 0.4 to 1 g / l.
- the amount of the complexing agent (s) depends on the solution content of ions of the polyvalent metals. It must be sufficient to keep the ions mentioned in solution.
- the surfaces are brought into contact with a solution which contains complexing agents in an amount of from 0.05 to 10 g / l, preferably from 1 to 5 g / l (based on the sodium salt of hexahydroxy heptanoic acid) . If other complexing agents are used, equivalent amounts are advantageous.
- the metal surface is brought into contact with a solution which contains chromium III ions in an amount of 0.04 to 0.4 g / l, preferably 0.1 to 0.3 g / l if ferri ions are used, with a solution which contains these ions in an amount of 0.1 to 0.3 g / l, and if they have a cobalt and / or nickel ion content, with a solution containing these ions in an amount of 0.15 to 0.4 g / l.
- the amount should be such that 15 to 60%, preferably 20 to 40%, of the total metal ions is assigned a corresponding anion.
- the treatment of the zinc or zinc alloy surfaces takes place according to conventional technology, e.g. by diving, but especially by spraying.
- the treatment temperature can in principle reach up to 90 ° C., it is preferably carried out at a temperature below 60 ° C., in particular below 50 ° C. but above 20 ° C.
- a particular advantage of the invention is that it is possible to achieve very good results at a treatment temperature of 20 to 35 ° C, especially at about 25 ° C.
- the treatment time is generally 2 to 60 seconds, preferably 5 to 30 seconds.
- solutions with a lower metal ion concentration require higher temperatures and longer treatment times than those with higher metal ion concentrations.
- the solution used in the method according to the invention is usually free of chromate ions. Although satisfactory results can also be achieved in other ways, it can be advantageous to use a solution containing chromate ions, advantageously after Treat water rinse.
- drying can be carried out and, if necessary, a varnish or other coating can be applied.
- the metal surface to be treated also has exposed iron or steel areas, it can be advantageous to connect a phosphating treatment with solutions based on zinc phosphate or alkali phosphate to the process according to the invention.
- the cobalt and iron III ions were each introduced via their nitrates, and the chromium III ions were each introduced as acetates.
- Hot-dip galvanized steel sheets with a zinc coating of 275 g / m2 and usual surface structure were cleaned and sprayed with solution l for 20 seconds at 45 ° C., rinsed with water, treated with a solution containing chromate ions, dried and with an epoxy basecoat and a top coat made of fluorinated polyvinyl fluoride (PVF2).
- PVF2 fluorinated polyvinyl fluoride
- the sheets were then scratched diagonally down to the metal surface and exposed to the salt spray test in accordance with ASTM B ll7 for 1000 h.
- the bubble size and density were then assessed in accordance with BS 3900 Part H 1. Neither blistering nor paint peeling was found. Only a small amount of white rust had formed at the scratch points.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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- Chemical Treatment Of Metals (AREA)
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Abstract
Bei einem Verfahren zum Erzeugen von Konversionsüberzügen auf Zink- oder Zinklegierungsoberflächen mittels wäßriger Lösungen, die einen Gehalt an Ionen mehrwertiger Metalle und an Komplexbildner aufweisen und deren pH-Wert größer als ll ist, bringt man zwecks Verbesserung der Eigenschaften der Konversionsüberzüge und insbesondere der Applikationsbedingungen die Oberflächen mit einer Lösung in Kontakt, die Chrom-III-ionen und Ionen mindestens zweier weiterer mehrwertiger Metalle, vorzugsweise Eisen-III-ionen sowie Kobalt- und/oder Nickelionen enthält. Die Gesamtmenge an Ionen mehrwertiger Metalle sollte 0,3 bis 3 g/l, vorzugsweise 0,4 bis l g/l, betragen. Als Komplexbildner sind Gluconsäure und Hexahydroxiheptansäure bzw. deren Salze besonders geeignet.In a process for producing conversion coatings on zinc or zinc alloy surfaces by means of aqueous solutions which contain ions of polyvalent metals and complexing agents and whose pH is greater than 11, the properties of the conversion coatings and in particular the application conditions are improved in order to improve the properties of the conversion coatings Surfaces in contact with a solution which contains chromium III ions and ions of at least two other polyvalent metals, preferably iron III ions and cobalt and / or nickel ions. The total amount of ions of polyvalent metals should be 0.3 to 3 g / l, preferably 0.4 to 1 g / l. Gluconic acid and hexahydroxiheptanoic acid or their salts are particularly suitable as complexing agents.
Description
Die Erfindung betrifft ein Verfahren zum Erzeugen von Konversionsüberzügen auf Zink- oder Zinklegierungsoberflächen mittels wäßriger Lösungen, die einen Gehalt an Ionen mehrwertiger Metalle und an Komplexbildner in genügender Menge, um die Ionen der mehrwertigen Metalle in Lösung zu halten, aufweisen und deren pH-Wert größer als ll ist.The invention relates to a process for producing conversion coatings on zinc or zinc alloy surfaces by means of aqueous solutions which contain ions of polyvalent metals and complexing agents in sufficient amounts to keep the ions of polyvalent metals in solution and their pH is greater than ll is.
Ein derartiges Verfahren ist aus der DE - C - l5 2l 854 bekannt. Dabei kommen Lösungen zum Einsatz, die ein oder mehrere der Metalle Magnesium, Cadmium, Aluminium, Zinn, Titan, Antimon, Molybdän, Chrom, Cer, Wolfram, Mangan, Kobalt, Eisen und Nickel enthalten. Als besonders geeignet sind Lösungen beschrieben, die Kobalt- oder Eisen-III-ionen sowie mindestens ein weiteres sogenanntes Nichtalkalimetall enthalten. Die Kationenkombination Eisen-III und Kobalt ist in den Vordergrund gestellt.Such a method is known from DE - C - 15 2l 854. Solutions are used that contain one or more of the metals magnesium, cadmium, aluminum, tin, titanium, antimony, molybdenum, chromium, cerium, tungsten, manganese, cobalt, iron and nickel. Solutions which contain cobalt or iron III ions and at least one further so-called non-alkali metal are described as particularly suitable. The cation combination iron-III and cobalt is in the foreground.
Obgleich das bekannte Verfahren zufriedenstellende Ergebnisse hinsichtlich Korrosionsschutz und Lackhaftung erzielen läßt, besteht die Aufgabe der Erfindung darin, diese Eigenschaften der erzeugten Konversionsüberzüge zu verbessern und zugleich die Konzentration der Behandlungslösung und/oder ihre Applikationstemperatur zu verringern.Although the known method can achieve satisfactory results with regard to corrosion protection and paint adhesion, the object of the invention is to improve these properties of the conversion coatings produced and at the same time to reduce the concentration of the treatment solution and / or its application temperature.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Oberfläche mit einer Lösung in Kontakt bringt, die Chrom-III-ionen und Ionen mindestens zweier weiterer mehrwertiger Metalle enthält.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surface is brought into contact with a solution, the chromium III ions and ions contains at least two other polyvalent metals.
Die außer Chrom-III-ionen weiterhin in der wäßrigen Lösung eingesetzten Kationen mehrwertiger Metalle können von der vorgenannten Art sein. Eine besonders vorteilhafte Ausgestaltung der Erfindung sieht vor, die Oberflächen mit einer Lösung in Kontakt zu bringen, die als weitere Ionen mehrwertiger Metalle Eisen-III-ionen sowie Kobalt- und/oder Nickelionen enthält.The cations of polyvalent metals that are also used in the aqueous solution in addition to chromium III ions can be of the aforementioned type. A particularly advantageous embodiment of the invention provides for the surfaces to be brought into contact with a solution which contains iron III ions and cobalt and / or nickel ions as further ions of polyvalent metals.
Für das erfindungsgemäße Verfahren geeignete Komplexbildner sind organische Chelatbildner der verschiedensten Gruppen, wie z.B. Dicarbonsäuren (Malonsäure, Fumarsäure usw.); Aminosäuren (z.B. Glycin); Hydroxycarbonsäuren (Zitronensäure, Glukonsäure, Milchsäure usw.); Hydroxyaldehyde (z.B. Acetylaceton); aliphatische Polyalkohole (z.B. Sorbit, l,2-Äthandiol); aromatische Carbonsäuren (z.B. Salicylsäure, Phthalsäure); Aminocarbonsäuren (z.B. Äthylendiamintetraessigsäure); auch andere Verbindungen, wie beispielsweise Methanphosphonsäurediäthanolamid oder Salze von niedrigmolekularen Ligninsulfonsäuren, die bei der Zellstoffgewinnung anfallen, brauchbar. Die Menge an komplexbildendem Mittel, die anwesend sein muß, ist die Menge, die mindestens ausreichend ist, um die vorhandenen Ionen mehrwertiger Metalle vollständig komplex zu binden. Wenn somit der Gehalt an mehrwertigen Metallionen in der Lösung ansteigt, muß der Gehalt an komplexbildendem Mittel ebenfalls erhöht werden. Da zunehmende Mengen bestimmter komplexbildender Mittel, die ihrer Natur nach sauer sind, die wirksame Alkalinität der Lösung herabsetzen können, werden vorzugsweise komplexbildende Mittel in Form der Neutralsalze, insbesondere der Alkalimetallsalze, verwendet. Es wurde festgestellt, daß überschüssige, über die zur Komplexbildung benötigten Mengen an Komplexbildner hinaus keinen Vorteil erbringen.Complexing agents suitable for the process according to the invention are organic chelating agents from a wide variety of groups, such as, for example, dicarboxylic acids (malonic acid, fumaric acid, etc.); Amino acids (eg glycine); Hydroxy carboxylic acids (citric acid, gluconic acid, lactic acid, etc.); Hydroxy aldehydes (e.g. acetylacetone); aliphatic polyalcohols (eg sorbitol, 1,2-ethanediol); aromatic carboxylic acids (eg salicylic acid, phthalic acid); Aminocarboxylic acids (eg ethylenediaminetetraacetic acid); other compounds, such as, for example, methanephosphonic acid diethanolamide or salts of low molecular weight lignosulphonic acids which are obtained in the production of cellulose, can also be used. The amount of complexing agent that must be present is the amount that is at least sufficient to fully complex bind the existing ions of polyvalent metals. Thus, if the polyvalent metal ion content in the solution increases, the complexing agent content must also be increased. Since increasing amounts of certain complexing agents, which are acidic in nature, can reduce the effective alkalinity of the solution, complexing agents in the form of the neutral salts, in particular the alkali metal salts, are preferably used. used. It was found that excess complexing agents beyond the amounts required for complex formation have no advantage.
Besonders günstige Ergebnisse werden erzielt, wenn als Komplexbildner Gluconsäure, insbesondere aber Hexahydroxiheptansäure bzw. deren Salze, eingesetzt werden.Particularly favorable results are achieved if gluconic acid, but especially hexahydroxy heptanoic acid or its salts, are used as complexing agents.
Es hat sich gezeigt, daß es nachteilig sein kann, wenn sämtliche Metallionen als Salze anorganischer Säuren, beispielsweise in Form ihrer Nitrate, in die wäßrige Lösung eingebracht werden. In der Regel ist es zweckmäßiger, die Ionen wenigstens eines mehrwertigen Metalles als Salz einer organischen Säure zuzufügen oder aber die Lösung mit organischer Säure zu versetzen. Hierbei kann die organische Säure selbst Komplexbildner sein. Besonders zweckmäßig vom Standpunkt sowohl der Kosten als auch der Wirksamkeit ist es, als organische Säure Ameisensäure, insbesondere Essigsäure, einzusetzen. Die vorteilhafteste Ausführungsform der Erfindung besteht darin, Chrom als Chromacetat und die Ionen der anderen mehrwertigen Metalle als Nitrate oder andere anorganische Salze zuzusetzen.It has been shown that it can be disadvantageous if all metal ions are introduced into the aqueous solution as salts of inorganic acids, for example in the form of their nitrates. As a rule, it is more expedient to add the ions of at least one polyvalent metal as a salt of an organic acid or to add organic acid to the solution. The organic acid can itself be a complexing agent. It is particularly useful from the standpoint of both costs and effectiveness to use formic acid, especially acetic acid, as the organic acid. The most advantageous embodiment of the invention consists in adding chromium as chromium acetate and the ions of the other polyvalent metals as nitrates or other inorganic salts.
Obwohl es vorzuziehen ist, die Ionen der mehrwertigen Metalle als Kationen einzubringen, können auch diejenigen Metalle, die in der Lage sind, Anionen zu bilden, in dieser Form zugegeben werden.Although it is preferable to incorporate the ions of the polyvalent metals as cations, those metals which are capable of forming anions can also be added in this form.
Die wäßrige Lösung muß einen pH-Wert oberhalb ll aufweisen. Beste Ergebnisse werden im pH-Bereich von l2,2 bis l3,3 erzielt.The aqueous solution must have a pH above II. Best results are achieved in the pH range from l2.2 to l3.3.
Die Einstellung des pH-Wertes kann z.B. durch Triethanolamin, Alkalihydroxide, Alkalicarbonate, Alkaliphosphate, Alkaliborate, Alkalisilikate, Alkalipolyphosphate, Alkalipyrophosphate oder Mischungen hiervon erfolgen. Am vorteilhaftesten sind jedoch Alkalihydroxide, speziell Natriumhydroxid. Die zur Einstellung des pH-Wertes erforderliche Menge liegt üblicherweise zwischen 5 und 35 g/l.The adjustment of the pH value can e.g. by triethanolamine, alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, alkali metal borates, alkali metal silicates, alkali metal polyphosphates, alkali metal pyrophosphates or mixtures thereof. However, the most advantageous are alkali hydroxides, especially sodium hydroxide. The amount required to adjust the pH is usually between 5 and 35 g / l.
Entsprechend einer bevorzugten Ausgestaltung der Erfindung bringt man die Metalloberflächen mit einer Lösung in Kontakt, die Ionen der mehrwertigen Metalle in einer Gesamtmenge von 0,3 bis 3 g/l, vorzugsweise von 0,4 bis l g/l, enthält.According to a preferred embodiment of the invention, the metal surfaces are brought into contact with a solution which contains ions of the polyvalent metals in a total amount of 0.3 to 3 g / l, preferably 0.4 to 1 g / l.
Die Menge des oder der Komplexbildner(s) richtet sich nach dem Gehalt der Lösung an Ionen der mehrwertigen Metalle. Sie muß ausreichen, um die genannten Ionen in Lösung zu halten. Gemäß einer weiteren zweckmäßigen Ausgestaltung der Erfindung bringt man die Oberflächen mit einer Lösung in Kontakt, die Komplexbildner in einer Menge von 0,05 bis l0 g/l, vorzugsweise von l bis 5 g/l (bezogen auf das Natriumsalz der Hexahydroxiheptansäure), enthält. Bei Verwendung anderer Komplexbildner sind äquivalente Mengen vorteilhaft.The amount of the complexing agent (s) depends on the solution content of ions of the polyvalent metals. It must be sufficient to keep the ions mentioned in solution. According to a further expedient embodiment of the invention, the surfaces are brought into contact with a solution which contains complexing agents in an amount of from 0.05 to 10 g / l, preferably from 1 to 5 g / l (based on the sodium salt of hexahydroxy heptanoic acid) . If other complexing agents are used, equivalent amounts are advantageous.
Gemäß weiterer vorteilhafter Ausführungsformen der Erfindung bringt man die Metalloberfläche in Kontakt mit einer Lösung, die Chrom-III-ionen in einer Menge von 0,04 bis 0,4 g/l, vorzugsweise 0,l bis 0,3 g/l, enthält, sofern Ferriionen eingesetzt werden, mit einer Lösung, die diese Ionen in einer Menge von 0,l bis 0,3 g/l enthält, und, sofern sie einen Kobalt- und/oder Nickelionengehalt aufweisen, mit einer Lösung, die diese Ionen in einer Menge von 0,l5 bis 0,4 g/l enthält.According to further advantageous embodiments of the invention, the metal surface is brought into contact with a solution which contains chromium III ions in an amount of 0.04 to 0.4 g / l, preferably 0.1 to 0.3 g / l if ferri ions are used, with a solution which contains these ions in an amount of 0.1 to 0.3 g / l, and if they have a cobalt and / or nickel ion content, with a solution containing these ions in an amount of 0.15 to 0.4 g / l.
Falls die Zugabe von organischer Säure bzw. Salzen hiervon, insbesondere Essigsäure oder Acetat, vorgesehen ist, sollte die Menge derart bemessen werden, daß l5 bis 60 %, vorzugsweise 20 bis 40 %, der gesamten Metallionen ein entsprechendes Anion zugeordnet ist.If the addition of organic acid or salts thereof, in particular acetic acid or acetate, is provided, the amount should be such that 15 to 60%, preferably 20 to 40%, of the total metal ions is assigned a corresponding anion.
Die Behandlung der Zink- oder Zinklegierungsoberflächen erfolgt nach konventioneller Technik, z.B. durch Tauchen, insbesondere aber durch Spritzen. Obgleich die Behandlungstemperatur prinzipiell bis 90°C reichen kann, wird vorzugsweise bei einer Temperatur unter 60°C, insbesondere unter 50°C, aber oberhalb 20°C, gearbeitet. Ein besonderer Vorzug der Erfindung liegt darin, daß es möglich ist, sehr gute Ergebnisse bei einer Behandlungstemperatur von 20 bis 35°C, insbesondere bei etwa 25°C, zu erzielen.The treatment of the zinc or zinc alloy surfaces takes place according to conventional technology, e.g. by diving, but especially by spraying. Although the treatment temperature can in principle reach up to 90 ° C., it is preferably carried out at a temperature below 60 ° C., in particular below 50 ° C. but above 20 ° C. A particular advantage of the invention is that it is possible to achieve very good results at a treatment temperature of 20 to 35 ° C, especially at about 25 ° C.
Die Behandlungsdauer liegt in der Regel bei 2 bis 60 sec, vorzugsweise bei 5 bis 30 sec. Im allgemeinen gilt, daß Lösungen mit geringerer Metallionenkonzentration höhere Temperaturen und längere Behandlungszeiten verlangen als solche mit höheren Metallionenkonzentrationen.The treatment time is generally 2 to 60 seconds, preferably 5 to 30 seconds. In general, solutions with a lower metal ion concentration require higher temperatures and longer treatment times than those with higher metal ion concentrations.
Die innerhalb des erfindungsgemäßen Verfahrens zum Einsatz kommende Lösung ist üblicherweise frei von Chromationen. Obgleich auch sonst zufriedenstellende Ergebnisse erzielt werden können, kann es aber von Vorteil sein, mit einer Chromationen enthaltenden Lösung, zweckmäßigerweise nach Wasserspülung nachzubehandeln.The solution used in the method according to the invention is usually free of chromate ions. Although satisfactory results can also be achieved in other ways, it can be advantageous to use a solution containing chromate ions, advantageously after Treat water rinse.
Im Anschluß an die Nachbehandlung oder die Wasserspülung kann getrocknet und gegebenenfalls ein Lack oder anderer Überzug aufgebracht werden.After the aftertreatment or the water rinse, drying can be carried out and, if necessary, a varnish or other coating can be applied.
Sofern die zu behandelnde Metalloberfläche auch freiliegende Eisen- oder Stahlbereiche aufweist, kann es von Vorteil sein, an das erfindungsgemäße Verfahren eine Phosphatierbehandlung mit Lösungen auf Basis Zinkphosphat oder Alkaliphosphat anzuschließen.If the metal surface to be treated also has exposed iron or steel areas, it can be advantageous to connect a phosphating treatment with solutions based on zinc phosphate or alkali phosphate to the process according to the invention.
Die Erfindung wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.
Es wurden zwei Behandlungslösungen angesetzt, die folgende Gehalte an wirksamen Bestandteilen aufwiesen:
Die Kobalt und Eisen-III-ionen waren jeweils über ihre Nitrate, die Chrom-III-ionen jeweils als Acetate eingebracht worden.The cobalt and iron III ions were each introduced via their nitrates, and the chromium III ions were each introduced as acetates.
Feuerverzinkte Stahlbleche mit einer Zinkauflage von 275 g/m² und üblicher Oberflächenstruktur wurden gereinigt und für die Dauer von 20 sec bei 45°C mit Lösung l im Spritzen behandelt, mit Wasser gespült, mit Chromationen enthaltender Lösung nachbehandelt, getrocknet und mit einem Epoxy-Grundlack sowie einem Decklack aus fluoriertem Polyvinylfluorid (PVF₂) versehen.Hot-dip galvanized steel sheets with a zinc coating of 275 g / m² and usual surface structure were cleaned and sprayed with solution l for 20 seconds at 45 ° C., rinsed with water, treated with a solution containing chromate ions, dried and with an epoxy basecoat and a top coat made of fluorinated polyvinyl fluoride (PVF₂).
Anschließend wurden die Bleche diagonal bis auf die Metalloberfläche angeritzt und für die Dauer von l000 h dem Salzsprühtest gemäß ASTM B ll7 ausgesetzt. Danach wurden Blasengröße und -dichte gemäß BS 3900 Teil H l bewertet. Es wurde weder eine Blasenbildung noch eine Lackablösung festgestellt. Es hatte sich lediglich eine geringe Menge Weißrost an den Ritzstellen gebildet.The sheets were then scratched diagonally down to the metal surface and exposed to the salt spray test in accordance with ASTM B ll7 for 1000 h. The bubble size and density were then assessed in accordance with BS 3900 Part H 1. Neither blistering nor paint peeling was found. Only a small amount of white rust had formed at the scratch points.
Nach dem vorgenannten Verfahrensgang wurde eine zweite Partie Zinkblech behandelt, wobei Lösung 2 eingesetzt wurde. Die Behandlungstemperatur betrug hier 25°C, die Behandlungsdauer lag bei 2 bis l5 sec. Die nach der Salzsprühbehandlung erhaltenen Testergebnisse waren mit den vorgenannten gleich.After the aforementioned process, a second batch of zinc sheet was treated using solution 2. The treatment temperature here was 25 ° C., the treatment time was 2 to 15 seconds. The test results obtained after the salt spray treatment were the same as those mentioned above.
In Vergleichsversuchen, ebenfalls nach dem oben skizzierten Verfahrensgang, wurden weitere Partien Zinkbleche behandelt, wobei die Lösungen l und 2 frei von Chromionen waren. Der Gehalt an Natriumsalz der Hexahydroxiheptansäure war entsprechend verringert. Der Test zeigte mit Blasen bedeckte Bleche, wobei die Blasendichte 3 und die Blasengröße 3 waren. Außerdem war beginnende Ausbreitung von Weißrost von der Ritzstelle ab über das Testblech hinweg feststellbar.In comparative experiments, also according to the procedure outlined above, further batches of zinc sheets were treated, solutions 1 and 2 being free from chromium ions. The content of the sodium salt of hexahydroxiheptanoic acid was reduced accordingly. The Test showed blistered sheets with bubble density 3 and bubble size 3. In addition, the spreading of white rust from the scratch point across the test panel was observed.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8608508 | 1986-04-08 | ||
| GB868608508A GB8608508D0 (en) | 1986-04-08 | 1986-04-08 | Coating metal surfaces |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0240943A2 true EP0240943A2 (en) | 1987-10-14 |
| EP0240943A3 EP0240943A3 (en) | 1988-10-26 |
| EP0240943B1 EP0240943B1 (en) | 1990-10-10 |
Family
ID=10595841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87104930A Expired - Lifetime EP0240943B1 (en) | 1986-04-08 | 1987-04-02 | Process for applying conversion coatings to zinc or zinc alloy surfaces |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4801337A (en) |
| EP (1) | EP0240943B1 (en) |
| KR (1) | KR870010219A (en) |
| CN (1) | CN87103418A (en) |
| CA (1) | CA1284762C (en) |
| DE (2) | DE3711095A1 (en) |
| ES (1) | ES2018188B3 (en) |
| GB (2) | GB8608508D0 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20102198A1 (en) * | 2010-11-26 | 2012-05-27 | Np Coil Dexter Ind Srl | PRE-TREATMENT PROCESS ON GALVANIZED STAINLESS STEEL COIL FREE OF HEAVY METALS |
| EP2503025A1 (en) * | 2011-03-22 | 2012-09-26 | Henkel AG & Co. KGaA | Multi-step corrosion-resistant treatment of metallic workpieces having at least partially zinc or zinc alloy surfaces |
| US9228088B2 (en) | 2010-02-09 | 2016-01-05 | Henkel Ag & Co. Kgaa | Composition for the alkaline passivation of zinc surfaces |
| IT201800009491A1 (en) | 2018-10-17 | 2020-04-17 | Condoroil Chemical Srl | Conversion treatment for cobalt-free hot-dip galvanized coils. |
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| GB8802788D0 (en) * | 1988-02-08 | 1988-03-09 | Brent Chemicals Int | Composition & process for treating metal surfaces |
| GB2215740B (en) * | 1988-02-08 | 1992-06-03 | Brent Chemicals Int | Composition and process for treating metal surfaces |
| TW222678B (en) * | 1991-10-24 | 1994-04-21 | Nippon Pakunosei Co Ltd | Pre-treating the surface of a zinc-plated or zinc alloy-plated steel before conventional chromation to imporve rust resistance |
| US7314671B1 (en) | 1996-04-19 | 2008-01-01 | Surtec International Gmbh | Chromium(VI)-free conversion layer and method for producing it |
| DE19615664A1 (en) * | 1996-04-19 | 1997-10-23 | Surtec Produkte Und Systeme Fu | Chromium (VI) free chromate layer and process for its production |
| DE19733972A1 (en) * | 1997-08-06 | 1999-02-11 | Henkel Kgaa | Alkaline band passivation |
| US7029541B2 (en) * | 2002-01-24 | 2006-04-18 | Pavco, Inc. | Trivalent chromate conversion coating |
| DE10223022A1 (en) * | 2002-05-22 | 2003-12-11 | Christoph Schulz | Conversion layer for substrates made of zinc or alloys containing zinc |
| JP4492434B2 (en) * | 2005-05-16 | 2010-06-30 | 日立電線株式会社 | Copper foil for printed wiring board, method for producing the same, and trivalent chromium chemical conversion treatment solution used for the production |
| JP5198727B2 (en) * | 2005-10-07 | 2013-05-15 | ディップソール株式会社 | Treatment solution for forming black hexavalent chromium-free conversion coating on zinc or zinc alloy |
| CA2642365C (en) * | 2006-02-14 | 2015-12-15 | Henkel Kommanditgesellschaft Auf Aktien | Composition and processes of a dry-in-place trivalent chromium corrosion-resistant coating for use on metal surfaces |
| JP5690485B2 (en) * | 2006-05-10 | 2015-03-25 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ．ＫＧａＡ | Improved trivalent chromium-containing composition for use as a corrosion resistant coating on metal surfaces |
| US20110070429A1 (en) * | 2009-09-18 | 2011-03-24 | Thomas H. Rochester | Corrosion-resistant coating for active metals |
| US9573162B2 (en) * | 2011-02-08 | 2017-02-21 | Henkel Ag & Co., Kgaa | Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces |
| CN103282547A (en) * | 2011-02-08 | 2013-09-04 | 汉高股份有限及两合公司 | Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces |
| US10156016B2 (en) | 2013-03-15 | 2018-12-18 | Henkel Ag & Co. Kgaa | Trivalent chromium-containing composition for aluminum and aluminum alloys |
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- 1987-04-01 GB GB8707748A patent/GB2188946B/en not_active Expired - Fee Related
- 1987-04-02 ES ES87104930T patent/ES2018188B3/en not_active Expired - Lifetime
- 1987-04-02 DE DE19873711095 patent/DE3711095A1/en not_active Withdrawn
- 1987-04-02 US US07/043,288 patent/US4801337A/en not_active Expired - Fee Related
- 1987-04-02 DE DE8787104930T patent/DE3765445D1/en not_active Expired - Lifetime
- 1987-04-02 EP EP87104930A patent/EP0240943B1/en not_active Expired - Lifetime
- 1987-04-07 CN CN87103418A patent/CN87103418A/en active Pending
- 1987-04-08 KR KR870003347A patent/KR870010219A/en not_active Application Discontinuation
- 1987-04-08 CA CA000534152A patent/CA1284762C/en not_active Expired - Lifetime
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| BE652525A (en) * | 1963-09-23 | 1964-12-16 | ||
| US3515600A (en) * | 1966-10-19 | 1970-06-02 | Hooker Chemical Corp | Metal treating process and composition |
| FR2152576A1 (en) * | 1971-09-07 | 1973-04-27 | Parker Ste Continentale | |
| US3929514A (en) * | 1974-03-05 | 1975-12-30 | Heatbath Corp | Composition and method for forming a protective coating on a zinc metal surface |
| EP0038122A1 (en) * | 1980-03-19 | 1981-10-21 | Amchem Products, Inc. | Forming corrosion-resistant coatings upon the surfaces of metals, especially zinc |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9228088B2 (en) | 2010-02-09 | 2016-01-05 | Henkel Ag & Co. Kgaa | Composition for the alkaline passivation of zinc surfaces |
| ITMI20102198A1 (en) * | 2010-11-26 | 2012-05-27 | Np Coil Dexter Ind Srl | PRE-TREATMENT PROCESS ON GALVANIZED STAINLESS STEEL COIL FREE OF HEAVY METALS |
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| EP2503025A1 (en) * | 2011-03-22 | 2012-09-26 | Henkel AG & Co. KGaA | Multi-step corrosion-resistant treatment of metallic workpieces having at least partially zinc or zinc alloy surfaces |
| WO2012126734A1 (en) * | 2011-03-22 | 2012-09-27 | Henkel Ag & Co. Kgaa | Multi-stage anti-corrosion treatment of metal components having zinc surfaces |
| US9534301B2 (en) | 2011-03-22 | 2017-01-03 | Henkel Ag & Co. Kgaa | Multi-stage anti-corrosion treatment of metal components having zinc surfaces |
| IT201800009491A1 (en) | 2018-10-17 | 2020-04-17 | Condoroil Chemical Srl | Conversion treatment for cobalt-free hot-dip galvanized coils. |
Also Published As
| Publication number | Publication date |
|---|---|
| US4801337A (en) | 1989-01-31 |
| EP0240943B1 (en) | 1990-10-10 |
| CA1284762C (en) | 1991-06-11 |
| KR870010219A (en) | 1987-11-30 |
| DE3765445D1 (en) | 1990-11-15 |
| GB2188946B (en) | 1990-08-01 |
| ES2018188B3 (en) | 1991-04-01 |
| CN87103418A (en) | 1987-11-11 |
| GB8707748D0 (en) | 1987-05-07 |
| EP0240943A3 (en) | 1988-10-26 |
| GB8608508D0 (en) | 1986-05-14 |
| DE3711095A1 (en) | 1987-10-15 |
| GB2188946A (en) | 1987-10-14 |
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