EP1403402A1 - Process for the electrolytic deposition of materials with aluminium, magnesium or alloys of aluminium and magnesium - Google Patents
Process for the electrolytic deposition of materials with aluminium, magnesium or alloys of aluminium and magnesium Download PDFInfo
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- EP1403402A1 EP1403402A1 EP02021402A EP02021402A EP1403402A1 EP 1403402 A1 EP1403402 A1 EP 1403402A1 EP 02021402 A EP02021402 A EP 02021402A EP 02021402 A EP02021402 A EP 02021402A EP 1403402 A1 EP1403402 A1 EP 1403402A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/42—Electroplating: Baths therefor from solutions of light metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
Definitions
- the present invention relates to a method for the electrolytic coating of materials with aluminum, magnesium or alloys of aluminum and magnesium, the material being dipped into an electrolyte for pretreatment and being anodically switched there, and the electrolytic coating being carried out in the same electrolyte immediately thereafter.
- the quality of the deposited aluminum, magnesium or aluminum / magnesium coating is improved by the method according to the invention.
- the deposition of aluminum, magnesium or aluminum / magnesium alloys on materials consisting of base metals is a tried and tested means of protecting these materials from corrosion. At the same time, they are provided with a decorative coating.
- the protective metal layer is mainly galvanically deposited on the material. It is advantageous here if the aluminum, magnesium or aluminum / magnesium layer is carried out on the material without the application of metallic intermediate layers between said metal layer and the material. If intermediate layers between the material and the surface layer made of aluminum, magnesium or aluminum / magnesium alloy are applied, there is a risk of contact corrosion due to the applied intermediate layer. In addition, thermal problems can arise due to the different expansion coefficients of the surface layer and the intermediate layer.
- the electrolytes that have proven themselves in the prior art include melt flow electrolytes, such as electrolytes, which contain aluminum halides or aluminum alkyl complexes. All these electrolyte systems have in common that the material on its surface must be cleaned before coating. This is particularly the case for materials made from base metal exist which form an oxide layer, the problem that this oxide layer must be completely removed before coating. If the surface of the materials is not completely cleaned, impurities or residues of the oxide layer of the metal from which the material is made adhere to the surface and impair the adhesion of the subsequently electrolytically applied metal layer. Furthermore, it is possible that no metal layer is applied at the points where contaminants are present on the surface, since the contaminants are generally not electrically conductive and thus electrolytic deposition is prevented at this point. This then inevitably leads to corrosion problems of the finished coated material at the point where the metal layer was not completely applied.
- DE-C3-22 60 191 describes a method for the preparation of materials made of electrically conductive materials.
- the last step in the process of shaping the materials, in which a new bare surface is created on the material, is carried out in a suitable inert gas or inert liquid medium with the exclusion of atmospheric oxygen and moisture.
- This method has the disadvantage that, in particular when using an inert liquid medium which covers the surface of the material and can thus be placed in the coating electrolyte, the latter subsequently contaminates or hydrolyzes the electrolyte.
- inert gas media When using inert gas media, the problem arises in large-scale industrial use that an absolutely oxygen-free inert gas atmosphere is practically impossible to achieve.
- DE-AS-12 12 213 describes the pretreatment of a material in a protective gas atmosphere.
- the oxide layer on the surface of the material can be removed by anodically switching the material before depositing the aluminum layer in the electrolyte, which is made from sodium fluoride and aluminum triethyl. Then the polarity of the current is reversed and aluminum is deposited on the material.
- the electrolyte can only be used for the deposition of aluminum on materials.
- the deposition of magnesium or aluminum / magnesium layers is not possible, since the presence of halide ions in the electrolyte during the anodic polarization would result in immediately insoluble magnesium halide compounds which prevent the deposition of magnesium or aluminum / magnesium on the material.
- the resulting magnesium halides would immediately prevent the current flow in the electrolyte by blocking the electrodes.
- DE-AS-21 22 610 describes a process for the anodic pretreatment of light metals for the galvanic deposition of aluminum.
- the components are cleaned by treating the light metal materials in a melt electrolyte, the materials being anodically loaded.
- the light metal materials cleaned in this way are immersed in an electrolytic cell, moist with electrolyte, i.e. still loaded with the molten electrolyte. It cannot be ruled out that atmospheric oxygen will still reach the pretreated material and oxidize it again on the surface.
- the aluminum electrolyte is contaminated by the surface treatment electrolyte, which is a melt electrolyte.
- the material consists of beryllium or aluminum is it possible that the material in the melt electrolyte, which is used for surface treatment by anodic oxidation of the material, also for the galvanic deposition of aluminum on the Beryllium or aluminum material is used.
- the melting electrolyte described in DE-AS-21 22 610 is only suitable for pretreating beryllium or aluminum materials in order to subsequently coat them with aluminum in the same melting electrolyte.
- the melting electrolyte is not suitable for the galvanic application of aluminum, magnesium or aluminum / magnesium layers on other materials.
- DE-A1-198 55 666 describes an electrolyte which is suitable for the deposition of aluminum / magnesium alloy layers.
- the disclosed aluminum-organic electrolyte contains K [AIEt 4 ] or Na [Et 3 Al-H-AlEt 3 ], as well as Na [AlEt 4 ], and trialkyl aluminum.
- the electrolyte can be in the form of a toluene solution.
- the electrolytic deposition of aluminum / magnesium alloy layers from the described electrolyte is carried out using a soluble aluminum and a likewise soluble magnesium anode or using an anode made of aluminum / magnesium alloy.
- the electrolyte composition is adjusted by pre-electrolysis so that the deposited layer has the desired aluminum / magnesium ratio.
- Mg [AlEt 4 ] 2 can also be added to the electrolyte.
- DE-A1-198 55 666 thus teaches that the ratio of aluminum and magnesium in the deposited aluminum / magnesium layer depends very much on the concentration ratio of magnesium and aluminum in the electrolyte.
- great care is required in the pretreatment of the materials to be coated, since contamination of the material surface by oxidation or other influences leads to a reduced quality of the galvanically deposited metal layer.
- the technical object of the present invention is to provide a method in which aluminum, magnesium or aluminum / magnesium layers can be applied to materials, the quality of the metal coating being increased by an improved pretreatment of the material.
- a method is to be made available be, in which the materials to be coated are reliably and inexpensively freed from adhering oxide layers or other impurities, wherein after the pretreatment of the materials a renewed contamination or oxidation of the materials should be prevented.
- the technical object of the present invention is achieved by a method for the electrolytic coating of materials with aluminum, magnesium or alloys of aluminum and magnesium, the material being immersed in the electrolyte for pretreatment, being anodically switched there and immediately thereafter the electrolytic coating in the same Electrolytes take place, the electrolyte bath organoaluminum compounds of the general formula M [(R 1 ) 3 Al- (H-Al (R 2 ) 2 ) n -R 3 ] (I) and Al (R 4 ) 3 (II) as the electrolyte contains and n is 0 or 1, M is sodium or potassium and R 1 , R 2 , R 3 , R 4 may be the same or different, where R 1 , R 2 , R 3 , R 4 is a C 1 - bis C 4 alkyl group and a halogen-free, aprotic solvent is used as the solvent for the electrolyte.
- the method according to the invention makes it possible to pretreat the material in the bath in which the electrolytic coating takes place later. Surprisingly, impurities that adhere to the non-pretreated material and any oxide layers on the material are removed.
- the impurities which are thus introduced into the electrolyte bath surprisingly do not hinder the deposition of magnesium, aluminum or alloys of aluminum and magnesium on the material. Insoluble impurities can be continuously removed from the electrolyte bath using suitable filtration systems.
- an electrolyte is used as a mixture of the complexes K [AlEt 4 ], Na [AlEt 4 ] and AlEt 3 used.
- the molar ratio of the complexes to AIEt 3 is 1: 0.5 to 1: 3, the ratio of 1: 2 being preferred.
- 0 to 25 mol%, preferably 5 to 20 mol% Na [AlEt 4 ], based on the mixture of the complexes K [AlEt 4 ] and Na [AlEt 4 ], are used.
- a mixture of 0.8 mol of K [AlEt 4 ] , 0.2 mol of Na [AlEt 4 ], 2.0 mol of AlEt 3 in 3.3 mol of toluene can preferably be used as the electrolyte.
- a mixture of Na [Et 3 Al-H-AlEt 3 ] and Na [AlEt4] and AIEt 3 can be used as the electrolyte in the process according to the invention.
- the molar ratio of Na [Et 3 Al-H-AlEt 3 ] to Na [AlEt 4 ] is 4: 1 to 1: 1, with a ratio of 2: 1 being preferred. It is further preferred that the molar ratio of Na [AlEt 4 ] to AlEt 3 is 1: 2.
- a mixture of 1 mol of Na [Et 3 Al-H-AlEt 3 ], 0.5 mol of Na [AlEt 4 ] and 1 mol of AlEt 3 in 3 mol of toluene is used as the electrolyte.
- the electrolytic coating of materials with magnesium, aluminum or aluminum / magnesium alloys is preferably carried out at a temperature of 80 to 105 ° C. A temperature of the electroplating bath of 91 to 100 ° C. is preferred.
- the electrolytic deposition of aluminum, magnesium, or aluminum / magnesium layers on the materials is carried out using a soluble aluminum and a likewise soluble magnesium anode or using an anode made of an aluminum / magnesium alloy.
- a soluble aluminum and a likewise soluble magnesium anode or using an anode made of an aluminum / magnesium alloy are soluble aluminum and a likewise soluble magnesium anode or using an anode made of an aluminum / magnesium alloy.
- the anodic switching of the material for pretreatment can be carried out for a period of 1 to 20 minutes, with 5 to 15 minutes being preferred.
- the anodic loading of the materials required for the pretreatment is carried out with a current density of 0.2 to 2 A / dm 2 , preferably 0.5 to 1.5 A / dm 2 .
- the material consists of a metal and / or a metal alloy and / or is a metallized, electrolyte-resistant material that can be dissolved in the electrolyte by anodic switching.
- the materials to be coated are preferably rack goods, bulk goods or continuous products such as wire, square sheets, screws or nuts.
- the method according to the invention is characterized in that impurities or oxide layers which adhere to the materials are reliably removed.
- impurities or oxide layers which adhere to the materials are reliably removed.
- there is no disadvantageous change in the electrolyte composition that would prevent high-quality deposition of aluminum, magnesium or aluminum / magnesium layers on the materials.
- the galvanically applied metal layers are firmly adhering and homogeneously applied to the material, since after the cleaning a renewed contamination of the material is prevented.
- the process steps mentioned also achieve a cost optimization of coating molded parts with metal layers.
- Phase b) The dry part was introduced into a coating cell flooded with argon or nitrogen and, after a pre-rinsing in toluene, was introduced immediately into the coating electrolyte. A mixture of the complexes K [AlEt 4 ], K [AlEt 4 ] and AlEt 3 was used as the electrolyte, dissolved in toluene. An AIMg25 alloy plate served as the counter electrode. The product to be coated was first anodically poled and treated at a current density of 1 A / dm 2 for 5 minutes at an electrolyte temperature of 95 C. Then the polarity was reversed without removing the part from the electrolyte and immediately for 45 minutes at a current density of 1 , 5 A / dm 2 coated. An AIMg alloy layer approximately 14 ⁇ m thick was deposited.
- the adhesive strength of the layer was checked by means of a cross cut test and a heat shock test (1 h at 220 ° C. and quenching in cold water). It was found that the deposited layer had excellent adhesion to the base material. No detachments or bubbles were found.
- a part treated as a comparative sample was pretreated and coated as in Example 1, but without anodic polarity beforehand.
- the layer could be peeled off as a film during the cross cut test. In the heat shock test, the layer showed bubbles.
- a magnesium die-cast part made of an AZ-91 alloy was blasted with corundum (grain size 0-50 ⁇ m) at 2 bar pressure. The part was then immediately placed in the inert gas atmosphere of the coating cell, rinsed in toluene and immersed in the electrolyte bath as described in Example 1.
- the product to be coated was anodized for 10 minutes at a current density of 1 A / dm 2 .
- a layer of approx. 2 ⁇ m was removed from the product surface.
- the polarity was then reversed and the part was connected cathodically for 1 hour at 1.5 A / dm 2 .
- An AIMg layer with 23-25% Mg content and a layer thickness of approx. 18 ⁇ m was deposited.
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur elektrolytischen Beschichtung von Werkstoffen mit Aluminium, Magnesium oder Legierungen von Aluminium und Magnesium, wobei der Werkstoff zur Vorbehandlung in einen Elektrolyten getaucht wird und dort anodisch geschaltet wird und unmittelbar danach die elektrolytische Beschichtung in demselben Elektrolyten erfolgt. Durch das erfindungsgemäße Verfahren wird die Qualität der abgeschiedenen Aluminium-, Magnesium- oder Aluminium/Magnesium-Beschichtung verbessert.The present invention relates to a method for the electrolytic coating of materials with aluminum, magnesium or alloys of aluminum and magnesium, the material being dipped into an electrolyte for pretreatment and being anodically switched there, and the electrolytic coating being carried out in the same electrolyte immediately thereafter. The quality of the deposited aluminum, magnesium or aluminum / magnesium coating is improved by the method according to the invention.
Die Abscheidung von Aluminium, Magnesium oder Aluminium/Magnesium-Legierungen auf Werkstoffen, die aus unedlen Metallen bestehen ist ein probates Mittel um diese Werkstoffe vor Korrosion zu schützen. Sie werden dabei gleichzeitig mit einer dekorativen Beschichtung versehen. Die schützende Metallschicht wird hierbei vorwiegend galvanisch auf dem Werkstoff abgeschieden. Hierbei ist es vorteilhaft, wenn die Aluminium-, Magnesium- oder Aluminium/Magnesium-Schicht auf dem Werkstoff ohne die Aufbringung von metallischen Zwischenschichten zwischen besagter Metallschicht und dem Werkstoff erfolgt. Falls Zwischenschichten zwischen dem Werkstoff und der Oberflächenschicht aus Aluminium, Magnesium oder Aluminium/Magnesium-Legierung aufgebracht sind, besteht die Gefahr der Kontaktkorrosion bedingt durch die aufgebrachte Zwischenschicht. Zusätzlich können thermische Probleme bedingt durch die unterschiedlichen Ausdehnungskoeffizienten der Oberflächenschicht und der Zwischenschicht auftreten.The deposition of aluminum, magnesium or aluminum / magnesium alloys on materials consisting of base metals is a tried and tested means of protecting these materials from corrosion. At the same time, they are provided with a decorative coating. The protective metal layer is mainly galvanically deposited on the material. It is advantageous here if the aluminum, magnesium or aluminum / magnesium layer is carried out on the material without the application of metallic intermediate layers between said metal layer and the material. If intermediate layers between the material and the surface layer made of aluminum, magnesium or aluminum / magnesium alloy are applied, there is a risk of contact corrosion due to the applied intermediate layer. In addition, thermal problems can arise due to the different expansion coefficients of the surface layer and the intermediate layer.
Zu den Elektrolyten, die sich im Stand der Technik bewährt haben, gehören Schmelzflusselektrolyte, wie Elektrolyte, die Aluminiumhalogenide oder Aluminiumalkylkomplexe enthalten. Allen diesen Elektrolytsystemen ist gemeinsam, dass der Werkstoff vor der Beschichtung an seiner Oberfläche gereinigt werden muss. So stellt sich vor allem bei Werkstoffen, die aus unedlen Metallen bestehen welche eine Oxidschicht bilden, das Problem, dass diese Oxidschicht vor der Beschichtung vollständig entfernt werden muss. Falls die Oberfläche der Werkstoffe nicht vollständig gereinigt ist, führen auf der Oberfläche anhaftende Verunreinigungen oder Reste der Oxidschicht des Metalls, aus dem der Werkstoff besteht, zu einer Beeinträchtigung der Haftung der nachfolgend elektrolytisch aufgebrachten Metallschicht. Weiterhin ist es möglich, dass an den Stellen, an denen Verunreinigungen auf der Oberfläche vorhanden sind, gar keine Metallschicht aufgebracht wird, da die Verunreinigungen in der Regel nicht elektrisch leitend sind und somit eine elektrolytische Abscheidung an dieser Stelle verhindert wird. Dies führt dann zwangsläufig zu Korrosionsproblemen des fertig beschichteten Werkstoffs an der Stelle, an der die Metallschicht nicht vollständig aufgebracht wurde.The electrolytes that have proven themselves in the prior art include melt flow electrolytes, such as electrolytes, which contain aluminum halides or aluminum alkyl complexes. All these electrolyte systems have in common that the material on its surface must be cleaned before coating. This is particularly the case for materials made from base metal exist which form an oxide layer, the problem that this oxide layer must be completely removed before coating. If the surface of the materials is not completely cleaned, impurities or residues of the oxide layer of the metal from which the material is made adhere to the surface and impair the adhesion of the subsequently electrolytically applied metal layer. Furthermore, it is possible that no metal layer is applied at the points where contaminants are present on the surface, since the contaminants are generally not electrically conductive and thus electrolytic deposition is prevented at this point. This then inevitably leads to corrosion problems of the finished coated material at the point where the metal layer was not completely applied.
DE-C3-22 60 191 beschreibt ein Verfahren zur Vorbereitung von Werkstoffen aus elektrisch leitfähigen Materialien. Hierbei wird der letzte zur Formgebung der Werkstoffe dienende Verfahrensschritt, bei dem eine neue blanke Oberfläche auf dem Werkstoff entsteht, unter Ausschluss von Luftsauerstoff und Feuchtigkeit in einem geeigneten Inertgas oder Inertflüssigkeitsmedium durchgeführt. Nachteilig stellt sich bei diesem Verfahren heraus, dass insbesondere bei der Verwendung von Inertflüssigkeitsmedium, welches die Oberfläche des Werkstoffes bedeckt und somit in den Beschichtungselektrolyten verbracht werden kann, dieses nachfolgend den Elektrolyten verunreinigt oder hydrolysiert. Bei der Verwendung von Inertgasmedien zeigt sich bei der großtechnischen Anwendung das Problem, dass eine absolut sauerstofffreie Inertgasatmosphäre praktisch nicht zu realisieren ist. Spuren von Sauerstoff, die in der Inertgasatmosphäre vorhanden sind, oxidieren sofort die blanke Metalloberfläche des Werkstoffes und führen so zu den bereits beschriebenen Qualitätseinbußen der nachfolgend galvanisch aufgebrachten Metallschicht. Wenn, wie in DE-C3-22 60 191 beschrieben, die blanke Oberfläche durch ein mechanisches Verfahren, wie z. B. Fräsen, Spanen, Sägen oder Bohren, oder durch starkes Verformen des Werkstoffes mit z. B. Walzen oder durch Drahtziehen, Extrudieren oder anderen Verfahren durchgeführt wird, bedingen diese Verfahren eine Zunahme der Fertigungstoleranz des fertigen Werkstoffes. Dies macht Werkstoffe, die nach diesem Verfahren hergestellt werden, nicht geeignet für Anwendungen, bei denen eine hohe Qualitätsund Fertigungskonstanz notwendig ist.DE-C3-22 60 191 describes a method for the preparation of materials made of electrically conductive materials. The last step in the process of shaping the materials, in which a new bare surface is created on the material, is carried out in a suitable inert gas or inert liquid medium with the exclusion of atmospheric oxygen and moisture. This method has the disadvantage that, in particular when using an inert liquid medium which covers the surface of the material and can thus be placed in the coating electrolyte, the latter subsequently contaminates or hydrolyzes the electrolyte. When using inert gas media, the problem arises in large-scale industrial use that an absolutely oxygen-free inert gas atmosphere is practically impossible to achieve. Traces of oxygen that are present in the inert gas atmosphere immediately oxidize the bare metal surface of the material and thus lead to the loss of quality of the subsequently electroplated metal layer. If, as described in DE-C3-22 60 191, the bare surface by a mechanical method such. B. milling, cutting, sawing or drilling, or by strong deformation of the material with z. B. rolling or by wire drawing, extrusion or other methods, these methods require an increase in the manufacturing tolerance of finished material. This makes materials that are manufactured using this process unsuitable for applications in which a high level of quality and manufacturing consistency is required.
In der DE-AS-12 12 213 wird die Vorbehandlung eines Werkstoffes in einer Schutzgasatmosphäre beschrieben. Alternativ kann die Oxidschicht an der Oberfläche des Werkstoffes dadurch entfernt werden, dass der Werkstoff vor Abscheidung der Aluminiumschicht im Elektrolyten, der aus Natriumfluorid und Aluminiumtriethyl hergestellt wird, anodisch geschaltet wird. Anschließend findet eine Umpolung des Stromes statt, sowie eine Abscheidung von Aluminium auf dem Werkstoff. Nachteilig stellt sich heraus, dass der Elektrolyt nur zur Abscheidung von Aluminium auf Werkstoffen verwendet werden kann. Die Abscheidung von Magnesium oder Aluminium/Magnesium-Schichten ist nicht möglich, da durch die Anwesenheit von Halogenidionen in dem Elektrolyten bei der anodischen Polung unmittelbar unlösliche Magnesiumhalogenid-Verbindungen entstehen würden, die eine Abscheidung von Magnesium oder Aluminium/Magnesium auf dem Werkstoff verhindern. Die entstehenden Magnesiumhalogenide würden sofort den Stromfluss im Elektrolyten durch Blockierung der Elektroden unterbinden.DE-AS-12 12 213 describes the pretreatment of a material in a protective gas atmosphere. Alternatively, the oxide layer on the surface of the material can be removed by anodically switching the material before depositing the aluminum layer in the electrolyte, which is made from sodium fluoride and aluminum triethyl. Then the polarity of the current is reversed and aluminum is deposited on the material. It turns out disadvantageously that the electrolyte can only be used for the deposition of aluminum on materials. The deposition of magnesium or aluminum / magnesium layers is not possible, since the presence of halide ions in the electrolyte during the anodic polarization would result in immediately insoluble magnesium halide compounds which prevent the deposition of magnesium or aluminum / magnesium on the material. The resulting magnesium halides would immediately prevent the current flow in the electrolyte by blocking the electrodes.
DE-AS-21 22 610 beschreibt ein Verfahren zur anodischen Vorbehandlung von Leichtmetallen für die galvanische Abscheidung von Aluminium. Die Reinigung der Bauteile erfolgt durch Behandlung der Leichtmetallwerkstoffe in einem Schmelzelektrolyten, wobei die Stoffe anodisch belastet werden. Die so gereinigten Leichtmetallwerkstoffe werden elektrolytfeucht, also noch mit dem Schmelzelektrolyten belastet, in eine Aluminierzelle eingesenkt. Hierbei ist nicht auszuschließen, dass noch Luftsauerstoff an den vorbehandelten Werkstoff gelangt und diesen an der Oberfläche wieder oxidiert. Weiterhin findet eine Verunreinigung des Aluminierelektrolyten durch den Oberflächenbehandlungselektrolyten, der ein Schmelzelektrolyt ist, statt. Nur dann, wenn der Werkstoff aus Beryllium oder Aluminium besteht, ist es möglich, dass der Werkstoff in dem Schmelzelektrolyten, der zur Oberflächenbehandlung durch anodische Oxidation des Werkstoffes dient, auch zur galvanischen Abscheidung von Aluminium auf dem Beryllium- oder Aluminiumwerkstoff benutzt wird. Der in DE-AS- 21 22 610 beschriebene Schmelzelektrolyt ist nur geeignet Beryllium- oder Aluminiumwerkstoffe vorzubehandeln, um diese nachfolgend in demselben Schmelzelektrolyten mit Aluminium zu beschichten. Der Schmelzelektrolyt ist nicht geeignet um Aluminium-, Magnesium- oder Aluminium/Magnesium-Schichten auf anderen Werkstoffen galvanisch aufzubringen.DE-AS-21 22 610 describes a process for the anodic pretreatment of light metals for the galvanic deposition of aluminum. The components are cleaned by treating the light metal materials in a melt electrolyte, the materials being anodically loaded. The light metal materials cleaned in this way are immersed in an electrolytic cell, moist with electrolyte, i.e. still loaded with the molten electrolyte. It cannot be ruled out that atmospheric oxygen will still reach the pretreated material and oxidize it again on the surface. Furthermore, the aluminum electrolyte is contaminated by the surface treatment electrolyte, which is a melt electrolyte. Only if the material consists of beryllium or aluminum is it possible that the material in the melt electrolyte, which is used for surface treatment by anodic oxidation of the material, also for the galvanic deposition of aluminum on the Beryllium or aluminum material is used. The melting electrolyte described in DE-AS-21 22 610 is only suitable for pretreating beryllium or aluminum materials in order to subsequently coat them with aluminum in the same melting electrolyte. The melting electrolyte is not suitable for the galvanic application of aluminum, magnesium or aluminum / magnesium layers on other materials.
DE-A1-198 55 666 beschreibt einen Elektrolyten, der zur Abscheidung von Aluminium/Magnesium-Legierungsschichten geeignet ist. Der offenbarte aluminium-organische Elektrolyt enthält K[AIEt4] oder Na[Et3Al-H-AlEt3], sowie Na[AlEt4], sowie Trialkylaluminium. Der Elektrolyt kann als toluolische Lösung vorliegen. Die elektrolytische Abscheidung von Aluminium/Magnesium-Legierungsschichten aus dem beschriebenen Elektrolyten wird unter Verwendung einer löslichen Aluminium- und einer ebenfalls löslichen Magnesiumanode oder unter Verwendung einer Anode aus Aluminium/Magnesium-Legierung durchgeführt. Bei dem beschriebenen Verfahren wird durch eine Vorelektrolyse die Elektrolytzusammensetzung so eingestellt, dass die abgeschiedene Schicht das gewünschte Aluminium/Magnesium-Verhältnis aufweist. Alternativ kann auch Mg[AlEt4]2 zum Elektrolyten zugegeben werden. DE-A1-198 55 666 lehrt somit, dass das Verhältnis von Aluminium und Magnesium in der abgeschiedenen Aluminium/Magnesium-Schicht sehr stark von dem Konzentrationsverhältnis von Magnesium und Aluminium in dem Elektrolyten abhängt. Wie bei allen Verfahren des Standes der Technik ist eine große Sorgfalt bei der Vorbehandlung der zu beschichtenden Werkstoffe notwendig, da Verunreinigungen der Werkstoffoberfläche durch Oxidation oder durch andere Einflüsse zu einer verminderten Qualität der galvanisch abgeschiedenen Metallschicht führen.DE-A1-198 55 666 describes an electrolyte which is suitable for the deposition of aluminum / magnesium alloy layers. The disclosed aluminum-organic electrolyte contains K [AIEt 4 ] or Na [Et 3 Al-H-AlEt 3 ], as well as Na [AlEt 4 ], and trialkyl aluminum. The electrolyte can be in the form of a toluene solution. The electrolytic deposition of aluminum / magnesium alloy layers from the described electrolyte is carried out using a soluble aluminum and a likewise soluble magnesium anode or using an anode made of aluminum / magnesium alloy. In the described method, the electrolyte composition is adjusted by pre-electrolysis so that the deposited layer has the desired aluminum / magnesium ratio. Alternatively, Mg [AlEt 4 ] 2 can also be added to the electrolyte. DE-A1-198 55 666 thus teaches that the ratio of aluminum and magnesium in the deposited aluminum / magnesium layer depends very much on the concentration ratio of magnesium and aluminum in the electrolyte. As with all methods of the prior art, great care is required in the pretreatment of the materials to be coated, since contamination of the material surface by oxidation or other influences leads to a reduced quality of the galvanically deposited metal layer.
Die technische Aufgabe der vorliegenden Erfindung ist es ein Verfahren bereitzustellen, bei dem Aluminium-, Magnesium- oder Aluminium/Magnesium-Schichten auf Werkstoffen aufgebracht werden können, wobei die Qualität der Metallbeschichtung durch eine verbesserte Vorbehandlung des Werkstoffes erhöht wird. So soll insbesondere ein Verfahren zur Verfügung gestellt werden, bei dem die zu beschichtenden Werkstoffe zuverlässig und kostengünstig von anhaftenden Oxidschichten oder anderen Verunreinigungen befreit werden, wobei nach der Vorbehandlung der Werkstoffe eine erneute Verunreinigung oder Oxidation der Werkstoffe verhindert werden soll.The technical object of the present invention is to provide a method in which aluminum, magnesium or aluminum / magnesium layers can be applied to materials, the quality of the metal coating being increased by an improved pretreatment of the material. In particular, a method is to be made available be, in which the materials to be coated are reliably and inexpensively freed from adhering oxide layers or other impurities, wherein after the pretreatment of the materials a renewed contamination or oxidation of the materials should be prevented.
Die technische Aufgabe der vorliegenden Erfindung wird durch ein Verfahren zur elektrolytischen Beschichtung von Werkstoffen mit Aluminium, Magnesium oder Legierungen von Aluminium und Magnesium gelöst, wobei der Werkstoff zur Vorbehandlung in den Elektrolyten getaucht wird, dort anodisch geschaltet wird und unmittelbar danach die elektrolytische Beschichtung in demselben Elektrolyten erfolgt, wobei das Elektrolytbad aluminiumorganische Verbindungen der allgemeinen Formel M[(R1)3Al-(H-Al(R2)2)n-R3] (I) und AI(R4)3 (II) als Elektrolyt enthält und n gleich 0 oder 1 ist, M gleich Natrium oder Kalium ist und R1, R2, R3, R4 gleich oder verschieden sein können, wobei R1, R2, R3, R4 eine C1- bis C4-Alkylgruppe ist und als Lösungsmittel für den Elektrolyten ein halögenfreies, aprotisches Lösungsmittel verwendet wird. Durch das erfindungsgemäße Verfahren ist es möglich den Werkstoff in dem Bad, in dem später die elektrolytische Beschichtung stattfindet, vorzubehandeln. Überraschenderweise werden Verunreinigungen, die dem nicht vorbehandelten Werkstoff anhaften, sowie vorhandene Oxidschichten auf dem Werkstoff abgelöst. Die Verunreinigungen, die somit in das Elektrolytbad eingebracht werden behindern überraschenderweise die Abscheidung von Magnesium, Aluminium oder Legierungen von Aluminium und Magnesium auf dem Werkstoff nicht. Unlösliche Verunreinigungen können mittels geeigneter Filtrationssysteme kontinuierlich aus dem Elektrolytbad entfernt werden.The technical object of the present invention is achieved by a method for the electrolytic coating of materials with aluminum, magnesium or alloys of aluminum and magnesium, the material being immersed in the electrolyte for pretreatment, being anodically switched there and immediately thereafter the electrolytic coating in the same Electrolytes take place, the electrolyte bath organoaluminum compounds of the general formula M [(R 1 ) 3 Al- (H-Al (R 2 ) 2 ) n -R 3 ] (I) and Al (R 4 ) 3 (II) as the electrolyte contains and n is 0 or 1, M is sodium or potassium and R 1 , R 2 , R 3 , R 4 may be the same or different, where R 1 , R 2 , R 3 , R 4 is a C 1 - bis C 4 alkyl group and a halogen-free, aprotic solvent is used as the solvent for the electrolyte. The method according to the invention makes it possible to pretreat the material in the bath in which the electrolytic coating takes place later. Surprisingly, impurities that adhere to the non-pretreated material and any oxide layers on the material are removed. The impurities which are thus introduced into the electrolyte bath surprisingly do not hinder the deposition of magnesium, aluminum or alloys of aluminum and magnesium on the material. Insoluble impurities can be continuously removed from the electrolyte bath using suitable filtration systems.
Es ist daher nicht mehr notwendig, die Werkstoffe nach der Vorbehandlung aus dem Vorbehandlungsbad in das Elektrolytbad zu überführen. Dieser Schritt, der immer die Gefahr einer erneuten Verunreinigung der Oberfläche des Werkstoffes birgt, kann so vermieden werden.It is therefore no longer necessary to transfer the materials from the pretreatment bath to the electrolyte bath after the pretreatment. This step, which always carries the risk of renewed contamination of the surface of the material, can be avoided in this way.
In einer bevorzugten Ausführungsform wird in dem erfindungsgemäßen Verfahren ein Elektrolyt als ein Gemisch aus den Komplexen K[AlEt4], Na[AlEt4] und AlEt3 eingesetzt. Das molare Verhältnis der Komplexe zu AIEt3 beträgt 1 : 0,5 bis 1 : 3, wobei das Verhältnis von 1 : 2 bevorzugt ist.In a preferred embodiment, in the process according to the invention, an electrolyte is used as a mixture of the complexes K [AlEt 4 ], Na [AlEt 4 ] and AlEt 3 used. The molar ratio of the complexes to AIEt 3 is 1: 0.5 to 1: 3, the ratio of 1: 2 being preferred.
In einer bevorzugten Ausführungsform werden 0 bis 25 Mol-%, vorzugsweise 5 bis 20 Mol-% Na[AlEt4], bezogen auf das Gemisch aus den Komplexen K[AlEt4] und Na[AlEt4] eingesetzt.In a preferred embodiment, 0 to 25 mol%, preferably 5 to 20 mol% Na [AlEt 4 ], based on the mixture of the complexes K [AlEt 4 ] and Na [AlEt 4 ], are used.
Vorzugsweise kann als Elektrolyt ein Gemisch aus 0,8 Mol K[AlEt4], 0,2 Mol Na[AlEt4], 2,0 Mol AlEt3 in 3,3 Mol Toluol eingesetzt werden.A mixture of 0.8 mol of K [AlEt 4 ] , 0.2 mol of Na [AlEt 4 ], 2.0 mol of AlEt 3 in 3.3 mol of toluene can preferably be used as the electrolyte.
Alternativ kann in dem erfindungsgemäßen Verfahren als Elektrolyt ein Gemisch aus Na[Et3Al-H-AlEt3] und Na[AlEt4] und AIEt3 eingesetzt werden. Vorzugsweise ist das molare Verhältnis von Na[Et3Al-H-AlEt3] zu Na[AlEt4] 4 : 1 bis 1 : 1, wobei ein Verhältnis von 2 : 1 bevorzugt ist. Weiterhin ist bevorzugt, dass das molare Verhältnis von Na[AlEt4] zu AlEt3 1 : 2 ist.Alternatively, a mixture of Na [Et 3 Al-H-AlEt 3 ] and Na [AlEt4] and AIEt 3 can be used as the electrolyte in the process according to the invention. Preferably the molar ratio of Na [Et 3 Al-H-AlEt 3 ] to Na [AlEt 4 ] is 4: 1 to 1: 1, with a ratio of 2: 1 being preferred. It is further preferred that the molar ratio of Na [AlEt 4 ] to AlEt 3 is 1: 2.
In einer weiteren bevorzugten Ausführungsform wird als Elektrolyt ein Gemisch aus 1 Mol Na[Et3Al-H-AlEt3], 0,5 Mol Na[AlEt4] und 1 Mol AlEt3 in 3 Mol Toluol eingesetzt.In a further preferred embodiment, a mixture of 1 mol of Na [Et 3 Al-H-AlEt 3 ], 0.5 mol of Na [AlEt 4 ] and 1 mol of AlEt 3 in 3 mol of toluene is used as the electrolyte.
Die elektrolytische Beschichtung von Werkstoffen mit Magnesium, Aluminium oder Aluminium/Magnesium-Legierungen wird vorzugsweise bei einer Temperatur von 80 bis 105°C durchgeführt. Bevorzugt ist eine Temperatur des Galvanisierungsbades von 91 bis 100°C.The electrolytic coating of materials with magnesium, aluminum or aluminum / magnesium alloys is preferably carried out at a temperature of 80 to 105 ° C. A temperature of the electroplating bath of 91 to 100 ° C. is preferred.
Die elektrolytische Abscheidung von Aluminium-, Magnesium-, oder Aluminium/Magnesium-Schichten auf den Werkstoffen wird unter Verwendung einer löslichen Aluminium- und einer ebenfalls löslichen Magnesiumanode oder unter Verwendung einer Anode aus einer Aluminium/Magnesium-Legierung durchgeführt. Es ist allerdings auch möglich, nur eine Aluminium- oder eine Magnesiumanode zu verwenden.The electrolytic deposition of aluminum, magnesium, or aluminum / magnesium layers on the materials is carried out using a soluble aluminum and a likewise soluble magnesium anode or using an anode made of an aluminum / magnesium alloy. However, it is also possible to use only one aluminum or one magnesium anode.
In dem erfindungsgemäßen Verfahren kann die anodische Schaltung des Werkstoffes zur Vorbehandlung für eine Zeitdauer von 1 bis 20 min, wobei 5 bis 15 min bevorzugt sind, durchgeführt werden.In the method according to the invention, the anodic switching of the material for pretreatment can be carried out for a period of 1 to 20 minutes, with 5 to 15 minutes being preferred.
Die für die Vorbehandlung notwendige anodische Belastung der Werkstoffe wird mit einer Stromdichte von 0,2 bis 2 A/dm2, vorzugsweise 0,5 bis 1,5 A/dm2 durchgeführt.The anodic loading of the materials required for the pretreatment is carried out with a current density of 0.2 to 2 A / dm 2 , preferably 0.5 to 1.5 A / dm 2 .
Als Werkstoff kann jeder Werkstoff verwendet werden, der zum galvanischen Abscheiden geeignet ist. Es ist bevorzugt, dass der Werkstoff aus einem Metall und/oder aus einer Metalllegierung besteht und/oder ein metallisierter, elektrolytbeständiger Werkstoff ist, der im Elektrolyt durch anodische Schaltung aufgelöst werden kann. Die zu beschichtenden Materialien sind vorzugsweise Gestellwaren, Schüttgutwaren oder Endlosprodukte wie Draht, Vierkantbleche, Schrauben oder Muttern.Any material that is suitable for galvanic deposition can be used as the material. It is preferred that the material consists of a metal and / or a metal alloy and / or is a metallized, electrolyte-resistant material that can be dissolved in the electrolyte by anodic switching. The materials to be coated are preferably rack goods, bulk goods or continuous products such as wire, square sheets, screws or nuts.
Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, dass Verunreinigungen oder Oxidschichten, die auf den Werkstoffen anhaften, sicher entfernt werden. Hierbei tritt überraschenderweise keine nachteilige Veränderung der Elektrolytzusammensetzung auf, die eine hochqualitative Abscheidung von Aluminium-, Magnesium- oder Aluminium/Magnesium-Schichten auf den Werkstoffen unterbinden würde. Weiterhin sind die galvanisch aufgebrachten Metallschichten fest anhaftend und homogen auf dem Werkstoff aufgebracht, da nach der Reinigung eine erneute Verunreinigung des Werkstoffes unterbunden wird. Neben den genannten Qualitätsvorteilen wird durch die genannten Verfahrensschritte zusätzlich eine Kostenoptimierung des Beschichtens von Formteilen mit Metallschichten erreicht.The method according to the invention is characterized in that impurities or oxide layers which adhere to the materials are reliably removed. Surprisingly, there is no disadvantageous change in the electrolyte composition that would prevent high-quality deposition of aluminum, magnesium or aluminum / magnesium layers on the materials. Furthermore, the galvanically applied metal layers are firmly adhering and homogeneously applied to the material, since after the cleaning a renewed contamination of the material is prevented. In addition to the quality advantages mentioned, the process steps mentioned also achieve a cost optimization of coating molded parts with metal layers.
Das erfindungsgemäße Verfahren zur elektrolytischen Beschichtung von Werkstoffen mit Magnesium, Aluminium oder Legierungen von Aluminium und Magnesium wird an den folgenden Beispielen erläutert, ohne jedoch auf diese beschränkt zu sein.The process according to the invention for the electrolytic coating of materials with magnesium, aluminum or alloys of aluminum and magnesium is illustrated in the following examples, but without being limited to these.
Phase a) Ein Stanzteil aus einer AIMg3-Legierung wurde zuerst 2 Minuten alkalisch gebeizt in einer Lösung von 100 g/l NaOH bei einer Temperatur von 60° C. Nach anschließendem Spülen in Wasser wurde das Teil in 10 % Salpetersäure dekapiert, anschließend gespült in destilliertem Wasser und getrocknet.Phase a) A stamped part made from an AIMg 3 alloy was first alkali pickled in a solution of 100 g / l NaOH at a temperature of 60 ° C. for 2 minutes. After subsequent rinsing in water, the part was picked up in 10% nitric acid and then rinsed in distilled water and dried.
Phase b) Das trockene Teil wurde in einer mit Argon bzw. Stickstoff geflutete Beschichtungszelle eingebracht und nach einer Vorspülung in Toluol sofort im Beschichtungselektrolyt eingebracht. Als Elektrolyt wurde ein Gemisch aus den Komplexen K[AlEt4], K[AlEt4] und AlEt3 eingesetzt gelöst in Toluol. Als Gegenelektrode diente eine AIMg25-Legierungsplatte. Das zu beschichtende Produkt wurde zuerst anodisch gepolt und bei einer Stromdichte von 1 A/dm2 5 Minuten lang behandelt bei einer Elektrolytentemperatur von 95 C. Anschließend wurde umgepolt ohne das Teil aus dem Elektrolyten zu entfernen und sofort 45 Minuten lang bei einer Stromdichte von 1,5 A/dm2 beschichtet. Es wurde eine AIMg-Legierungsschicht von ca. 14 µm Dicke abgeschieden.Phase b) The dry part was introduced into a coating cell flooded with argon or nitrogen and, after a pre-rinsing in toluene, was introduced immediately into the coating electrolyte. A mixture of the complexes K [AlEt 4 ], K [AlEt 4 ] and AlEt 3 was used as the electrolyte, dissolved in toluene. An AIMg25 alloy plate served as the counter electrode. The product to be coated was first anodically poled and treated at a current density of 1 A / dm 2 for 5 minutes at an electrolyte temperature of 95 C. Then the polarity was reversed without removing the part from the electrolyte and immediately for 45 minutes at a current density of 1 , 5 A / dm 2 coated. An AIMg alloy layer approximately 14 µm thick was deposited.
Die Haftfestigkeit der Schicht wurde mittels Gitterschnitttest und Hitzeschocktest (1 h bei 220° C und Abschrecken in kaltem Wasser) geprüft. Es zeigte sich, dass eine ausgezeichnete Haftung der abgeschiedenen Schicht auf dem Grundmaterial vorhanden war. Es konnten keine Ablösungen oder Blasen festgestellt werden.The adhesive strength of the layer was checked by means of a cross cut test and a heat shock test (1 h at 220 ° C. and quenching in cold water). It was found that the deposited layer had excellent adhesion to the base material. No detachments or bubbles were found.
Ein als Vergleichsprobe behandeltes Teil wurde wie in Beispiel 1 vorbehandelt und beschichtet, jedoch ohne anodischer Polung vorab. Die Schicht konnte beim Gitterschnitttest als Folie abgezogen werden. Beim Hitzeschocktest zeigte die Schicht Blasen.A part treated as a comparative sample was pretreated and coated as in Example 1, but without anodic polarity beforehand. The layer could be peeled off as a film during the cross cut test. In the heat shock test, the layer showed bubbles.
Ein Magnesiumdruckgussteil aus einer AZ-91-Legierung wurde mit Korund (Körnung 0-50 µm) bei 2 bar Druck gestrahlt. Das Teil wurde danach sofort in die Inertgasatmosphäre der Beschichtungszelle eingebracht, in Toluol vorgespült und im Elektrolytbad eingetaucht wie in Beispiel 1 beschrieben. Zuerst wurde das zu beschichtende Produkt 10 Minuten lang bei einer Stromdichte von 1 A/dm2 anodisch geschaltet. Dabei wurde an der Produktoberfläche eine Schicht von ca. 2 µm abgetragen. Danach wurde umgepolt und das Teil 1 Stunde bei 1,5 A/dm2 kathodisch geschaltet. Es wurde eine AIMg-Schicht mit 23-25% Mg-Anteil und einer Schichtstärke von ca. 18 µm abgeschieden.A magnesium die-cast part made of an AZ-91 alloy was blasted with corundum (grain size 0-50 µm) at 2 bar pressure. The part was then immediately placed in the inert gas atmosphere of the coating cell, rinsed in toluene and immersed in the electrolyte bath as described in Example 1. First, the product to be coated was anodized for 10 minutes at a current density of 1 A / dm 2 . A layer of approx. 2 µm was removed from the product surface. The polarity was then reversed and the part was connected cathodically for 1 hour at 1.5 A / dm 2 . An AIMg layer with 23-25% Mg content and a layer thickness of approx. 18 µm was deposited.
Anschließende Haftfestigkeitstests zeigten sowohl beim Gitterschnitttest als auch beim Wärmeschocktest keine Schichtablösungen.Subsequent adhesive strength tests showed no delamination in either the cross-cut test or the thermal shock test.
Claims (12)
M [(R1)3Al-(H-Al(R2)2)n-R3] (I)
AI(R4)3 (II)
als Elektrolyt enthält, n gleich 0 oder 1 ist, M gleich Natrium oder Kalium ist und R1, R2, R3, R4 gleich oder verschieden sein können, wobei R1, R2, R3, R4 eine C1 bis C4 Alkylgruppe sind und als Lösungsmittel für den Elektrolyt ein halogenfreies, aprotisches Lösungsmittel eingesetzt wird.Process for the electrolytic coating of materials with aluminum, magnesium or alloys of aluminum and magnesium, wherein the material for pretreatment is immersed in an electrolyte and anodically switched there and immediately afterwards the electrolytic coating takes place in the same electrolyte, the electrolytic bath organoaluminum compounds of the general Formulas (I) and (II)
M [(R 1 ) 3 Al- (H-Al (R 2 ) 2 ) n -R 3 ] (I)
AI (R 4 ) 3 (II)
contains as electrolyte, n is 0 or 1, M is sodium or potassium and R 1 , R 2 , R 3 , R 4 may be the same or different, where R 1 , R 2 , R 3 , R 4 is a C 1 to C 4 are alkyl groups and a halogen-free, aprotic solvent is used as the solvent for the electrolyte.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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EP02021402A EP1403402A1 (en) | 2002-09-25 | 2002-09-25 | Process for the electrolytic deposition of materials with aluminium, magnesium or alloys of aluminium and magnesium |
EP03807748A EP1543180B1 (en) | 2002-09-25 | 2003-07-15 | Method for electrolytic coating of materials with aluminium, magnesium or aluminium and magnesium alloys |
CN038230569A CN1685087B (en) | 2002-09-25 | 2003-07-15 | Method for electrolytic coating of materials with aluminium, magnesium or aluminium and magnesium alloys |
JP2004542263A JP2006500476A (en) | 2002-09-25 | 2003-07-15 | Electrolytic coating of materials with aluminum, magnesium, or an alloy of aluminum and magnesium |
PCT/EP2003/007632 WO2004033762A1 (en) | 2002-09-25 | 2003-07-15 | Method for electrolytic coating of materials with aluminium, magnesium or aluminium and magnesium alloys |
US10/528,125 US7468123B2 (en) | 2002-09-25 | 2003-07-15 | Method for electrolytic coating of materials with aluminum, magnesium or aluminum and magnesium alloys |
AU2003250061A AU2003250061A1 (en) | 2002-09-25 | 2003-07-15 | Method for electrolytic coating of materials with aluminium, magnesium or aluminium and magnesium alloys |
DE50303610T DE50303610D1 (en) | 2002-09-25 | 2003-07-15 | METHOD OF ELECTROLYTIC COATING OF MATERIALS USING ALUMINUM, MAGNESIUM OR ALLOYS OF ALUMINUM AND MAGNESIUM |
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EP02021402A EP1403402A1 (en) | 2002-09-25 | 2002-09-25 | Process for the electrolytic deposition of materials with aluminium, magnesium or alloys of aluminium and magnesium |
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EP02021402A Withdrawn EP1403402A1 (en) | 2002-09-25 | 2002-09-25 | Process for the electrolytic deposition of materials with aluminium, magnesium or alloys of aluminium and magnesium |
EP03807748A Expired - Fee Related EP1543180B1 (en) | 2002-09-25 | 2003-07-15 | Method for electrolytic coating of materials with aluminium, magnesium or aluminium and magnesium alloys |
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US (1) | US7468123B2 (en) |
EP (2) | EP1403402A1 (en) |
JP (1) | JP2006500476A (en) |
CN (1) | CN1685087B (en) |
AU (1) | AU2003250061A1 (en) |
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WO (1) | WO2004033762A1 (en) |
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EP1524336A1 (en) * | 2003-10-18 | 2005-04-20 | Aluminal Oberflächtentechnik GmbH & Co. KG | Workpieces coated with an aluminum magnesium alloy |
JP2016000838A (en) * | 2012-10-15 | 2016-01-07 | 住友電気工業株式会社 | Aluminum film, aluminum film formed body and production method of aluminum film |
US9689057B2 (en) | 2012-12-26 | 2017-06-27 | Posco | Steel sheet coated with aluminum-magnesium |
TWI464276B (en) * | 2013-06-19 | 2014-12-11 | China Steel Corp | Aluminum-magnesium alloy sheet for anode and method of making the same |
CN104674219A (en) * | 2015-03-25 | 2015-06-03 | 东莞仁海科技股份有限公司 | Novel technology for surface treatment of pressure casting |
Citations (3)
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---|---|---|---|---|
DE1212213B (en) * | 1964-02-29 | 1966-03-10 | Aluminium Walzwerke Singen | Process for the production of rod-shaped or wire-shaped electrodes for electrolytic capacitors |
DE2122610A1 (en) * | 1971-05-07 | 1972-11-23 | Siemens Ag | Process for coating and surface refinement of fittings made of light metals and alloys |
DE19855666A1 (en) * | 1998-12-01 | 2000-06-08 | Studiengesellschaft Kohle Mbh | Organoaluminum electrolytes and processes for electrolytic coating with aluminum or aluminum-magnesium alloys |
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US4148204A (en) * | 1971-05-07 | 1979-04-10 | Siemens Aktiengesellschaft | Process of mechanically shaping metal articles |
US3969195A (en) * | 1971-05-07 | 1976-07-13 | Siemens Aktiengesellschaft | Methods of coating and surface finishing articles made of metals and their alloys |
-
2002
- 2002-09-25 EP EP02021402A patent/EP1403402A1/en not_active Withdrawn
-
2003
- 2003-07-15 EP EP03807748A patent/EP1543180B1/en not_active Expired - Fee Related
- 2003-07-15 WO PCT/EP2003/007632 patent/WO2004033762A1/en active IP Right Grant
- 2003-07-15 US US10/528,125 patent/US7468123B2/en not_active Expired - Fee Related
- 2003-07-15 DE DE50303610T patent/DE50303610D1/en not_active Expired - Lifetime
- 2003-07-15 JP JP2004542263A patent/JP2006500476A/en active Pending
- 2003-07-15 CN CN038230569A patent/CN1685087B/en not_active Expired - Fee Related
- 2003-07-15 AU AU2003250061A patent/AU2003250061A1/en not_active Abandoned
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1212213B (en) * | 1964-02-29 | 1966-03-10 | Aluminium Walzwerke Singen | Process for the production of rod-shaped or wire-shaped electrodes for electrolytic capacitors |
DE2122610A1 (en) * | 1971-05-07 | 1972-11-23 | Siemens Ag | Process for coating and surface refinement of fittings made of light metals and alloys |
DE19855666A1 (en) * | 1998-12-01 | 2000-06-08 | Studiengesellschaft Kohle Mbh | Organoaluminum electrolytes and processes for electrolytic coating with aluminum or aluminum-magnesium alloys |
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EP1543180B1 (en) | 2006-05-31 |
CN1685087B (en) | 2010-12-29 |
US7468123B2 (en) | 2008-12-23 |
DE50303610D1 (en) | 2006-07-06 |
CN1685087A (en) | 2005-10-19 |
AU2003250061A1 (en) | 2004-05-04 |
WO2004033762A1 (en) | 2004-04-22 |
JP2006500476A (en) | 2006-01-05 |
US20060137990A1 (en) | 2006-06-29 |
EP1543180A1 (en) | 2005-06-22 |
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