EP0459549A1 - Production of conversion coatings on zinc or zinc alloy surfaces - Google Patents
Production of conversion coatings on zinc or zinc alloy surfaces Download PDFInfo
- Publication number
- EP0459549A1 EP0459549A1 EP91201020A EP91201020A EP0459549A1 EP 0459549 A1 EP0459549 A1 EP 0459549A1 EP 91201020 A EP91201020 A EP 91201020A EP 91201020 A EP91201020 A EP 91201020A EP 0459549 A1 EP0459549 A1 EP 0459549A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rinsing
- solution
- zinc
- carried out
- adjusted
- 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
Links
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
- C23C22/73—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 producing conversion coatings on surfaces of zinc or zinc alloys, in which in a first step the surfaces are brought into contact with a solution containing at least two different polyvalent metal ions and complexing agents in such an amount that the polyvalent metal ions are kept in solution, and has a pH ⁇ 11, and in which rinsing with a rinsing solution is carried out in a subsequent stage, and its use as a pretreatment for subsequent painting, film coating or adhesive coating.
- Such a method for producing a conversion layer is known in particular from DE-C-1 521 854 as pretreatment before painting and film coating.
- aqueous alkaline solutions which act as so-called non-alkali metal ions of one or more of the metals silver, magnesium, cadmium, aluminum, tin, titanium, antimony, molybdenum, chromium, cerium, tungsten, manganese, cobalt , Iron and nickel included.
- Particularly suitable solutions are those which contain ions of iron or cobalt with another of the metals mentioned as non-alkali metal ions.
- the solutions contain sufficient organic complexing agents to keep the non-alkali metal ions in solution.
- the conversion coatings produced by means of these ions increase the corrosion resistance and improve the adhesion of subsequently applied organic coatings.
- Corrosion resistance and adhesion are further improved if the surfaces are rinsed with an acidic, hexavalent chromium and possibly additionally trivalent chromium solution after the conversion layer has been produced.
- the object of the invention is to provide a method for producing conversion coatings on surfaces made of zinc or zinc alloys, which avoids the disadvantages of the known method and in particular does not or only to a very small extent burden the environment and is at least equally good in terms of corrosion protection and paint adhesion behaves.
- 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 rinsing is carried out with a rinsing solution which contains aluminum, zirconium and fluoride and is adjusted to a pH ⁇ 5.
- the method according to the invention is suitable for all surfaces which contain zinc or zinc alloys, such as, for example, materials made of solid zinc or solid zinc alloys, but also for those whose surface is electrolytically galvanized or alloy-galvanized by deposition from the gas phase or in the hot-dip process has been.
- zinc or zinc alloys such as, for example, materials made of solid zinc or solid zinc alloys, but also for those whose surface is electrolytically galvanized or alloy-galvanized by deposition from the gas phase or in the hot-dip process has been.
- Aluminum, silicon, lead, iron, nickel, cobalt and manganese are particularly suitable alloying partners for zinc.
- both one-sided and two-sided galvanizing or alloy galvanizing can be present.
- the surfaces should be bare and as free of grease as possible. If necessary, they are cleaned alkaline, neutral or acidic before the conversion treatment and then expediently rinsed with water.
- the application of the alkaline solution used in the first stage can e.g. in spraying, dipping or flooding.
- alkaline solutions have been found to be those containing iron (III) ions and additionally cobalt and / or nickel and / or chromium (III) and / or aluminum ions, the total content of which was between 0.3 and 3 g / l, preferably between 0.4 and 1.2 g / l.
- the polyvalent metal ions can be used as salts of inorganic acids, for example nitric acid, or as salts of organic acids, for example formic acid, in particular also Acetic acid can be used. Salts of organic acids, which can simultaneously serve as complexing agents, are also suitable.
- Amphoteric metals, such as aluminum, can also be dissolved in the form of the hydroxyl complex without an additional anion or complexing agent.
- organic chelating agents of various types can be used as complexing agents: for example dicarboxylic acids (malonic acid, fumaric acid etc.); Amino acids (eg glycine); Hydroxycarboxylic acids (e.g. citric acid, gluconic acid, lactic acid); 1,3-diketones (e.g. acetylacetone); aliphatic polyalcohols (e.g. sorbitol, 1,2-ethanediol); aromatic carboxylic acids (eg salicylic acid, phthalic acid); Aminocarboxylic acid (e.g. ethylenediaminetetraacetic acid).
- Other complexing agents such as methanephosphonic acid diethanolamide, can also be used.
- the solution must contain at least such an amount of complexing agent that the multivalent metal ions present can be bound in a completely complex manner.
- the content of complexing agents must also be increased. Since increasing amounts of certain complexing agents, which are acidic in nature, can reduce the alkalinity of the solution, complexing agents are preferably used in Form of neutral salts, especially the alkali metal salts used. It has been found that excess amounts of complexing agents are of no benefit.
- salts of gluconic acid but especially hexahydroxyheptanoic acid
- the content of complexing agent in the solution should be between 0.05 and 10 g / l, in most applications between 1.5 and 5.5 g / l (based on the sodium salt of hexahydroxyheptanoic acid).
- the aqueous solution must have a pH ⁇ 11.
- the best results are achieved in the pH range from 12.2 to 13.3.
- the adjustment of the pH value can e.g. by triethanolamine, alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, alkali metal polyphosphates, alkali metal pyrophosphates, alkali metal borates, alkali metal silicates or mixtures thereof.
- the most advantageous are alkali hydroxides, especially sodium hydroxide.
- the temperature of the solution of the first stage can in principle be between 20 ° C and 90 ° C.
- the preferred temperature range is 45 to 65 ° C.
- the treatment time is usually 2 to 60 seconds, preferably 5 to 30 seconds. It depends, among other things, on the application technology. For example, the duration of treatment in spraying is shorter than in diving under otherwise the same circumstances.
- solutions with a lower metal ion concentration require higher temperatures and longer treatment times than those with a higher metal ion concentration.
- excess treatment solution should be removed as far as possible from the zinc or zinc alloy surface. This can e.g. by draining, squeezing, blowing off or rinsing with water or with an aqueous solution which has been acidified, for example with an inorganic or organic acid (hydrofluoric acid, boric acid, nitric acid, formic acid, acetic acid etc.).
- an inorganic or organic acid hydrofluoric acid, boric acid, nitric acid, formic acid, acetic acid etc.
- the application of the rinse solution can e.g. by dipping, flooding, spraying or rolling.
- a preferred embodiment of the invention consists in rinsing with a solution which contains aluminum, zirconium and fluoride in a total concentration Al + Zr + F between 0.1 and 8 g / l, preferably between 0.2 and 5 g / l.
- the molar ratios Al: Zr: F should advantageously be set to (0.15 to 8): 1: (5 to 52), in particular to (0.15 to 2.0): 1: (5 to 16).
- the Al: Zr: F ratio in the rinse solution is (0.15 to 0.67): 1: (5 to 7).
- the pH is set to 2 to 5.
- the rinse solutions used in the process according to the invention contain, inter alia, acidic aluminum fluorozirconates and, in the case of an excess of aluminum, other salts of aluminum (for example fluorides, Tetrafluoroborates, nitrates). They can be produced, for example, by first dissolving metallic zirconium or zirconium carbonate in aqueous hydrofluoric acid, with complex fluorozirconic acid being formed. Then metallic aluminum or aluminum hydroxide or an aluminum salt, for example nitrate, fluoride, tetrafluoroborate, formate, acetate, preferably in dissolved form, is added and, if necessary, dissolved. A possible slight clouding of the solution does not affect the effectiveness. Although the described manufacturing route is preferred, the solutions can also be prepared in other ways.
- the pH of the solution is preferably adjusted with cations of volatile bases. These include in particular ammonium, ethanolammonium and di- and tri-ethanolammonium.
- volatile bases include in particular ammonium, ethanolammonium and di- and tri-ethanolammonium.
- the surfaces provided with a conversion coating are rinsed with an aqueous solution which additionally contain at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of preferably 0.05 to 0.5 g / l.
- anions can be introduced via the corresponding acids or their salts.
- the duration of the application of the rinse solution is between about 1 and 120 seconds, in particular between 1 and 30 seconds.
- the application temperature can be between 20 ° C and 80 ° C. Temperatures between 20 and 50 ° C are preferred.
- Demineralized or low-salt water is preferably used for the preparation of the rinse bath. Water with a high salt content is less suitable for bath preparation.
- the surface can e.g. air-dried or oven-dried, if necessary rinsed with deionized water beforehand.
- An advantageous embodiment of the invention provides that the surface is accelerated after the passivating rinsing, e.g. dry with hot air or infrared radiation.
- the method according to the invention serves primarily as preparation of the zinc or zinc alloy surfaces before painting, film coating or the application of adhesives. It increases the adhesion of the organic films to the metallic substrate, improves their resistance to blistering when exposed to corrosion and inhibits the corrosion penetration from damage points in the film.
- the sheets were then rinsed with water and rinsed passively. For this purpose, the sheets were immersed in the rinse solution for 5 seconds and then excess solution was removed by squeezing. After a drying time of 0.5 min in a forced air oven at 75 ° C, the pretreated sheets were coated with an epoxy primer and an acrylate top coat. The layer thickness of the total lacquer was approx. 25 ⁇ m.
- the treated sheets were then subjected to the following tests:
- the proportion of the chipped paint surface of the total curved surface is given as the tested size in%.
- the rinsing solutions used were diluted 1.6 g / l (rinsing solution A) or 20 g / l (rinsing solution B) of an aqueous concentrate with 0.855% by weight Al and 8.62% by weight Zr and 10 , 7 wt .-% F using deionized water.
- the pH in both solutions had been adjusted to approximately 3.6 with ammonia.
- Rinse A Al 0.014 g / l Zr 0.14 g / l F 0.17 g / l NH4 0.016 g / l Rinse solution B: Al 0.17 g / l Zr 1.72 g / l F 2.14 g / l NH4 0.40 g / l Rinse solution C: Cr6+ 2.0 g / l Cr3+ 0.8 g / l F 0.2 g / l Zn 0.3 g / l
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung von Konversionsüberzügen auf Oberflächen von Zink- oder Zinklegierungen, bei dem in einer ersten Stufe die Oberflächen mit einer Lösung in Kontakt gebracht werden, die einen Gehalt an mindestens zwei verschiedenen mehrwertigen Metallionen, sowie an Komplexbildner in einer derartigen Menge, daß die mehrwertigen Metallionen in Lösung gehalten werden, aufweist und einen pH-Wert ≧ 11 besitzt, und bei dem in einer folgenden Stufe mit einer Nachsspüllösung gespült wird, sowie dessen Anwendung als Vorbehandlung für eine anschließende Lackierung, Folienbeschichtung oder Kleberbeschichtung.The invention relates to a method for producing conversion coatings on surfaces of zinc or zinc alloys, in which in a first step the surfaces are brought into contact with a solution containing at least two different polyvalent metal ions and complexing agents in such an amount that the polyvalent metal ions are kept in solution, and has a pH ≧ 11, and in which rinsing with a rinsing solution is carried out in a subsequent stage, and its use as a pretreatment for subsequent painting, film coating or adhesive coating.
Ein derartiges Verfahren zur Erzeugung einer Konversionsschicht ist insbesondere als Vorbehandlung vor einer Lackierung und Folienbeschichtung aus der DE-C-1 521 854 bekannt.Such a method for producing a conversion layer is known in particular from DE-C-1 521 854 as pretreatment before painting and film coating.
Zur Schichtbildung auf der Zink- oder Zinklegierungsoberfläche werden dabei wäßrige alkalische Lösungen eingesetzt, die als sogenannte Nichtalkalimetallionen Ionen eines oder mehrerer der Metalle Silber, Magnesium, Cadmium, Aluminium, Zinn, Titan, Antimon, Molybdän, Chrom, Cer, Wolfram, Mangan, Kobalt, Eisen und Nickel enthalten. Als besonders geeignete Lösungen werden solche hervorgehoben, die als Nichtalkalimetallionen Ionen des Eisens oder des Kobalts mit einem weiteren der genannten Metalle enthalten. Außerdem enthalten die Lösungen organische Komplexbildner in ausreichender Menge, um die Nichtalkalimetallionen in Lösung zu halten. Die mittels dieser Ionen erzeugten Konversionsüberzüge erhöhen die Korrosionsbeständigkeit und verbessern die Haftung nachfolgend aufgebrachter organischer Beschichtungen.For the formation of layers on the zinc or zinc alloy surface, aqueous alkaline solutions are used which act as so-called non-alkali metal ions of one or more of the metals silver, magnesium, cadmium, aluminum, tin, titanium, antimony, molybdenum, chromium, cerium, tungsten, manganese, cobalt , Iron and nickel included. Particularly suitable solutions are those which contain ions of iron or cobalt with another of the metals mentioned as non-alkali metal ions. In addition, the solutions contain sufficient organic complexing agents to keep the non-alkali metal ions in solution. The conversion coatings produced by means of these ions increase the corrosion resistance and improve the adhesion of subsequently applied organic coatings.
Korrosionsbeständigkeit und Haftung werden weiterhin verbessert, wenn die Oberflächen nach Erzeugung der Konversionsschicht mit einer sauren, sechswertiges Chrom und ggf. zusätzlich dreiwertiges Chrom enthaltenden Lösung nachgespült werden.Corrosion resistance and adhesion are further improved if the surfaces are rinsed with an acidic, hexavalent chromium and possibly additionally trivalent chromium solution after the conversion layer has been produced.
Obgleich dieses bekannte Verfahren gute Ergebnisse hinsichtlich Korrosionsschutz und Lackhaftung zeigt, ist der Einsatz von drei- und insbesondere von sechswertigen Chromionen in der passivierenden Nachspüllösung wegen der Giftigkeit und der Notwendigkeit zur speziellen Entsorgung des sechswertigen Chroms (Chromat-Entgiftung) sehr nachteilig.Although this known method shows good results with regard to corrosion protection and paint adhesion, the use of trivalent and in particular hexavalent chromium ions in the passivating rinse solution is very disadvantageous because of the toxicity and the need for special disposal of the hexavalent chromium (chromate detoxification).
Die Aufgabe der Erfindung besteht darin, ein Verfahren zur Erzeugung von Konversionsüberzügen auf Oberflächen aus Zink oder Zinklegierungen bereitzustellen, welches die Nachteile des bekannten Verfahrens vermeidet und insbesondere die Umwelt nicht bzw. nur in sehr geringem Maße belastet und sich bezüglich Korrosionsschutz und Lackhaftung wenigstens gleich gut verhält.The object of the invention is to provide a method for producing conversion coatings on surfaces made of zinc or zinc alloys, which avoids the disadvantages of the known method and in particular does not or only to a very small extent burden the environment and is at least equally good in terms of corrosion protection and paint adhesion behaves.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man mit einer Nachspüllösung spült, die einen Gehalt an Aluminium, Zirkonium und Fluorid aufweist sowie auf einen pH-Wert ≦ 5 eingestellt ist.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 rinsing is carried out with a rinsing solution which contains aluminum, zirconium and fluoride and is adjusted to a pH ≦ 5.
Das erfindungsgemäße Verfahren eigenet sich für alle Oberflächen, die Zink oder Zinklegierungen enthalten, wie z.B. Werkstoffe aus massivem Zink oder massiven Zinklegierungen, aber auch für solche, deren Oberfläche elektrolytisch, durch Abscheidung aus der Gasphase oder im Schmelztauchverfahren verzinkt oder legierungsverzinkt worden ist. Als geeignete Legierungspartner von Zink kommen insbesondere Aluminium, Silizium, Blei, Eisen, Nickel, Kobalt und Mangan in Betracht. Bei flächigen Werkstücken kann sowohl eine einseitige als auch beidseitige Verzinkung oder Legierungsverzinkung vorliegen.The method according to the invention is suitable for all surfaces which contain zinc or zinc alloys, such as, for example, materials made of solid zinc or solid zinc alloys, but also for those whose surface is electrolytically galvanized or alloy-galvanized by deposition from the gas phase or in the hot-dip process has been. Aluminum, silicon, lead, iron, nickel, cobalt and manganese are particularly suitable alloying partners for zinc. In the case of flat workpieces, both one-sided and two-sided galvanizing or alloy galvanizing can be present.
Die Oberflächen sollen blank und möglichst fettfrei sein. Gegebenenfalls werden sie vor der Konversionsbehandlung alkalisch, neutral oder sauer gereinigt und anschließend zweckmäßigerweise mit Wasser gespült.The surfaces should be bare and as free of grease as possible. If necessary, they are cleaned alkaline, neutral or acidic before the conversion treatment and then expediently rinsed with water.
Wenn die Zink- oder Zinklegierungsoberfläche nur relativ wenig befettet oder beschmutzt ist, kann ggf. eine vorangestellte Reinigung und Entfettung der Oberfläche entfallen. Stattdessen werden in diesen Fällen durch Zusatz von Tensiden zur Behandlung in der ersten Stufe die Reinigung und Entfettung mit derselben Behandlungslösung vorgenommen, mittels derer auch der Konversionsüberzug erzeugt wird. Diese Ausführungsform bietet vor allem den Vorteil, daß die gesamte Vorbehandlung der Oberfläche in weniger Stufen durchgeführt werden kann, da die separate Reinigung und die dazugehörende Wasserspülung entfallen.If the zinc or zinc alloy surface is only slightly greased or soiled, a preliminary cleaning and degreasing of the surface may not be necessary. Instead, in these cases, by adding surfactants to the treatment in the first stage, cleaning and degreasing are carried out using the same treatment solution that is used to produce the conversion coating. This embodiment has the particular advantage that the entire pretreatment of the surface can be carried out in fewer steps, since the separate cleaning and the associated water rinsing are not necessary.
Die Applikation der in der ersten Stufe eingesetzten alkalischen Lösung kann z.B. im Spritzen, Tauchen oder Fluten erfolgen.The application of the alkaline solution used in the first stage can e.g. in spraying, dipping or flooding.
Als besonders geeignete alkalische Lösungen haben sich solche mit einem Gehalt an Eisen(III)-Ionen und zusätzlich Kobalt- und/oder Nickel- und/oder Chrom(III)- und/oder Aluminium-Ionen erwiesen, deren Gesamtgehalt zwischen 0,3 und 3 g/l, vorzugsweise zwischen 0,4 und 1,2 g/l, liegt. Die mehrwertigen Metallionen können als Salze anorganischer Säuren, z.B. der Salpetersäure, oder als Salze organischer Säuren, z.B. der Ameisensäure, insbesondere auch der Essigsäure, eingesetzt werden. Auch sind Salze organischer Säuren, die gleichzeitig als Komplexbildner dienen können, geeignet. Amphotere Metalle, z.B. Aluminium, lassen sich auch ohne zusätzliches Anion bzw. Komplexbildner in Form des Hydroxikomplexes lösen.Particularly suitable alkaline solutions have been found to be those containing iron (III) ions and additionally cobalt and / or nickel and / or chromium (III) and / or aluminum ions, the total content of which was between 0.3 and 3 g / l, preferably between 0.4 and 1.2 g / l. The polyvalent metal ions can be used as salts of inorganic acids, for example nitric acid, or as salts of organic acids, for example formic acid, in particular also Acetic acid can be used. Salts of organic acids, which can simultaneously serve as complexing agents, are also suitable. Amphoteric metals, such as aluminum, can also be dissolved in the form of the hydroxyl complex without an additional anion or complexing agent.
Infolge eines Beizprozesses während der Behandlung in der ersten Stufe können weitere mehrwertige Kationen, die in der zu behandelnden Oberfläche anwesend und in der frisch angesetzten Badlösung nicht enthalten sind, aus der Zink- oder Zinklegierungsoberfläche in die Behandlungslösung gelangen. Hierbei handelt es sich z.B. um Zink, Aluminium und Blei bei schmelztauchverzinkten Oberflächen. Die Gesamtkonzentration dieser Kationen kann bis zu einigen g/l ansteigen. Die Bildung des Konversionsüberzuges wird hierdurch im allgemeinen nicht gestört.As a result of a pickling process during the treatment in the first stage, further polyvalent cations, which are present in the surface to be treated and are not present in the freshly prepared bath solution, can get into the treatment solution from the zinc or zinc alloy surface. This is e.g. around zinc, aluminum and lead on hot-dip galvanized surfaces. The total concentration of these cations can increase up to a few g / l. This does not generally interfere with the formation of the conversion coating.
Als Komplexbildner sind insbesondere organische Chelatbildner verschiedenster Art einsetzbar: z.B. Dicarbonsäuren (Malonsäure, Fumarsäure etc.); Aminosäuren (z.B. Glycin); Hydroxycarbonsäuren (z.B. Zitronensäure, Gluconsäure, Milchsäure); 1,3-Diketone (z.B. Acetylaceton); aliphatische Polyalkohole (z.B. Sorbit, 1,2-Ethan-diol); aromatische Carbonsäuren (z.B. Salicylsäure, Phthalsäure); Aminocarbonsäure (z.B: Ethylendiamintetraessigsäure). Auch andere Komplexbildner, wie z.B. Methanphosphonsäurediethanolamid, sind anwendbar. Es muß mindestens eine solche Menge Komplexbildner in der Lösung enthalten sein, daß die vorhandenen mehrwertigen Metallionen vollständig komplex gebunden werden können. Wenn somit der Gehalt an mehrwertigen Metallionen in der Lösung ansteigt, muß der Gehalt an Komplexbildnern ebenfalls erhöht werden. Da zunehmende Mengen bestimmter Komplexbildner, die ihrer Natur nach sauer sind, die Alkalinität der Lösung herabsetzen können, werden vorzugsweise Komplexbildner in Form der Neutralsalze, insbesondere der Alkalimetallsalze, verwendet. Es wurde festgestellt, daß überschüssige Mengen an Komplexbildner keinen Vorteil erbringen.In particular, organic chelating agents of various types can be used as complexing agents: for example dicarboxylic acids (malonic acid, fumaric acid etc.); Amino acids (eg glycine); Hydroxycarboxylic acids (e.g. citric acid, gluconic acid, lactic acid); 1,3-diketones (e.g. acetylacetone); aliphatic polyalcohols (e.g. sorbitol, 1,2-ethanediol); aromatic carboxylic acids (eg salicylic acid, phthalic acid); Aminocarboxylic acid (e.g. ethylenediaminetetraacetic acid). Other complexing agents, such as methanephosphonic acid diethanolamide, can also be used. The solution must contain at least such an amount of complexing agent that the multivalent metal ions present can be bound in a completely complex manner. Thus, if the content of polyvalent metal ions in the solution increases, the content of complexing agents must also be increased. Since increasing amounts of certain complexing agents, which are acidic in nature, can reduce the alkalinity of the solution, complexing agents are preferably used in Form of neutral salts, especially the alkali metal salts used. It has been found that excess amounts of complexing agents are of no benefit.
Besonders günstige Ergebnisse werden erzielt, wenn als Komplexbildner Salze der Gluconsäure, insbesondere aber der Hexahydroxyheptansäure, eingesetzt werden. Der Gehalt an Komplexbildner in der Lösung sollte zwischen 0,05 und 10 g/l, in den meisten Anwendungsfällen zwischen 1,5 und 5,5 g/l, liegen (bezogen auf das Natriumsalz der Hexahydroxyheptansäure).Particularly favorable results are achieved if salts of gluconic acid, but especially hexahydroxyheptanoic acid, are used as complexing agents. The content of complexing agent in the solution should be between 0.05 and 10 g / l, in most applications between 1.5 and 5.5 g / l (based on the sodium salt of hexahydroxyheptanoic acid).
Die wäßrige Lösung muß einen pH-Wert ≧ 11 aufweisen. Die besten Ergebnisse werden im pH-Bereich von 12,2 bis 13,3 erzielt. Die Einstellung des pH-Wertes kann z.B. durch Triethanolamin, Alkalihydroxide, Alkalicarbonate, Alkaliphosphate, Alkalipolyphosphate, Alkalipyrophosphate, Alkaliborate, Alkalisilikate oder Mischungen hiervon erfolgen. Am vorteilhaftesten sind jedoch Alkalihydroxide, insbesondere Natriumhydroxid.The aqueous solution must have a pH ≧ 11. The best results are achieved in the pH range from 12.2 to 13.3. The adjustment of the pH value can e.g. by triethanolamine, alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, alkali metal polyphosphates, alkali metal pyrophosphates, alkali metal borates, alkali metal silicates or mixtures thereof. However, the most advantageous are alkali hydroxides, especially sodium hydroxide.
Die Temperatur der Lösung der ersten Stufe kann prinzipiell zwischen 20°C und 90°C betragen. Der bevorzugte Temperaturbereich liegt bei 45 bis 65°C.The temperature of the solution of the first stage can in principle be between 20 ° C and 90 ° C. The preferred temperature range is 45 to 65 ° C.
Die Behandlungsdauer liegt in der Regel bei 2 bis 60 Sekunden, vorzugsweise bei 5 bis 30 Sekunden. Sie ist u.a. abhängig von der Applikationstechnik. Beispielsweise ist die Behandlungsdauer im Spritzen unter sonst gleichen Umständen kürzer als im Tauchen.The treatment time is usually 2 to 60 seconds, preferably 5 to 30 seconds. It depends, among other things, on the application technology. For example, the duration of treatment in spraying is shorter than in diving under otherwise the same circumstances.
Im allgemeinen gilt, daß Lösungen mit geringerer Metallionenkonzentration höhere Temperaturen und längere Behandlungszeiten verlangen als solche mit höherer Metallionenkonzentration.In general, solutions with a lower metal ion concentration require higher temperatures and longer treatment times than those with a higher metal ion concentration.
Nach der Erzeugung eines Konversionsüberzuges sollte überschüssige Behandlungslösung möglichst weitgehend von der Zink- oder Zinklegierungsoberfläche entfernt werden. Dies kann z.B. durch Abtropfen, Abquetschen, Abblasen oder Spülen mit Wasser oder mit einer wäßrigen Lösung, die beispielsweise mit einer anorganischen oder organischen Säure (Flußsäure, Borsäure, Salpetersäure, Ameisensäure, Essigsäure etc.) sauer eingestellt ist, erfolgen.After generating a conversion coating, excess treatment solution should be removed as far as possible from the zinc or zinc alloy surface. This can e.g. by draining, squeezing, blowing off or rinsing with water or with an aqueous solution which has been acidified, for example with an inorganic or organic acid (hydrofluoric acid, boric acid, nitric acid, formic acid, acetic acid etc.).
Die Applikation der Nachspüllösung kann z.B. durch Tauchen, Fluten, Spritzen oder Aufwalzen erfolgen.The application of the rinse solution can e.g. by dipping, flooding, spraying or rolling.
Eine bevorzugte Ausgestaltung der Erfindung besteht darin, mit einer Lösung zu spülen, die Aluminium, Zirkonium und Fluorid in einer Gesamtkonzentration Al + Zr + F zwischen 0,1 und 8 g/l, vorzugsweise zwischen 0,2 und 5 g/l enthält. Die Molverhältnisse Al : Zr : F sollten vorteilhafterweise auf (0,15 bis 8) : 1 : (5 bis 52), insbesondere auf (0,15 bis 2,0) : 1 : (5 bis 16) eingestellt sein. In einer besonders bevorzugten Ausführungsform des Verfahrens beträgt das Al : Zr : F -Verhältnis in der Nachspüllösung (0,15 bis 0,67) : 1 : (5 bis 7). Der pH-Wert ist entsprechend einer weiteren vorteilhaften Ausgestaltung der Erfindung auf 2 bis 5 eingestellt.A preferred embodiment of the invention consists in rinsing with a solution which contains aluminum, zirconium and fluoride in a total concentration Al + Zr + F between 0.1 and 8 g / l, preferably between 0.2 and 5 g / l. The molar ratios Al: Zr: F should advantageously be set to (0.15 to 8): 1: (5 to 52), in particular to (0.15 to 2.0): 1: (5 to 16). In a particularly preferred embodiment of the method, the Al: Zr: F ratio in the rinse solution is (0.15 to 0.67): 1: (5 to 7). According to a further advantageous embodiment of the invention, the pH is set to 2 to 5.
Die beim erfindungsgemäßen Verfahren zum Einsatz kommenden Nachspüllösungen enthalten u.a. saure Aluminiumfluorozirkonate und bei einem Aluminiumüberschuß zusätzlich andere Salze des Aluminiums (z.B. Fluoride, Tetrafluoroborate, Nitrate). Ihre Herstellung kann z.B. so erfolgen, daß zunächst metallisches Zirkonium oder Zirkoniumcarbonat in wäßriger Flußsäure aufgelöst wird, wobei sich komplexe Fluorozirkonsäure bildet. Dann wird metallisches Aluminium oder Aluminiumhydroxid oder ein Aluminiumsalz, z.B. Nitrat, Fluorid, Tetrafluoroborat, Formiat, Acetat, vorzugsweise in gelöster Form, zugesetzt und ggfs. aufgelöst. Eine eventuelle leichte Trübung der Lösung beeinträchtigt die Wirksamkeit nicht. Obgleich der beschriebene Herstellweg bevorzugt wird, lassen sich die Lösungen auch auf andere Weise zubereiten.The rinse solutions used in the process according to the invention contain, inter alia, acidic aluminum fluorozirconates and, in the case of an excess of aluminum, other salts of aluminum (for example fluorides, Tetrafluoroborates, nitrates). They can be produced, for example, by first dissolving metallic zirconium or zirconium carbonate in aqueous hydrofluoric acid, with complex fluorozirconic acid being formed. Then metallic aluminum or aluminum hydroxide or an aluminum salt, for example nitrate, fluoride, tetrafluoroborate, formate, acetate, preferably in dissolved form, is added and, if necessary, dissolved. A possible slight clouding of the solution does not affect the effectiveness. Although the described manufacturing route is preferred, the solutions can also be prepared in other ways.
Die Einstellung des pH-Wertes der Lösung erfolgt vorzugsweise mit Kationen flüchtiger Basen. Hierzu zählen insbesondere Ammonium, Ethanolammonium sowie Di- und Tri-Ethanolammonium. Bei der Einstellung insbesonder von höheren pH-Werten im angegebenen pH-Bereich und bei höheren Konzentrationen im angegebenen Bereich der Gesamtkonzentration Al + Zr + F kann es zu einer Trübung der Lösung kommen, die auf die Wirksamkeit des Verfahrens keinen negativen Einfluß hat.The pH of the solution is preferably adjusted with cations of volatile bases. These include in particular ammonium, ethanolammonium and di- and tri-ethanolammonium. When setting in particular higher pH values in the specified pH range and at higher concentrations in the specified range of the total concentration Al + Zr + F, the solution may become cloudy, which has no negative effect on the effectiveness of the process.
Gemäß einer weiteren vorteilhaften Ausführungsform der Erfindung spült man die mit einem Konversionsüberzug versehenen Oberflächen mit einer wäßrigen Lösung, die zusätzlich mindestens eines der Anionen Benzoat, Caprylat, Ethylhexoat, Salicylat in einer Gesamtkonzentration von vorzugsweise 0,05 bis 0,5 g/l enthalten. Hierdurch wird besonders der Blankkorrosionsschutz weiter gesteigert. Das Einbringen der Anionen kann über die entsprechenden Säuren bzw. deren Salze erfolgen.According to a further advantageous embodiment of the invention, the surfaces provided with a conversion coating are rinsed with an aqueous solution which additionally contain at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of preferably 0.05 to 0.5 g / l. This particularly increases the protection against bright corrosion. The anions can be introduced via the corresponding acids or their salts.
Die Dauer der Applikation der Nachspüllösung liegt gemäß einer weiteren zweckmäßigen Ausgestaltung der Erfindung zwischen etwa 1 und 120 Sekunden, insbesondere zwischen 1 und 30 Sekunden. Die Anwendungstemperatur kann zwischen 20°C und etwa 80°c liegen. Temperaturen zwischen 20 und 50°C werden bevorzugt.According to a further expedient embodiment of the invention, the duration of the application of the rinse solution is between about 1 and 120 seconds, in particular between 1 and 30 seconds. The application temperature can be between 20 ° C and 80 ° C. Temperatures between 20 and 50 ° C are preferred.
Für den Ansatz des Nachspülbades wird vorzugsweise vollentsalztes bzw. salzarmes Wasser verwendet. Wasser mit hohem Salzgehalt ist zum Badansatz weniger geeignet.Demineralized or low-salt water is preferably used for the preparation of the rinse bath. Water with a high salt content is less suitable for bath preparation.
Nach der passivierenden Nachspülung kann die Oberfläche z.B. an der Luft oder im Ofen getrocknet, ggf. zuvor mit vollentsalztem Wasser nachgespült werden. Eine vorteilhafte Ausführungsform der Erfindung sieht vor, die Oberfläche nach der passivierenden Nachspülung beschleunigt, z.B. durch Heißluft oder Infrarotstrahlung zu trocknen.After the passivating rinse, the surface can e.g. air-dried or oven-dried, if necessary rinsed with deionized water beforehand. An advantageous embodiment of the invention provides that the surface is accelerated after the passivating rinsing, e.g. dry with hot air or infrared radiation.
Das erfindungsgemäße Verfahren dient in erster Linie als Vorbereitung der Zink- oder Zinklegierungsoberflächen vor der Lackierung, Folienbeschichtung oder dem Auftrag von Klebern. Es erhöht die Haftung der organischen Filme auf dem metallischen Untergrund, verbessert ihre Beständigkeit gegen Blasenbildung bei Korrosionsbeanspruchung und hemmt die von Beschädigungsstellen im Film ausgehende Korrosionsunterwanderung.The method according to the invention serves primarily as preparation of the zinc or zinc alloy surfaces before painting, film coating or the application of adhesives. It increases the adhesion of the organic films to the metallic substrate, improves their resistance to blistering when exposed to corrosion and inhibits the corrosion penetration from damage points in the film.
Anhand des folgenden Beispiels wird das erfindungsgemäße Verfahren beispielhaft und näher erläutert.The method according to the invention is explained by way of example and in more detail using the following example.
Gereinigte und entfettete Bleche aus feuerverzinktem Stahl wurden zur Erzeugung eines Konversionsüberzuges 30 Sekunden in eine Lösung getaucht, deren Temperatur 55°C betrug und die folgende Zusammensetzung aufwies:
Die Bleche wurden anschließend mit Wasser gespült und passivierend nachgespült. Hierzu wurden die Bleche 5 Sekunden in die Nachspüllösung getaucht und anschließend von überschüssiger Lösung durch Abquetschen befreit. Nach einer Trocknungsdauer von 0,5 min im Umluftofen bei 75°C wurden die vorbehandelten Bleche mit einem Epoxid-Primer und einem Acrylat-Decklack lackiert. Die Schichtdicke des Gesamtlacks betrug ca. 25µm.The sheets were then rinsed with water and rinsed passively. For this purpose, the sheets were immersed in the rinse solution for 5 seconds and then excess solution was removed by squeezing. After a drying time of 0.5 min in a forced air oven at 75 ° C, the pretreated sheets were coated with an epoxy primer and an acrylate top coat. The layer thickness of the total lacquer was approx. 25 µm.
Anschließend wurden die behandelten Bleche folgenden Prüfungen unterzogen:
Die Lackhaftung wurde im T-Bend-Test ermittelt, wobei die Bleche um 180° gebogen wurden und die verschiedenen Krümmungsradien als n-faches der Blechdicke (n=0,1,2...) angegeben werden (Tn). Als geprüfte Größe wird der Anteil der abgeplatzten Lackfläche an der gesamten gekrümmten Fläche in % angegeben.The treated sheets were then subjected to the following tests:
The paint adhesion was determined in the T-Bend test, the sheets being bent through 180 ° and the different radii of curvature being stated as n times the sheet thickness (n = 0.1.2 ...) (Tn). The proportion of the chipped paint surface of the total curved surface is given as the tested size in%.
An weiteren behandelten Blechen wurden mit einer Blechnadel Ritze bis zum Metalluntergrund und mit einer Blechschere eine Schnittkante angebracht. Die Bleche wurden dann dem Salzsprühtest nach DIN 50021 SS für 1008 Stunden unterworfen. Als geprüfte Größe wird die Lackunterwanderung (mm) angegeben, die vom Ritz bzw. der Schnittkante ausgeht.On further treated sheets, a metal needle was used to make cracks down to the metal surface and a cutting edge with sheet metal scissors. The sheets were then subjected to the salt spray test according to DIN 50021 SS for 1008 hours. The undercut of the paint (mm) starting from the scratch or the cut edge is specified as the tested size.
Die zum Einsatz kommenden Nachspüllösungen wurden durch Verdünnen von 1,6 g/l (Nachspüllösung A) bzw. 20 g/l (Nachspüllösung B) eines wäßrigen Konzentrates mit 0,855 Gew.-% Al und 8,62 Gew.-% Zr und 10,7 Gew.-% F unter Verwendung von vollentsalztem Wasser hergestellt. Der pH-Wert war in beiden Lösungen mit Ammoniak auf ca. 3,6 eingestellt worden.The rinsing solutions used were diluted 1.6 g / l (rinsing solution A) or 20 g / l (rinsing solution B) of an aqueous concentrate with 0.855% by weight Al and 8.62% by weight Zr and 10 , 7 wt .-% F using deionized water. The pH in both solutions had been adjusted to approximately 3.6 with ammonia.
Zu Vergleichszwecken diente eine Cr(VI)/Cr(III)-haltige Nachspüllösung (Nachspüllösung C) mit einem pH-Wert von ca. 3,3.A Cr (VI) / Cr (III) -containing rinse solution (rinse solution C) with a pH of approximately 3.3 was used for comparison purposes.
Die Zusammensetzung der Nachspüllösungen war:
Die Prüfergebnisse sind in den nachfolgenden Tabellen angegeben.
Ein Vergleich der Tabellenwerte zeigt, daß das erfindungsgemäße Verfahren in jedem Fall mindestens so gute bzw. bessere Werte lieferte wie das mitgeprüfte Vergleichsverfahren mit einer Nachspüllösung auf Basis Cr(VI)/Cr(III).A comparison of the table values shows that the method according to the invention in any case gave at least as good or better values as the comparison method also tested with a rinsing solution based on Cr (VI) / Cr (III).
Claims (11)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4017186A DE4017186A1 (en) | 1990-05-29 | 1990-05-29 | GENERATION OF CONVERSION OVERHEADS ON ZINC OR ZINC ALLOY SURFACES |
DE4017186 | 1990-05-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0459549A1 true EP0459549A1 (en) | 1991-12-04 |
EP0459549B1 EP0459549B1 (en) | 1994-08-17 |
Family
ID=6407363
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91201020A Expired - Lifetime EP0459549B1 (en) | 1990-05-29 | 1991-04-29 | Production of conversion coatings on zinc or zinc alloy surfaces |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0459549B1 (en) |
JP (1) | JP3083872B2 (en) |
AU (1) | AU633728B2 (en) |
BR (1) | BR9102173A (en) |
CA (1) | CA2041892C (en) |
DE (2) | DE4017186A1 (en) |
ES (1) | ES2057734T3 (en) |
ZA (1) | ZA914085B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999007917A1 (en) * | 1997-08-06 | 1999-02-18 | Henkel Kommanditgesellschaft Auf Aktien | Alkaline strip passivation |
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 |
WO2012109339A2 (en) | 2011-02-08 | 2012-08-16 | Henkel Ag & Co. Kgaa | Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010001686A1 (en) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Composition for the alkaline passivation of zinc surfaces |
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 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE684954A (en) * | 1965-08-02 | 1967-01-16 | ||
FR2117256A5 (en) * | 1970-12-02 | 1972-07-21 | Amchem Prod | |
FR2207199A1 (en) * | 1972-11-20 | 1974-06-14 | Pennwalt Corp | |
EP0153973A1 (en) * | 1982-09-30 | 1985-09-11 | Nihon Parkerizing Co., Ltd. | Process for heating metal surfaces |
EP0161667A1 (en) * | 1984-05-18 | 1985-11-21 | PARKER CHEMICAL COMPANY (a Delaware company) | Process for the treatment of metal surfaces |
US4650526A (en) * | 1986-03-18 | 1987-03-17 | Man-Gill Chemical Company | Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3924984A1 (en) * | 1989-07-28 | 1991-01-31 | Metallgesellschaft Ag | METHOD FOR PASSIVATING RINSING OF PHOSPHATE LAYERS |
-
1990
- 1990-05-29 DE DE4017186A patent/DE4017186A1/en not_active Withdrawn
-
1991
- 1991-04-29 DE DE59102544T patent/DE59102544D1/en not_active Expired - Fee Related
- 1991-04-29 AU AU76178/91A patent/AU633728B2/en not_active Ceased
- 1991-04-29 EP EP91201020A patent/EP0459549B1/en not_active Expired - Lifetime
- 1991-04-29 ES ES91201020T patent/ES2057734T3/en not_active Expired - Lifetime
- 1991-05-06 CA CA002041892A patent/CA2041892C/en not_active Expired - Fee Related
- 1991-05-28 JP JP03152482A patent/JP3083872B2/en not_active Expired - Fee Related
- 1991-05-28 BR BR919102173A patent/BR9102173A/en unknown
- 1991-05-29 ZA ZA914085A patent/ZA914085B/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE684954A (en) * | 1965-08-02 | 1967-01-16 | ||
FR2117256A5 (en) * | 1970-12-02 | 1972-07-21 | Amchem Prod | |
FR2207199A1 (en) * | 1972-11-20 | 1974-06-14 | Pennwalt Corp | |
EP0153973A1 (en) * | 1982-09-30 | 1985-09-11 | Nihon Parkerizing Co., Ltd. | Process for heating metal surfaces |
EP0161667A1 (en) * | 1984-05-18 | 1985-11-21 | PARKER CHEMICAL COMPANY (a Delaware company) | Process for the treatment of metal surfaces |
US4650526A (en) * | 1986-03-18 | 1987-03-17 | Man-Gill Chemical Company | Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999007917A1 (en) * | 1997-08-06 | 1999-02-18 | Henkel Kommanditgesellschaft Auf Aktien | Alkaline strip passivation |
US6346295B1 (en) | 1997-08-06 | 2002-02-12 | Henkel Kommanditgesellschaft Auf Aktien | Alkaline strip passivation |
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 |
EP2458032A1 (en) * | 2010-11-26 | 2012-05-30 | NP Coil Dexter Industries S.r.l. | Heavy-metal-free pre-treatment process for pre-painted galvanised steel coils |
WO2012109339A2 (en) | 2011-02-08 | 2012-08-16 | Henkel Ag & Co. Kgaa | Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces |
EP2673394A4 (en) * | 2011-02-08 | 2018-01-03 | Henkel AG & Co. KGaA | Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces |
Also Published As
Publication number | Publication date |
---|---|
ZA914085B (en) | 1993-01-27 |
CA2041892A1 (en) | 1991-11-30 |
EP0459549B1 (en) | 1994-08-17 |
DE59102544D1 (en) | 1994-09-22 |
DE4017186A1 (en) | 1991-12-05 |
JPH04231479A (en) | 1992-08-20 |
CA2041892C (en) | 2000-10-03 |
JP3083872B2 (en) | 2000-09-04 |
AU7617891A (en) | 1991-12-05 |
AU633728B2 (en) | 1993-02-04 |
ES2057734T3 (en) | 1994-10-16 |
BR9102173A (en) | 1991-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1933013C3 (en) | Process for the production of protective layers on aluminum, iron and zinc by means of solutions containing complex fluorides | |
DE3038699A1 (en) | AQUEOUS ACID CHROMATE COATING SOLUTION, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COATING ZINC, ZINC ALLOY AND CADIMIUM SURFACES | |
EP0240943B1 (en) | Process for applying conversion coatings to zinc or zinc alloy surfaces | |
DE3234558C2 (en) | ||
DE2100021A1 (en) | Process for applying phosphate layers to steel, iron and zinc surfaces | |
EP0056881A1 (en) | Method of phosphating metals | |
EP0261519B1 (en) | Passivation by coating for materials containing different metals | |
EP0359296B1 (en) | Phosphating process | |
DE19706482B4 (en) | A method of surface treating a metal body and composite produced by the method | |
EP0410497B1 (en) | Process for the passivate rinsing of phosphate coatings | |
EP0492713A1 (en) | Process for rinsing conversion coatings | |
EP0328908A1 (en) | Process for applying conversion coatings | |
DE2932822C2 (en) | Phosphate coating solution and method for creating phosphate coatings on surfaces of machined or tinned steel | |
EP0486576B1 (en) | Process for producing manganese-containing zinc phosphate coatings on galvanized steel | |
DE2701321A1 (en) | METHOD FOR AFTER-TREATMENT OF ZINC OR ZINC ALLOYS | |
EP0459549B1 (en) | Production of conversion coatings on zinc or zinc alloy surfaces | |
DE2031358C3 (en) | Process for the production of protective layers on aluminum, iron and zinc by means of acidic solutions containing complex fluorides | |
EP0078866B1 (en) | Formation of coatings on aluminium surfaces | |
EP2492371A1 (en) | Cobalt-free passivation solution and method for depositing cobalt-free passivation coatings on zinc and zinc alloy surfaces | |
EP0459550B1 (en) | Process for rinsing conversion coatings | |
DE2715291A1 (en) | PROCESS FOR PRODUCING AMORPHERIC, LIGHTWEIGHT, ADHESIVE PHOSPHATE COATINGS ON IRON METAL SURFACES | |
DE1521870A1 (en) | Aqueous acidic solutions and processes for the production of chemical coatings on zinc-containing surfaces | |
DE2521737C3 (en) | Method and solution for phosphating iron and steel surfaces | |
EP0154384B1 (en) | Process for pretreating zinc surfaces before lacquering | |
EP0355525B1 (en) | Process for producing coatings on zinc |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19920510 |
|
17Q | First examination report despatched |
Effective date: 19920703 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT NL SE |
|
REF | Corresponds to: |
Ref document number: 59102544 Country of ref document: DE Date of ref document: 19940922 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2057734 Country of ref document: ES Kind code of ref document: T3 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19941024 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 91201020.4 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011231 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: D3 |
|
NLS | Nl: assignments of ep-patents |
Owner name: CHEMETALL GMBH |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20070412 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20070413 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20070427 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20070502 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20070628 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20070426 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20070626 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20070416 Year of fee payment: 17 |
|
BERE | Be: lapsed |
Owner name: SOC. CONTINENTALE *PARKER Effective date: 20080430 |
|
EUG | Se: european patent has lapsed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20080429 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20081101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081101 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081101 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20081231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080430 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20080430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080430 |