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EP1270767B1 - Process for cleaning and passivating light metal alloy surfaces - Google Patents

Process for cleaning and passivating light metal alloy surfaces Download PDF

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Publication number
EP1270767B1
EP1270767B1 EP01114981A EP01114981A EP1270767B1 EP 1270767 B1 EP1270767 B1 EP 1270767B1 EP 01114981 A EP01114981 A EP 01114981A EP 01114981 A EP01114981 A EP 01114981A EP 1270767 B1 EP1270767 B1 EP 1270767B1
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EP
European Patent Office
Prior art keywords
solution
phosphoric acid
light metal
metal alloy
alcohol
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.)
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EP01114981A
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German (de)
French (fr)
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EP1270767A1 (en
Inventor
Wolf-Dieter Franz
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Franz Wolf-Dieter
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Franz Wolf-Dieter
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Priority to EP01114981A priority Critical patent/EP1270767B1/en
Application filed by Franz Wolf-Dieter filed Critical Franz Wolf-Dieter
Priority to DK01114981T priority patent/DK1270767T3/en
Priority to SI200130069T priority patent/SI1270767T1/en
Priority to AT01114981T priority patent/ATE256770T1/en
Priority to DE50101194T priority patent/DE50101194D1/en
Priority to KR10-2002-0034323A priority patent/KR100502863B1/en
Priority to CNB021248060A priority patent/CN1316067C/en
Priority to JP2002179814A priority patent/JP3839362B2/en
Priority to US10/176,308 priority patent/US20030056807A1/en
Publication of EP1270767A1 publication Critical patent/EP1270767A1/en
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Publication of EP1270767B1 publication Critical patent/EP1270767B1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution

Definitions

  • This invention relates to a new method of treating surfaces of light metal alloys.
  • the aim of the treatment is a cleansing and certain Preservation of the cleaned surface.
  • the light metal alloys, on which this invention aims to contain a substantial proportion of Al and / or a significant proportion of Mg.
  • the known cleaning and Passivi mecanicsclar are partially disadvantageous because they contain health problematic substances, such as nitric acid, the releases nitrous gases.
  • FR 2298619 A relates to a process for producing very thin and so that electrically not too strongly insulating oxide layers on aluminum alloys. It is in an AC treatment in a phosphoric acid solution with a surface-active agent etched for 3-10 seconds.
  • the XP002186406 speaks from the anodic etching of Al-Ag alloys in phosphoric acid and alcohol. Before that is cleaned mechanically and with solvents.
  • This invention is based on the overall technical problem, both in terms its cleaning properties as well as its insensitivity efficient against the alloy composition as well as economically Method for cleaning and passivating light metal alloy surfaces indicated.
  • the invention is directed to a method of cleaning light alloy surfaces with a treatment step in a solution, the phosphoric acid and an alcohol in which the surface is anodically connected, characterized by an oxidation step with an aqueous solution of an oxidizing agent or of fluoride ions.
  • the anodic cleaning step in the solution with phosphoric acid and The alcohol has both a degreasing and etching of the surface a good efficiency and is also able to handle even problematic residues such as to remove polysilane release agents.
  • alcohol the usual alcohols such as methanol, ethanol, propanol, butanol and higher alcohols and their derivatives such as isopropanol into consideration. But also also diols, polyethers and other alcohols. A cheap choice are Butanol and isopropanol. Of course, two or more alcohols may be mixed occur.
  • fluoride ions used to passivate the surface.
  • the fluoride ions are used in a solution also containing phosphoric acid, wherein the surface is also connected anodically in this treatment step.
  • This Treatment step moreover, with the already described treatment step in the phosphoric acid and the alcohol-containing solution coincide, the solution thus containing phosphoric acid, the alcohol and also fluoride ions.
  • the steps can also be separated, with the fluoride ion step containing solution after the first step described he follows. At this later time step, the solution can be to optimize their Cleaning properties besides the phosphoric acid and the fluoride ions as well also the or another alcohol (or the or another alcohol mixture) contain.
  • the fluoride ions can be present in various ways, for example as alkali fluoride, ammonium (bi) fluoride or hydrofluoric acid.
  • the treatment with the fluoride ion solution is particularly suitable for light metal alloys with a substantial Mg content, in which MgF 2 is then formed as or in the passivation layer.
  • Particularly preferred is the step with the fluoride ions when the light metal alloy has a Mg content of 50% by weight and above.
  • the fluoride ion step is preferred for light metal alloys with a Si content, preferably when this is 0.1, in particular 0.5 or 1 or 2 percent by weight and above it. At low Si concentrations you tend to be small Select fluoride concentrations.
  • the fluoride ion step can therefore also be used with light metal alloys be advantageous with a low or zero Mg content.
  • the cleaning and passivation process according to the invention can advantageously be concluded with an alkaline rinsing step, for example in alkalized water having a pH of preferably 10 and more.
  • the alkaline rinsing step is particularly favorable when the passivation surface dominates MgF 2 and less favorable when dominated by Al 2 O 3 , at least at the stated high pH values.
  • Further treatment steps finally an additional passivation step in to follow an aqueous oxidizing agent.
  • This oxidizing agent can for example, a persulfate solution or a solution of peroxomonosulfuric acid (Caro's acid).
  • the passivation step in the oxidant should thereby after a possible treatment step in a fluoride solution.
  • the oxidation step is on a fluoride-coated surface of a light metal alloy not necessary with high Mg content. If he is in too acidic area it can also damage fluoride passivation (at about pH 6) and under).
  • the fluoride ion content in the total solution concerned a value between 0.1, 0.3 or 0.5 weight percent as the lower limit and 30, 20 or 10 weight percent as Have upper limit.
  • the anodic current density on the anodically poled light metal alloy surface is between 10, advantageously 30 or 50 A / m 2 as the lower limit and 500 A / m 2 as the upper limit and is, as already stated, as an optimization parameter depending on the alloy composition, the acceptable material removal and the required cleaning effect used.
  • the total treatment time of the anodic cleaning steps (for several in the sum) is between 10 seconds and 5 minutes and depends strongly on the set current density, the reasonable material removal and the degree of pollution.
  • the proportion of phosphoric acid in the solutions for the anodic purification steps is 30-90% by volume, the phosphoric acid being within this volume fraction 50-95 weight percent can be.
  • the cleaning effect of the method according to the invention is so thorough and broad scattered that chemical pretreatment steps before incorporation into the phosphoric acid and the alcohol-containing solution can be omitted and for reasons of economy should also advantageously be eliminated.
  • the surfaces to be treated can therefore be introduced directly and dry.
  • a particular advantage of the invention is also that also regenerated Light metal alloys can achieve good results, in particular no mud is created.
  • the metallic impurities of regenerated material have significant problems with cleaning in conventional processes guided and often a cleaning and subsequent good coating completely prevented. Even with a larger Al content, the surfaces remain in the invention Anodic baths metallic bright, so that the mentioned subsequent oxidation can also be made nitric acid-free.
  • a preferred application of the invention is in the preparation of Alloy alloy surfaces for subsequent coating of any Art.
  • the quality of the coating depends on the cleanliness of the surface essential, both in terms of optical properties as well on the load capacity of the coating.
  • the invention relates doing so on a subsequent metallization, preferably without external power should be done.
  • the invention is also based on the overall process the described cleaning and passivation and the following Coating, in particular metallization.
  • AZ91 is chosen, although AM50 or AZ31 would also be suitable.
  • the AZ91 alloy is introduced dry without further dry cleaning in a bath of 60 percent phosphoric acid (H 3 PO 4 ) with 40 vol.% Butanol, and anodically poled.
  • the current density is, for example, 20 A / m 2 at a temperature of 25 ° C and a treatment time, which may be about 30 s.
  • the AZ91 alloy is placed in a second bath, one with the above Composition has identical composition, but above 2 wt% ammonium bifluoride. There is another anodic Cleaning at the same current density for another 20s.
  • the AZ91 parts are rinsed in alkalized water (pH slightly above 10).
  • the AZ91 surface is now passivated by a fluoride layer and can in conventional Be metallized way.
  • the embodiment becomes a chemical conversion coating with Zn, Ni or Cu or an alloy thereof selected.
  • the second embodiment is directed to a high Al alloy, ie technical aluminum, namely GdAlSi8Cu3. Since this alloy contains Si, The fluoride bath mentioned in the first embodiment is also used here. The same quantitative parameters can be selected, but omitted the rinsing step in the alkalized water. Instead, use neutral water (pH about 7) and then additionally oxidized with a persulfate solution to the Reinforce passivation layer. This treatment also applies to GdAl-Si9Cu3.
  • the parts treated in this way can then be chemically galvanized, nickel-plated or copper-plated or coated with alloys thereof.
  • the passivation layers are dissolved or converted, so that a good and direct contact between the metals arises.
  • a particular advantage is that the final oxidation of the Al alloy nitric acid-free, since there is a metallic bright surface.
  • no nitrous gases as in conventional methods which on the one hand the technical effort for suction and exhaust gas cleaning is eliminated and on the other hand, no permit requirement according to the relevant regulations (in Germany BlmschG) is present.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

Process for cleaning light metal alloy surfaces, in which the surface is passivated by an oxidation stage, includes a treatment stage in a solution (a) containing phosphoric acid and an alcohol, in which the surface is connected as anode. An Independent claim is also included for a method of coating a light metal alloy surface, in which the surface is first cleaned and passivated as above and then coated.

Description

Diese Erfindung bezieht sich auf ein neues Verfahren zum Behandeln von Oberflächen von Leichtmetalllegierungen. Ziel der Behandlung ist eine Reinigung und gewisse Konservierung der gereinigten Oberfläche. Die Leichtmetalllegierungen, auf die diese Erfindung abzielt, enthalten einen wesentlichen Anteil Al und/oder einen wesentlichen Anteil Mg.This invention relates to a new method of treating surfaces of light metal alloys. The aim of the treatment is a cleansing and certain Preservation of the cleaned surface. The light metal alloys, on which this invention aims to contain a substantial proportion of Al and / or a significant proportion of Mg.

Es sind eine Vielzahl von Verfahren zum Reinigen von Leichtmetalllegierungsoberflächen bekannt. Zum Teil leiden diese bekannten Verfahren an dem Nachteil, dass eine größere Zahl aufeinander folgender Behandlungsschritte und damit ein vergleichsweise großer Aufwand nötig sind. Zu einem anderen Teil weisen die bekannten Verfahren ungenügende Reinigungswirkungen bezüglich bestimmter Substanzen auf, beispielsweise werden Trennmittelrückstände, etwa Polysilane, nicht wirklich zuverlässig entfernt.There are a variety of methods for cleaning light alloy surfaces known. In part, these known methods suffer from the Disadvantage that a larger number of consecutive treatment steps and so that a relatively large effort is needed. Point to another part the known methods insufficient cleaning effects with respect to certain Substances, for example, release agent residues, such as polysilanes, not really reliable removed.

Es ist außerdem bekannt, dass Oberflächen von Leichtmetalllegierungen nach einem Reinigungsverfahren durch oxidierende Behandlungen passiviert und damit in gewissem Sinn konserviert werden können. Der Begriff Oxidation ist hierbei im chemischen Sinn allgemein zu verstehen, er umfasst also neben der Reaktion mit Sauerstoff, die bei Legierungen mit hohem Al-Anteil in Betracht kommt, auch eine Reaktion mit Fluoridionen bei Legierungen mit höherem Mg-Anteil. It is also known that surfaces of light alloys after a Purification process by oxidizing treatments passivated and thus in a certain Sense can be conserved. The term oxidation is here in the chemical Meaning in general, so besides the reaction with oxygen, it which is considered in alloys with high Al content, also a reaction with fluoride ions in alloys with a higher Mg content.

Die bekannten Reinigungs- und Passivierungsverfahren sind teilweise nachteilig, weil sie gesundheitlich problematische Substanzen enthalten, etwa Salpetersäure, die nitrose Gase freisetzt. Außerdem ist es konventionellerweise schwierig, den Passivierungsschritt mit der Reinigung in solcher Weise zu kombinieren, dass die gereinigte Oberfläche vor der Passivierung nicht wieder in ihrer Qualität verschlechtert wird.The known cleaning and Passivierungsverfahren are partially disadvantageous because they contain health problematic substances, such as nitric acid, the releases nitrous gases. In addition, it is conventionally difficult to passivate to combine with the cleaning in such a way that the purified Surface before passivation is not deteriorated again in quality.

Die FR 2298619 A bezieht sich auf ein Verfahren zur Herstellung sehr dünner und damit elektrisch nicht zu stark isolierender Oxidschichten auf Aluminiumlegierungen. Dabei wird bei einer Wechselstrombehandlung in einer Phosphorsäurelösung mit einem oberflächenaktivem Mittel 3-10 Sekunden geätzt. Die XP002186406 spricht von der anodischen Ätzung von Al-Ag-Legierungen in Phosphorsäure und Alkohol. Davor wird mechanisch und mit Lösungsmitteln gereinigt.FR 2298619 A relates to a process for producing very thin and so that electrically not too strongly insulating oxide layers on aluminum alloys. It is in an AC treatment in a phosphoric acid solution with a surface-active agent etched for 3-10 seconds. The XP002186406 speaks from the anodic etching of Al-Ag alloys in phosphoric acid and alcohol. Before that is cleaned mechanically and with solvents.

Dieser Erfindung liegt insgesamt das technische Problem zugrunde, ein sowohl hinsichtlich seiner Reinigungseigenschaften als auch hinsichtlich seiner Unempfindlichkeit gegen die Legierungszusammensetzung als auch in ökonomischer Hinsicht effizientes Verfahren zum Reinigen und Passivieren von Leichtmetalllegierungsoberflächen anzugeben.This invention is based on the overall technical problem, both in terms its cleaning properties as well as its insensitivity efficient against the alloy composition as well as economically Method for cleaning and passivating light metal alloy surfaces indicated.

Die Erfindung richtet sich auf ein Verfahren zum Reinigen von Leichtmetalllegierungsoberflächen mit einem Behandlungsschritt in einer Lösung, die Phosphorsäure und einen Alkohol enthält, bei dem die Oberfläche anodisch geschaltet ist, gekennzeichnet durch einen Oxidationsschritt mit einer wässrigen Lösung eines Oxidationsmittels oder von Fluoridionen.The invention is directed to a method of cleaning light alloy surfaces with a treatment step in a solution, the phosphoric acid and an alcohol in which the surface is anodically connected, characterized by an oxidation step with an aqueous solution of an oxidizing agent or of fluoride ions.

Vorteilhafte Ausgestaltungen des erfindungsgemäßen Verfahrens sind in den abhängigen Ansprüchen aufgeführt.Advantageous embodiments of the method according to the invention are in the dependent Claims listed.

Es hat sich herausgestellt, dass mit dem erfindungsgemäßen anodischen Reinigungsverfahren eine sehr gründliche und gleichzeitig breite Reinigungswirkung erzielt wird. Der anodische Reinigungsschritt in der Lösung mit Phosphorsäure und dem Alkohol hat sowohl hinsichtlich einer Entfettung als auch Anätzung der Oberfläche eine gute Effizienz und ist außerdem in der Lage, auch problematische Rückstände wie etwa Polysilantrennmittel zu entfernen. It has been found that with the anodic cleaning method according to the invention achieved a very thorough and at the same time broad cleaning effect becomes. The anodic cleaning step in the solution with phosphoric acid and The alcohol has both a degreasing and etching of the surface a good efficiency and is also able to handle even problematic residues such as to remove polysilane release agents.

Infolge des anodischen Betriebs ist dem erfindungsgemäßen Reinigungsverfahren eine gewisse inhibierende Wirkung inhärent, indem durch anodische Sauerstoffreaktionen der Leichtmetalloberfläche ein zu großer Materialabtrag verhindert wird. Dies gilt sowohl für Leichtmetalllegierungen mit höherem Al-Anteil als auch für solche mit höherem Mg-Anteil.As a result of the anodic operation is the cleaning method of the invention a certain inhibitory effect inherent by anodic Oxygen reactions of the light metal surface an excessive material removal is prevented. This applies both to light alloys with a higher Al content as well as for those with a higher Mg content.

Im Detail läßt sich die Reinigungswirkung und insbesondere die Ätzwirkung durch die Wahl der elektrischen Parameter des anodischen Reinigungsbetriebs einstellen und damit in Abhängigkeit von der speziell in Betracht kommenden Legierung optimieren. Beispielsweise kann mit einer bestimmten anodischen Stromdichte gearbeitet werden. Damit hat man einen Optimierungsparameter in der Hand, der die Lösungszusammensetzung nicht verändert. Es kann damit auch bei ein und derselben Lösung mit verschiedenen Legierungen optimal gearbeitet werden. Natürlich lässt sich auch die Lösungszusammensetzung legierungsabhängig optimieren, wenngleich die Erfinder hier keine kritischen Abhängigkeiten feststellen konnten.In detail, the cleaning effect and in particular the corrosivity through the choice of electrical parameters of the anodic cleaning operation adjust and thus depending on the alloy of particular interest optimize. For example, with a specific Anodic current density worked become. This gives you an optimization parameter in your hand that determines the solution composition not changed. It can be synonymous with one and the same Solution to work optimally with different alloys. Of course, lets Also optimize the solution composition alloy-dependent, although the inventors could not find any critical dependencies here.

Als Alkohol kommen die üblichen Alkohole wie Methanol, Ethanol, Propanol, Butanol und höherwertige Alkohole sowie deren Derivate wie etwa Isopropanol in Betracht. Außerdem aber auch Diole, Polyether und andere Alkohole. Eine günstige Wahl sind Butanol und Isopropanol. Natürlich können auch zwei oder mehrere Alkohole in Mischung auftreten.As alcohol, the usual alcohols such as methanol, ethanol, propanol, butanol and higher alcohols and their derivatives such as isopropanol into consideration. But also also diols, polyethers and other alcohols. A cheap choice are Butanol and isopropanol. Of course, two or more alcohols may be mixed occur.

Bei einer weiteren Ausgestaltung des erfindungsgemäßen Verfahrens werden Fluoridionen verwendet, um eine Passivierung der Oberfläche zu erzielen. Die Fluoridionen werden in einer außerdem Phosphorsäure enthaltenen Lösung eingesetzt, wobei die Oberfläche auch bei diesem Behandlungsschritt anodisch geschaltet ist. Dieser Behandlungsschritt kann im übrigen mit dem bereits geschilderten Behandlungsschritt in der Phosphorsäure und den Alkohol enthaltenden Lösung zusammenfallen, wobei die Lösung also Phosphorsäure, den Alkohol und außerdem Fluoridionen enthält. Die Schritte können jedoch auch getrennt werden, wobei der Schritt mit der Fluoridionen enthaltenden Lösung zeitlich nach dem zunächst beschriebenen Schritt erfolgt. Bei diesem zeitlich späteren Schritt kann die Lösung zur Optimierung ihrer Reinigungseigenschaften neben der Phosphorsäure und den Fluoridionen außerdem auch den oder einen anderen Alkohol (bzw. die oder eine andere Alkoholmischung) enthalten.In a further embodiment of the method according to the invention are fluoride ions used to passivate the surface. The fluoride ions are used in a solution also containing phosphoric acid, wherein the surface is also connected anodically in this treatment step. This Treatment step, moreover, with the already described treatment step in the phosphoric acid and the alcohol-containing solution coincide, the solution thus containing phosphoric acid, the alcohol and also fluoride ions. However, the steps can also be separated, with the fluoride ion step containing solution after the first step described he follows. At this later time step, the solution can be to optimize their Cleaning properties besides the phosphoric acid and the fluoride ions as well also the or another alcohol (or the or another alcohol mixture) contain.

Die Fluoridionen können in verschiedenster Weise vorliegen, etwa als Alkalifluorid, Ammonium-(bi)-Fluorid oder als Flusssäure.
Die Behandlung mit der Fluoridionenlösung bietet sich vor allem für Leichtmetalllegierungen mit einem wesentlichen Mg-Anteil an, in denen dann MgF2 als oder in der Passivierungsschicht entsteht. Besonders bevorzugt ist der Schritt mit den Fluoridionen dann, wenn die Leichtmetalllegierung einen Mg-Anteil von 50 Gewichtsprozent und darüber aufweist. The fluoride ions can be present in various ways, for example as alkali fluoride, ammonium (bi) fluoride or hydrofluoric acid.
The treatment with the fluoride ion solution is particularly suitable for light metal alloys with a substantial Mg content, in which MgF 2 is then formed as or in the passivation layer. Particularly preferred is the step with the fluoride ions when the light metal alloy has a Mg content of 50% by weight and above.

Außerdem ist der Fluoridionenschritt bevorzugt für Leichtmetalllegierungen mit einem Si-Anteil, vorzugsweise wenn dieser bei 0,1, insbesondere bei 0,5 oder 1 oder 2 Gewichtsprozent und darüber liegt. Bei kleinen Si-Konzentrationen wird man eher kleine Fluoridkonzentrationen wählen. Der Fluoridionenschritt kann also auch bei Leichtmetalllegierungen mit einem geringen oder verschwindenden Mg-Anteil vorteilhaft sein.In addition, the fluoride ion step is preferred for light metal alloys with a Si content, preferably when this is 0.1, in particular 0.5 or 1 or 2 percent by weight and above it. At low Si concentrations you tend to be small Select fluoride concentrations. The fluoride ion step can therefore also be used with light metal alloys be advantageous with a low or zero Mg content.

Das erfindungsgemäße Reinigungs- und Passivierungsverfahren kann vorteilhafterweise mit einem alkalischen Spülschritt, etwa in alkalisiertem Wasser mit einem pH-Wert von vorzugsweise 10 und darüber, abgeschlossen werden. Der alkalische Spülschritt ist insbesondere dann günstig, wenn die Passivierungsoberfläche von MgF2 dominiert, und weniger günstig dann, wenn sie von Al2O3 dominiert ist, jedenfalls bei den genannten hohen pH-Werten.The cleaning and passivation process according to the invention can advantageously be concluded with an alkaline rinsing step, for example in alkalized water having a pH of preferably 10 and more. The alkaline rinsing step is particularly favorable when the passivation surface dominates MgF 2 and less favorable when dominated by Al 2 O 3 , at least at the stated high pH values.

Bei wesentlichen Al-Anteilen, insbesondere bei solchen von 60 Gewichtsprozent und darüber, ist es bevorzugt, dass man dem Behandlungsschritt in der Lösung mit Phosphorsäure und dem Alkohol und gegebenenfalls dem Behandlungsschritt in der Lösung mit Fluorid und u.U. weiteren Behandlungsschritten (die erfindungsgemäß jedoch nicht bevorzugt sind) abschließend einen zusätzlichen Passivierungsschritt in einem wässrigen Oxidationsmittel nachfolgen lässt. Dieses Oxidationsmittel kann beispielsweise eine Persulfatlösung oder eine Lösung von Peroxomonoschwefelsäure (Carosche Säure) sein. Der Passivierungsschritt in dem Oxidationsmittel soll dabei nach einem eventuellen Behandlungsschritt in einer Fluoridlösung erfolgen.For essential Al contents, especially those of 60 weight percent and above, it is preferable that the treatment step in the solution with Phosphoric acid and the alcohol and optionally the treatment step in the Solution with fluoride and u.U. Further treatment steps (according to the invention but not preferred) finally an additional passivation step in to follow an aqueous oxidizing agent. This oxidizing agent can for example, a persulfate solution or a solution of peroxomonosulfuric acid (Caro's acid). The passivation step in the oxidant should thereby after a possible treatment step in a fluoride solution.

Der Oxidationsschritt ist auf einer fluoridbeschichteten Oberfläche einer Leichtmetalllegierung mit hohem Mg-Anteil nicht notwendig. Wenn er in zu saurem Bereich durchgeführt wird, kann er die Fluoridpassivierung auch beschädigen (etwa bei pH 6 und darunter).The oxidation step is on a fluoride-coated surface of a light metal alloy not necessary with high Mg content. If he is in too acidic area it can also damage fluoride passivation (at about pH 6) and under).

Folgende quantitative Bereiche haben sich als vorteilhaft herausgestellt: Der Fluoridionenanteil in der betreffenden Gesamtlösung kann einen Wert zwischen 0,1, 0,3 oder 0,5 Gewichtsprozent als Untergrenze und 30, 20 oder 10 Gewichtsprozent als Obergrenze haben.The following quantitative areas have proven to be advantageous: The fluoride ion content in the total solution concerned, a value between 0.1, 0.3 or 0.5 weight percent as the lower limit and 30, 20 or 10 weight percent as Have upper limit.

Die anodische Stromdichte auf der anodisch gepolten Leichtmetalllegierungsoberfläche liegt zwischen 10, vorteilhafterweise 30 oder 50 A/m2 als Untergrenze und 500 A/m2 als Obergrenze und wird, wie bereits zuvor ausgeführt, als Optimierungsparameter abhängig von der Legierungszusammensetzung, dem vertretbaren Materialabtrag und der erforderlichen Reinigungswirkung verwendet.The anodic current density on the anodically poled light metal alloy surface is between 10, advantageously 30 or 50 A / m 2 as the lower limit and 500 A / m 2 as the upper limit and is, as already stated, as an optimization parameter depending on the alloy composition, the acceptable material removal and the required cleaning effect used.

Günstige Temperaturen für die Lösungen der anodischen Reinigungsschritte liegen zwischen 10 und 40° C.Favorable temperatures for the solutions of anodic cleaning steps are between 10 and 40 ° C.

Die gesamte Behandlungszeit der anodischen Reinigungsschritte (bei mehreren in der Summe) liegt zwischen 10 Sekunden und 5 Minuten und hängt stark von der eingestellten Stromdichte, dem vertretbaren Materialabtrag und dem Verschmutzungsgrad ab.The total treatment time of the anodic cleaning steps (for several in the sum) is between 10 seconds and 5 minutes and depends strongly on the set current density, the reasonable material removal and the degree of pollution.

Der Anteil der Phosphorsäure an den Lösungen für die anodischen Reinigungsschritte liegt bei 30-90 Vol.%, wobei die Phosphorsäure innerhalb dieses Volumenanteils 50-95 gewichtsprozentig sein kann. Das bezieht sich insbesondere auf Lösungen mit Alkoholanteil, die vorteilhafterweise außer dem genannten Volumenanteil der Phosphorsäure von 30-90 Vol.% im Rest im wesentlichen aus dem Alkohol(-gemisch) und gegebenenfalls dem Fluorid besteht.The proportion of phosphoric acid in the solutions for the anodic purification steps is 30-90% by volume, the phosphoric acid being within this volume fraction 50-95 weight percent can be. This refers in particular to solutions Alcohol content, which advantageously except the said volume fraction of phosphoric acid from 30-90% by volume in the balance essentially of the alcohol (mixture) and optionally the fluoride is.

Die Reinigungswirkung des erfindungsgemäßen Verfahrens ist so gründlich und breit gestreut, dass chemische Vorbehandlungsschritte vor dem Einbringen in die Phosphorsäure und den Alkohol enthaltende Lösung entfallen können und aus Ökonomiegründen auch vorteilhafterweise wegfallen sollten. Die zu behandelnden Oberflächen können also direkt und trocken eingebracht werden.The cleaning effect of the method according to the invention is so thorough and broad scattered that chemical pretreatment steps before incorporation into the phosphoric acid and the alcohol-containing solution can be omitted and for reasons of economy should also advantageously be eliminated. The surfaces to be treated can therefore be introduced directly and dry.

Ein besonderer Vorteil der Erfindung liegt außerdem darin, dass sich auch auf regenerierten Leichtmetalllegierungen gute Ergebnisse erzielen lassen, insbesondere kein Schlamm entsteht. Die metallischen Verunreinigungen von Regeneratmaterial haben bei konventionellen Verfahren zu erheblichen Problemen in der Reinigung geführt und häufig eine Reinigung und nachfolgende gute Beschichtung ganz verhindert. Auch bei größerem Al-Anteil bleiben die Oberflächen in den erfindungsgemäßen anodischen Bädern metallisch blank, so dass die erwähnte anschließende Oxidation auch salpetersäurefrei erfolgen kann. A particular advantage of the invention is also that also regenerated Light metal alloys can achieve good results, in particular no mud is created. The metallic impurities of regenerated material have significant problems with cleaning in conventional processes guided and often a cleaning and subsequent good coating completely prevented. Even with a larger Al content, the surfaces remain in the invention Anodic baths metallic bright, so that the mentioned subsequent oxidation can also be made nitric acid-free.

Eine bevorzugte Anwendung der Erfindung liegt in der Vorbereitung von Leichtmetalllegierungsoberflächen für eine anschließende Beschichtung beliebiger Art. Für die Qualität der Beschichtung kommt es auf die Sauberkeit der Oberfläche wesentlich an, und zwar sowohl im Hinblick auf die optischen Eigenschaften als auch auf die Belastbarkeit der Beschichtung. Insbesondere bezieht sich die Erfindung dabei auf eine anschließende Metallisierung, die vorzugsweise außenstromlos erfolgen sollte. Insoweit richtet sich die Erfindung auch auf das Gesamtverfahren aus der beschriebenen Reinigung und Passivierung und der nachfolgenden Beschichtung, insbesondere Metallisierung.A preferred application of the invention is in the preparation of Alloy alloy surfaces for subsequent coating of any Art. The quality of the coating depends on the cleanliness of the surface essential, both in terms of optical properties as well on the load capacity of the coating. In particular, the invention relates doing so on a subsequent metallization, preferably without external power should be done. In that regard, the invention is also based on the overall process the described cleaning and passivation and the following Coating, in particular metallization.

Im Folgenden werden zwei Ausführungsbeispiele für die Erfindung beschrieben, wobei dabei offenbarte Einzelmerkmale auch in anderen Kombinationen erfindungswesentlich sein können.In the following two embodiments of the invention will be described, wherein thereby disclosed individual features essential to the invention in other combinations could be.

Als typisches Beispiel für eine Legierung mit höherem Mg-Anteil wird AZ91 gewählt, wobei auch AM50 oder AZ31 in Frage kämen. Die AZ91-Legierung wird ohne weitere chemische Reinigung trocken in ein Bad aus 60 prozentiger Phosphorsäure (H3PO4) mit 40 Vol.% Butanol eingebracht, und zwar anodisch gepolt. Die Stromdichte liegt beispielsweise bei 20 A/m2 bei einer Temperatur von 25° C und einer Behandlungszeit, die etwa bei 30 s liegen kann.As a typical example of an alloy with a higher Mg content, AZ91 is chosen, although AM50 or AZ31 would also be suitable. The AZ91 alloy is introduced dry without further dry cleaning in a bath of 60 percent phosphoric acid (H 3 PO 4 ) with 40 vol.% Butanol, and anodically poled. The current density is, for example, 20 A / m 2 at a temperature of 25 ° C and a treatment time, which may be about 30 s.

Danach wird die AZ91-Legierung in ein zweites Bad gebracht, das eine mit der genannten Zusammensetzung identische Zusammensetzung aufweist, jedoch darüber hinaus 2 Gewichtsprozent Ammoniumbifluorid enthält. Es erfolgt eine weitere anodische Reinigung bei gleicher Stromdichte für weitere 20s.Thereafter, the AZ91 alloy is placed in a second bath, one with the above Composition has identical composition, but above 2 wt% ammonium bifluoride. There is another anodic Cleaning at the same current density for another 20s.

Danach werden die AZ91-Teile in alkalisiertem Wasser (pH leicht über 10) gespült. Die AZ91-Oberfläche ist nun durch eine Fluoridschicht passiviert und kann in konventioneller Weise metallisiert werden. Bei dem Ausführungsbeispiel wird dazu eine chemische Konversionsbeschichtung mit Zn, Ni oder Cu oder einer Legierung daraus gewählt.Thereafter, the AZ91 parts are rinsed in alkalized water (pH slightly above 10). The AZ91 surface is now passivated by a fluoride layer and can in conventional Be metallized way. In the embodiment becomes a chemical conversion coating with Zn, Ni or Cu or an alloy thereof selected.

Das zweite Ausführungsbeispiel richtet sich auf eine Legierung mit hohem Al-Anteil, also technisches Aluminium, nämlich GdAlSi8Cu3. Da diese Legierung Si enthält, wird das bei dem ersten Ausführungsbeispiel erwähnte Fluoridbad auch hier verwendet. Es können die gleichen quantitativen Parameter gewählt werden, jedoch entfällt der Spülschritt in dem alkalisierten Wasser. Stattdessen wird mit neutralem Wasser (pH etwa 7) gespült und danach mit einer Persulfatlösung zusätzlich oxidiert, um die Passivierungsschicht zu verstärken. Diese Behandlung gilt auch etwa für GdAl-Si9Cu3.The second embodiment is directed to a high Al alloy, ie technical aluminum, namely GdAlSi8Cu3. Since this alloy contains Si, The fluoride bath mentioned in the first embodiment is also used here. The same quantitative parameters can be selected, but omitted the rinsing step in the alkalized water. Instead, use neutral water (pH about 7) and then additionally oxidized with a persulfate solution to the Reinforce passivation layer. This treatment also applies to GdAl-Si9Cu3.

Die so behandelten Teile können dann wiederum chemisch verzinkt, vernickelt oder verkupfert oder mit Legierungen daraus beschichtet werden. Bei der chemischen Konversionsbeschichtung werden die Passivierungsschichten gelöst bzw. konvertiert, so dass ein guter und direkter Kontakt zwischen den Metallen entsteht.The parts treated in this way can then be chemically galvanized, nickel-plated or copper-plated or coated with alloys thereof. In the chemical Conversion coating, the passivation layers are dissolved or converted, so that a good and direct contact between the metals arises.

Ein besonderer Vorteil besteht darin, dass die abschließende Oxidation der Al-Legierung salpetersäurefrei erfolgen kann, da eine metallisch blanke Oberfläche vorliegt. Somit entstehen keine nitrosen Gase wie bei konventionellen Verfahren, womit zum einen der technische Aufwand für Absaugung und Abgasreinigung entfällt und zum anderen keine Genehmigungspflicht nach den einschlägigen Vorschriften (in Deutschland BlmschG) vorliegt.A particular advantage is that the final oxidation of the Al alloy nitric acid-free, since there is a metallic bright surface. Thus, no nitrous gases as in conventional methods, which on the one hand the technical effort for suction and exhaust gas cleaning is eliminated and on the other hand, no permit requirement according to the relevant regulations (in Germany BlmschG) is present.

Wenn die Leichtmetalllegierungen beispielsweise aus einem Druckgussverfahren stammen, so sind sie in der Regel mit Formtrennmitteln kontaminiert. Auch diese werden bei den dargestellten Reinigungsverfahren zuverlässig und vollständig entfernt.For example, if the light metal alloys from a die-casting They are usually contaminated with mold release agents. These too are reliably and completely removed in the illustrated cleaning process.

Claims (16)

  1. A method of cleaning light metal alloy surfaces including a treatment step in a solution, which includes 30-90 vol.% phosphoric acid and an alcohol, in which the surface is anodically connected and is treated for between 10 s and 5 min with a current density in the range of 10-500 A/m2, in which method an oxidation step occurs with an aqueous solution of a strong oxidising agent, such as persulphate solution or peroxomonosulphuric acid solution, or a treatment in a solution of 0.1-10 wt.% fluoride ions.
  2. A method as claimed in Claim 1 including a treatment step in a solution, which contains phosphoric acid and fluoride ions, in which the surface is anodically connected.
  3. A method as claimed in Claim 1 or 2 including a final alkaline washing step.
  4. A method as claimed in Claim 2, also in conjunction with Claim 3, in which the light metal alloy contains Si in an amount of at least 0.1 weight percent.
  5. A method as claimed in Claim 2, also in conjunction with Claim 3 or Claim 4, in which the light metal alloy contains Mg in an amount of at least 50 weight percent.
  6. A method as claimed in Claim 2, also in conjunction with one of Claims 3-5, in which the treatment steps in the solution with phosphoric acid and an alcohol and in the solution with phosphoric acid and fluoride are combined into one treatment step in one solution, which contains the phosphoric acid, an alcohol and fluoride.
  7. A method as claimed in Claim 2, also in conjunction with one of Claims 3-5, in which firstly the treatment step in the solution with phosphoric acid and an alcohol is performed and then the treatment step in the solution with phosphoric acid and fluoride is performed separately.
  8. A method as claimed in Claim 7, in which the solution with phosphoric acid and fluoride also contains an alcohol.
  9. A method as claimed in Claim 1, in which the light metal alloy contains Al in an amount of at least 60 weight percent and in which after a treatment step in the solution with phosphoric acid and an alcohol a further treatment step occurs in an aqueous oxidising agent.
  10. A method as claimed in one of the preceding claims, in which, during the treatment step or steps in the solution or solutions with phosphoric acid, in which the light metal alloy is of anodic polarity, the temperature of the solution is between 10° and 40°C.
  11. A method as claimed in one of the preceding claims, in which the remainder of the solution substantially consists of at least one alcohol and optionally at least one fluoride.
  12. A method as claimed in Claim 11, in which the phosphoric acid in the volumetric proportion is 50-95 weight percent.
  13. A method as claimed in one of the preceding claims, in which the light metal alloy surface is introduced without chemical pretreatment into the solution with phosphoric acid and the alcohol.
  14. A method as claimed in one of the preceding claims, in which the light metal alloy consists of reclaimed material.
  15. A method of coating a light metal alloy surface, in which the light metal alloy surface is firstly cleaned and passivated with a method as claimed in one of Claims 1-14 and is then coated.
  16. A method as claimed in Claim 15, in which the coating process is a metallisation process without external current.
EP01114981A 2001-06-20 2001-06-20 Process for cleaning and passivating light metal alloy surfaces Expired - Lifetime EP1270767B1 (en)

Priority Applications (9)

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DK01114981T DK1270767T3 (en) 2001-06-20 2001-06-20 Process for cleaning and passivating light metal alloy surfaces
SI200130069T SI1270767T1 (en) 2001-06-20 2001-06-20 Process for cleaning and passivating light metal alloy surfaces
AT01114981T ATE256770T1 (en) 2001-06-20 2001-06-20 METHOD FOR CLEANING AND PASSIVATION OF LIGHT METAL ALLOY SURFACES
DE50101194T DE50101194D1 (en) 2001-06-20 2001-06-20 Process for cleaning and passivating light metal alloy surfaces
EP01114981A EP1270767B1 (en) 2001-06-20 2001-06-20 Process for cleaning and passivating light metal alloy surfaces
KR10-2002-0034323A KR100502863B1 (en) 2001-06-20 2002-06-19 Procedure for cleaning and passivating light metal alloy surface
US10/176,308 US20030056807A1 (en) 2001-06-20 2002-06-20 Method for cleaning and passivating a metal surface
JP2002179814A JP3839362B2 (en) 2001-06-20 2002-06-20 Methods for cleaning and passivating light alloy surfaces
CNB021248060A CN1316067C (en) 2001-06-20 2002-06-20 Method for purifying and decontaminating surface of light metal alloy

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EP01114981A EP1270767B1 (en) 2001-06-20 2001-06-20 Process for cleaning and passivating light metal alloy surfaces

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EP1270767B1 true EP1270767B1 (en) 2003-12-17

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AT (1) ATE256770T1 (en)
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US7578921B2 (en) * 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
AU2002338880A1 (en) * 2002-10-09 2004-05-04 Wolf-Dieter Franz Method for cleaning and passivating light alloy surfaces
EP1684914A1 (en) * 2003-11-20 2006-08-02 BAE Systems PLC Surface preparation prior to coating
CN101591797B (en) * 2008-05-30 2012-08-08 中芯国际集成电路制造(上海)有限公司 Al pad electrochemical etching method
CN101591799B (en) * 2008-05-30 2011-04-20 比亚迪股份有限公司 Electrolytic polishing solution of magnesium alloy and magnesium alloy surface polishing processing method
JP6557984B2 (en) * 2015-02-06 2019-08-14 栗田工業株式会社 Aluminum or aluminum alloy sealing method and sealing device
CN105603409B (en) * 2016-01-15 2018-10-09 华南理工大学 A kind of Aluminum Alloy Room Temperature alkalinity chromium-free passivation liquid and passivating method
DE102017109739A1 (en) * 2017-05-05 2018-11-08 Fischer Oberflächentechnik GmbH Aqueous solution and method for removing acid residues from metal surfaces
CN107829122A (en) * 2017-11-24 2018-03-23 绩溪山合机械有限公司 A kind of chain inactivating treatment liquid and its passivation process

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627654A (en) * 1969-11-19 1971-12-14 Atomic Energy Commission Electrolytic process for cleaning high-carbon steels
US3920471A (en) * 1974-10-10 1975-11-18 Teletype Corp Prevention of aluminum etching during silox photoshaping
FR2298619A1 (en) * 1975-01-22 1976-08-20 Pechiney Aluminium PROCESS AND SURFACE TREATMENT OF AN ALUMINUM WIRE FOR ELECTRICAL USE
JPS60248898A (en) * 1983-06-30 1985-12-09 Chobe Taguchi Derusting solution for electrolysis
FR2633945B1 (en) * 1988-07-06 1992-09-04 Pechiney Aluminium PROCESS OF CONTINUOUS ENAMELLING OF ALUMINUM ALLOY WIRES FOR THE MANUFACTURE OF ELECTRIC WINDINGS
US5015298A (en) * 1989-08-22 1991-05-14 Halliburton Company Composition and method for removing iron containing deposits from equipment constructed of dissimilar metals
US5217586A (en) * 1992-01-09 1993-06-08 International Business Machines Corporation Electrochemical tool for uniform metal removal during electropolishing
AU4267096A (en) * 1994-12-19 1996-07-10 Alcan International Limited Cleaning aluminium workpieces
CN1049259C (en) * 1994-12-29 2000-02-09 华中理工大学 Electrochemical Polishing Method for Aluminum and Aluminum Alloy Welding Wire
US5601695A (en) * 1995-06-07 1997-02-11 Atotech U.S.A., Inc. Etchant for aluminum alloys
US6579439B1 (en) * 2001-01-12 2003-06-17 Southern Industrial Chemicals, Inc. Electrolytic aluminum polishing processes

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JP3839362B2 (en) 2006-11-01
KR100502863B1 (en) 2005-07-25
CN1397667A (en) 2003-02-19
ATE256770T1 (en) 2004-01-15
CN1316067C (en) 2007-05-16
SI1270767T1 (en) 2004-06-30
EP1270767A1 (en) 2003-01-02
DK1270767T3 (en) 2004-04-13
JP2003049299A (en) 2003-02-21
KR20020097002A (en) 2002-12-31
DE50101194D1 (en) 2004-01-29

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