EP0975826B1 - Method for electroplating metallic and non-metallic endless products and device for carrying out said method - Google Patents

Method for electroplating metallic and non-metallic endless products and device for carrying out said method Download PDF

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Publication number
EP0975826B1
EP0975826B1 EP98922715A EP98922715A EP0975826B1 EP 0975826 B1 EP0975826 B1 EP 0975826B1 EP 98922715 A EP98922715 A EP 98922715A EP 98922715 A EP98922715 A EP 98922715A EP 0975826 B1 EP0975826 B1 EP 0975826B1
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EP
European Patent Office
Prior art keywords
continuous product
coating
continuous
chambers
coated
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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EP98922715A
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German (de)
French (fr)
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EP0975826A2 (en
Inventor
Hans De Vries
Jörg HELLER
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Aluminal Oberflachentechnik GmbH
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Aluminal Oberflachentechnik GmbH
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0607Wires
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/42Electroplating: Baths therefor from solutions of light metals
    • C25D3/44Aluminium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils
    • C25D7/0621In horizontal cells

Definitions

  • the invention relates to a method for electrolytic Coating metallic or non-metallic Continuous products with metals or alloys in a continuous process made of aprotic, water and oxygen-free electrolytes. Another object of the invention is a device to carry out this procedure.
  • hot-dip galvanizing can also be carried out with the fire aluminum can be combined.
  • Galvanic deposition processes are another state of the art of aluminum known in aprotic water and oxygen-free electrolytes.
  • the separation takes place here of aluminum from baths, the aluminum alkyl complexes from alkali metal halides and aluminum alkyls contain.
  • Aromatic solvents are generally used as solvents or aliphatic hydrocarbons used.
  • Electrolyte solutions are used, for example, in the EP 0 402 761 A and EP 0 084 816 A.
  • DE 3023827 C2 describes a system that addresses this Benefits from the process. It consists of a closed off to the outside Tube cell through which to be treated, cathodic Contacted material in the axial direction, preferably continuously is movable along anodes. To both the unwanted Leak of the electrolyte from the tubular cell as well Preventing the entry of air is the A protective gas can be applied to the tube cell. Will continue a tubular connector on both sides of the tube cell connected, the one the longitudinal passage of the electrolyte preventing, vertically deflecting the electrolyte current Has aperture.
  • the T-shaped connectors follow each a lock arrangement consisting of several chambers, in the for the mutual sealing of the individual chambers as Sealant inert gas and / or inert liquid introduced can be.
  • JP 63227797 describes the activation of a metal sheet an electrolytic coating with aluminum also non-aqueous Solvent used.
  • the technical object of the invention is a method to provide the disadvantages mentioned above the previously known coating processes for continuous products avoids, is inexpensive and for a better coating leads.
  • the process should continue without change of the base material can be carried out, in particular at low temperatures.
  • Continuous product in the sense of the invention are metallic or understood non-metallic materials that are rolled up in or folded form and are manufactured at the coating is endless in a continuous process be moved through the plant.
  • These include, for example Wires of all thicknesses, strips and long profiles, tubes and similar products.
  • Non-aqueous electrolytes in the sense of the invention Systems called, the controlled pure separation of the Metal or the metal alloy, in particular aluminum and aluminum alloys via the electrolysis process without Intermediate or carrier layer, allow.
  • Wire in a preferred embodiment, as continuous products Wire, strips, long profiles or tubes made of metallic or non-metallic materials. It is preferred that these materials with aluminum or aluminum alloys be coated.
  • Figure 1 shows a process diagram of the inventive method.
  • FIG. 2 shows an illustration of the lock system
  • FIG. 3 shows a coating cell.
  • Figure 4 shows the contacting cell.
  • FIG. 5 shows a diagram of the overall process.
  • Figure 1 shows the individual process steps of the invention Process.
  • the continuous product for example unwound from a reel and initially over a lock sluiced into the coating system.
  • a cleaning process can be carried out by using the continuous product a gas wiping or spray nozzle is guided (see also figure 2, paragraph 11).
  • Activation of the material to be coated With the Number 3 is a flushing unit in which the material rinsed after activation.
  • Section 4 describes a deflection unit with one or more rollers. This will used to reduce the overall size of the facility and is particularly useful for small diameter continuous products meaningful.
  • the following paragraphs 5 describe individual ones Contacting cells, the numbers 6 the coating cells and the numbers 7 the aftercare.
  • the coated product is then at the end of the process on an appropriate Reel rolled up.
  • the electrolytic Coating in the plant a chemical or electrochemical Post-treatment can be carried out. This can also be associated with a simultaneous or subsequent color design within the surface structure. During the after-treatment, mechanical surface compaction takes place, which results in a very shiny surface whereby this is not influenced in the aftertreatment.
  • the entire System designed with closed regeneration cycles, and all liquids used are circulating processed, cleaned and returned. This is particularly the case for the rinsing solutions, the electrolyte solutions and the Activation solution that filters and / or distils as needed can be.
  • the continuous product through the lock system and the flushing system each led to at least three chambers, the middle Chamber B is filled with a barrier liquid and the outer Chamber A contains air and the inner chamber C contains an inert gas contains (see also Figure 2).
  • the continuous products are not gas and liquid-tight guides into the chambers, so that the liquid in the chambers partially into the Neighboring chambers are running.
  • FIG. 5 The ones designated in FIG. 5 are similar Rinsing chambers constructed, so that here, too, from those in front Do not bath any liquid or gas in the following Can reach chambers.
  • the is the chambers through the overflow or through the guides Liquid cleaned via a circulation system and into the respective Chamber returned.
  • the contacting is preferably carried out in a liquid electrolyte filled chamber that contains no anode, being the continuous product via a cathodically connected metal contact to be led.
  • the liquid level of this contacting cell is preferably lower than that of the neighboring coating cell, so that electrolyte solution through the guides get from the coating chamber into the contacting chamber can and so by the purity of the electrolytic solution impurities carried in from the contacting chamber cannot be reduced
  • the electrolytic coating in a coating chamber, which is filled with electrolytic solution, the continuous product is passed through a socket that is insulated.
  • the order the contacting and coating cells can be in any frequency, depending on the length and size of the Investment.
  • the special feature of the invention is that also in this area the wire inside the electrolyte fluid must be located, but the contact outside of the direct Coating areas is.
  • the closure of the environment takes place in addition to the inert atmosphere via flood systems, similar to the lock systems mentioned.
  • the Contacting can be carried out according to the invention via spring-loaded Contact elements are made by grinding or rolling, one flexible diameter adjustment is possible.
  • the Wire through specially designed deflection systems several times Coating units are guided, so that a low Length limited highly effective facility is possible.
  • Especially appropriate design of the system technology and The method is provided by a storage container Plant shutdown, the continuous product in its original Leave position to unlike classic Procedure to get no start-up losses.
  • the invention ensures that mechanical or physico-chemical stripping processes not uniformity or homogeneity of the applied surface layer influence.
  • it is possible to the aluminum electrodes in the coating cells without any problems exchange and resume operation immediately.
  • the auxiliary units such as filters and storage systems for Lock fluid, cleaning media and electrolytes are designed according to the invention so that a closed environmentally independent operation is possible. waste products are recyclable in a concentrated form.
  • the described method offers the invention described components the possibility of a chemical Passivation of the coating, which is a significant increase which represents corrosion resistance.
  • One according to the invention possible color nuances of the coating itself, not as an order, increases the mechanical resistance of this Coloring significantly compared to paints.
  • the procedure Selection of the coating materials on which the invention is based and electrolytes increased over those shown classical methods of corrosion resistance considerable both in the acidic and in the alkaline range.
  • the exit areas of the wire from the coating and Rinsing tract it becomes possible to dry the wire in dryer or even in thickened form in the desired colors and to receive appropriate coating requirements.
  • Another object of the invention is a device for electrolytic coating of metallic or non-metallic Continuous products with metals or metal alloys in a continuous process from aprotic water and oxygen free Electrolytes, consisting of a coating system with at least one lock system 1, at least a contacting cell 5, at least one coating cell 6, these assemblies in any number are connected in series and the entire device is encapsulated airtight.
  • the coating system draws are characterized in that they have an activation unit 2 and a Rinsing unit 3 includes in this order and an unwinding unit for the uncoated continuous product outside of encapsulated coating system is arranged.
  • Such Device also serves to carry out the invention Process.
  • Figure 2 shows a view of the lock system 1.
  • the middle chamber B has a liquid overflow 16 and chambers A and C are designed as overflow chambers are.
  • Chambers A, B and C particularly preferably have one Drain 20, 22 and 23, with the middle chamber in addition has an inlet 21 through which the in the chambers A and C collected barrier liquid into the middle chamber B can be traced back.
  • the number 14 designates one Storage tank, the number 15 a corresponding pump. With the Number 9 denotes the wire guide, number 17 denotes Chamber A, Section 18 Chamber B and Section 19 Chamber C.
  • Numeral 12 denotes the continuous product, that is passed through the chamber and number 11 is preferred used gas wiping or spray nozzle for additional Cleaning the surface of the through the plant led continuous product 12.
  • the numbers 24 and 25 are designated the inner chamber walls, number 13 a removable plate for sockets. This makes it possible To use continuous products of different diameters, whereby then the corresponding socket can also be used got to.
  • Numeral 10 denotes the liquid level.
  • Figure 3 shows a coating cell.
  • Figures 3a, 3b and 3d show different views of the one in the cell Carrier 28 for the continuous product 12.
  • Figure 3a shows one Front view
  • Figure 3b is a side view
  • Figure 3d a At sight.
  • Figure 3c is a perspective view of the entire coating cell 6.
  • Section 27 shows the ceramic bushing divided into two parts. This is opposite to the direction of the imported continuous product arranged removably from the insulating material and can, for example, against sockets with a modified Diameter can be exchanged.
  • Figure 3c shows the entire coating cell 6 with the anode plates 26 and the carrier 28 arranged in the middle and the socket 27.
  • the coating cell 6 preferably has guides for guidance of the continuous product 12, which are designed so that a uniform distance between those in the coating cell arranged anodes 26 and the continuous product to be coated 12 is guaranteed.
  • the coating cell has an overflow and an inlet for electrolyte.
  • the guides in the coating cells consist of a Carrier 28 made of insulating material which pierces in the middle is, bushings 27 are arranged in the through bore, which can only be inserted on one side and in a preferred manner Made of ceramic material and for easy interchangeability for continuous products of different diameters are divided.
  • Figure 4 shows an image of the contacting cell 5.
  • Figure 4a represents an enlargement of the contact area as Side view.
  • Figure 4b shows a perspective view the contacting cell 5.
  • the Section 12 designates the continuous product. This is between a metal roller 29 which is under cathodic voltage and passed through a non-conductive ceramic tension roller 30, with the number 32 the notches in the metal rollers are designated for better guidance of the continuous product 12. With the number 33 are the holding elements for the metal rollers and the ceramic tension rollers.
  • Figure 4a shows one enlarged section of the contact area.
  • the digit 29 shows the metal roller, number 31 a bronze bushing Power supply, section 12 the continuous product and section 30 are the ceramic tensioners. With these the preload set via springs or set screws for the continuous product.
  • the contacting cell 5 is preferably designed such that that in it a metal roller or a sliding contact is arranged, via which the continuous product is connected cathodically becomes.
  • one or more ceramic tensioners can be used for setting the preload in the contacting cell be arranged.
  • the metal roller has a notch over which the continuous product is led.
  • an overflow is preferably arranged so that from the electrolysis cell urgent electrolytes in a collection system can be dissipated.
  • FIG. 5 shows a view of the coating cell 6 Contacting cell 5 and the rinsing units 3.
  • Figure 5a shows the supervision of these cells and
  • Figure 5b is a side view.
  • the rinsing units 3 in a similar way are designed like the ones described above Lock systems in Figure 2. They also have one Overflow, as well as neighboring overflow chambers, the middle Chamber is filled with liquid. This can run through the impervious guides into the neighboring chambers and is collected through appropriate processes and in the rinsing chambers returned.
  • the number 5 are the contacting cells described. These are preferably the coating cells 6 adjacent and filled with electrolyte.
  • the number 6 shows the coating cells with the anodes 26 and the carriers 28 made of insulating material with those therein Ceramic bushings 29 for guiding the continuous products 12 in the coating cells.
  • the coating cells are too filled with electrolyte and have an overflow, one Drain and an inlet through which the respective electrolyte liquids circulated, cleaned and returned can.
  • the device according to the invention has considerable advantages on previously known devices for metallization of continuous products. So the wire is over non-conductive Pipes and roller guides inside the device, specifically but in the electric field of the coating cell 6, stable positioning. It is through this stable guidance possible, several parallel strands of continuous products, for example several wires, also in a vertical arrangement to lead through the device without causing undesirable electrical contacts and an even distance to the anode is guaranteed.
  • rinsing units 3 and Contacting cells 5 is an electrical intermediate contact outside the area of effect of the anode material possible, with the continuous product remaining in the electrolyte.
  • the transmission of electrical energy in the contacting cells 5 can both form sliding contacts of flexible contact pins, which are spring-loaded, as well as via resilient contact rollers.
  • the continuous product can remain in the chambers without an overreaction on the Surface, such as over-pickling or one-sided over-coating, can take place, while maintaining the inert atmosphere in the system the reaction media in the intermediate containers be stored outside the reaction spaces.
  • an exchange of the anode material in the Standstill can take place without the material to be coated to remove from the system.
  • inventive method and the inventive It is possible to manufacture continuous products in an industrial device procedure to be carried out and a corresponding Coating device with metals, in particular aluminum.
  • the inventive method and the inventive Device thus replace the previously used Process of hot-dip aluminizing, hot-dip galvanizing and electrolytic Coating in aqueous media.

Abstract

The present invention is directed to processes and devices for performing the processes comprising electroplating one or more metallic or non-metallic continuous products with metals or metal alloys in a continuous process from aprotic electrolytes free of water and oxygen, wherein the continuous product is passed through a lock system (1) into an encapsulated coating plant under inert gas atmosphere, and the following steps are performed at temperatures <=120° C.:activating the continuous product to be coated;rinsing the continuous product to be coated;contacting the continuous product to be coated;electroplating the continuous product to be coated using a metal or metal alloy;drying the coated continuous product;discharge of the coated continuous product from the plant through a lock system.

Description

Gegenstand der Erfindung ist ein Verfahren zum elektrolytischen Beschichten von metallischen oder nichtmetallischen Endlosprodukten mit Metallen oder Legierungen im Durchlaufverfahren aus aprotischen wasser- und sauerstofffreien Elektrolyten. Ein weiterer Gegenstand der Erfindung ist eine Vorrichtung zur Durchführung dieses Verfahrens.The invention relates to a method for electrolytic Coating metallic or non-metallic Continuous products with metals or alloys in a continuous process made of aprotic, water and oxygen-free electrolytes. Another object of the invention is a device to carry out this procedure.

Gemäß dem Stand der Technik können Endlosprodukte wie Draht, Bänder, Langprofile oder Röhren mittels wässriger Elektrolyseverfahren, mittels Schmelzbadauftrag im Durchlauf oder mittels galvanischer Abscheideverfahren hergestellt werden.According to the prior art, continuous products such as wire, Strips, long profiles or tubes using aqueous electrolysis processes, by means of melt bath application in a continuous process or by means of galvanic deposition processes are produced.

Bei einem bekannten elektrolytischen Beschichtungsverfahren wird beispielsweise Draht mit verschiedenen Überzügen wie Zink, Nickel oder anderen Metallen beschichtet. Dabei durchläuft der Draht offene Reinigungs- und elektrolytische Beschichtungsbäder, die wässrige Lösungen enthalten. In diesen Bädern erfolgt eine Abscheidung des jeweiligen Metalls auf dem Draht. Die Dicke der Beschichtungsauflage ist dabei abhängig von Durchlaufgeschwindigkeit und elektrischer Feldstärke. Die Abscheidungsrate bei diesem Verfahren ist bezogen auf die Zeit jedoch ziemlich gering, und die abgeschiedene Schicht ist oft sehr porös und hart. Dies führt zu mangelnder Korrosionsbeständigkeit, insbesondere bei dünnen Schichten. Durch die fehlende Duktilität kann es bei anschließenden Verformungsvorgängen zu Rissen in der abgeschiedenen Schicht kommen oder sogar zum Abplatzen der Beschichtung. Eine solche Schicht verliert ihren Schutzcharakter gegen Korrosion vollständig und besitzt auch keine dekorative Oberfläche mehr. In a known electrolytic coating process For example, wire with different coatings such as Zinc, nickel or other metals coated. It goes through the wire open cleaning and electrolytic coating baths, which contain aqueous solutions. In these The respective metal is deposited on baths the wire. The thickness of the coating layer depends on it of throughput speed and electric field strength. The deposition rate in this process is related for the time being, however, quite small, and the secluded one Layer is often very porous and hard. This leads to a lack Corrosion resistance, especially with thin layers. Due to the lack of ductility, it can be used in subsequent deformation processes to cracks in the deposited layer come or even peel off the coating. Such Layer completely loses its protective character against corrosion and no longer has a decorative surface.

Bei einer elektrolytischen Abscheidung eines Beschichtungsmetalls aus einer wässrigen Lösung wird weiterhin niemals eine vollständige kathodische bzw. anodische Ausbeute erreicht. Bei den für die Durchlaufbeschichtung notwendigen hohen Stromdichten entstehen im allgemeinen Nebenreaktionen, die zu Zersetzungsprodukten im Elektrolyten führen und Gasentwicklung hervorrufen. Dabei tritt insbesondere auch eine Wasserstoffentwicklung am Produkt auf, die zu einer Versprödung des Grundmaterials führen kann.In the case of electrolytic deposition of a coating metal an aqueous solution will never become one complete cathodic or anodic yield achieved. At the high levels required for continuous coating Current densities generally result in side reactions that lead to Decomposition products in electrolytes and gas evolution cause. Hydrogen evolution occurs in particular on the product leading to embrittlement of the Basic material can lead.

Ein weiterer Nachteil ist, daß bei den elektrolytischen wässrigen Abscheideverfahren und Schmelztauchverfahren große Mengen toxischer Abluft und Abwässer anfallen, die über entsprechend aufwendige Verfahren einer Reinigung unterzogen werden müssen, wobei in jedem Fall toxische Sonderabfälle zurückbleiben. So entstehen, beispielsweise aufgrund der Anwesenheit von Fettresten auf den zu beschichtenden Metallen vor der alkalischen Reinigung in den entsprechenden Lösungen, auch Reste organischer Verbindungen, die aufgrund der hohen Temperaturen im Zinkkessel, die bei etwa 450° C liegen, zu äußerst giftigen organischen Verbindungen wie Dioxinen und Furanen reagieren können. Es fallen weiterhin Metallschlämme, Altsäuren und verbrauchte alkalische Reiniger an. Neben den vorstehend erwähnten Abgasen fallen weiterhin auch Säuredämpfe und alkalische Dämpfe an.Another disadvantage is that with the electrolytic aqueous Deposition processes and hot-dip processes large quantities Toxic exhaust air and waste water accrue over accordingly complex processes are subjected to cleaning must, whereby toxic hazardous waste remains in any case. So arise, for example, due to the presence of grease residues on the metals to be coated alkaline cleaning in the corresponding solutions, also remains of organic compounds due to the high Temperatures in the zinc kettle, which are around 450 ° C, too extremely toxic organic compounds such as dioxins and Furans can react. Metal sludge continues to fall, Used acids and used alkaline cleaners. In addition to the Exhaust gases mentioned above also continue to drop acid vapors and alkaline vapors.

Weitere Verfahren zur Beschichtung von Endlosprodukten sind bekannt. Diese basieren auf der Aufbringung von dekorativen und korrosionsmindernden Schichten im geschmolzenen Zustand. Hier ist die sogenannte Feuerverzinkung und auch die Feueraluminierung bekannt. Im Falle der Feuerverzinkung wird ein vorher gereinigtes und aktiviertes Endlosprodukt, beispielsweise ein dünner Draht, im Durchlauf durch geschmolzenes hochreines Zink geführt. Diese Reaktionen laufen bei Temperaturen über 440° C ab, so daß in jedem Fall auch eine mechanische Beeinflussung des zu beschichtenden Materials erfolgt. Bestimmte andere zu beschichtende Grundmaterialien können aufgrund der hohen Temperaturen gar nicht beschichtet werden. Weiterhin nachteilig ist die relative Ungleichmäßigkeit der aufgebrachten Beschichtung und deren sehr stark schichtabhängige Korrosionsbeständigkeit. Infolge des Abstreifverfahrens kann der Oberfläche vollständig der dekorative Charakter fehlen. Eine farbliche Gestaltung der Oberfläche ist nicht möglich.Other processes for coating continuous products are known. These are based on the application of decorative and corrosion-reducing layers in the molten state. Here is the so-called hot-dip galvanizing and also the hot-dip aluminum known. In the case of hot-dip galvanizing, a previously cleaned and activated continuous product, for example a thin wire, passing through melted high purity zinc. These reactions run at temperatures above 440 ° C, so that in any case also a mechanical The material to be coated is influenced. Certain other base materials to be coated can not be coated at all due to the high temperatures. Another disadvantage is the relative non-uniformity of the applied coating and its very strongly layer-dependent Corrosion resistance. As a result of the stripping process the surface can completely lack the decorative character. A colored design of the surface is not possible.

Bei allen mit Zink verbundenen Beschichtungsverfahren zeigt sich nach kurzer Zeit der Korrosion ein Aufblühen der Oberfläche durch Entstehung von Zinkoxiden und Zinkcarbonaten und damit von der Optik her ein sehr negatives Verändern der Oberfläche. Eine Gleichmäßigkeit der Beschichtung bei diesen thermischen Verfahren ist daher nicht gewährleistet.Shows in all coating processes associated with zinc after a short period of corrosion, the surface blooms through the formation of zinc oxides and zinc carbonates and thus a very negative change of the optics Surface. Uniformity of the coating in these thermal process is therefore not guaranteed.

Als weiteres Verfahren ist die sogenannte hochthermische Feueraluminierung bekannt. Bei diesem Verfahren wird in gleicher Weise wie bei Beschichtung mit Zink ein Draht durch ein geschmolzenes Aluminiumbad gezogen und anschließend einem Abstreifvorgang unterzogen. Man erhält so jedoch Schichten, die ähnliche Nachteile aufweisen, wie bei der zuvor beschriebenen Feuerverzinkung. Die mittels der Feueraluminierung aufgebrachten Schichten haben sich aufgrund ihrer unzureichenden Reinheit, der hohen Porösität und unvermeidlichen oxideinschlüsse und damit geringer Korrosionsbeständigkeit nicht bewährt. Weitere Nachteile sind, daß die Beschichtung nicht dekorativ aussieht und eine bei den für die Feueraluminierung notwendigen Temperaturen teilweise starke mechanische Beeinflussung des zu beschichtenden Materials erfolgt.Another process is the so-called high thermal fire aluminum known. This procedure is the same As with zinc coating a wire through a molten one Pulled aluminum bath and then a stripping process subjected. However, you get layers that Disadvantages similar to those described above Hot-dip galvanizing. The applied by means of fire aluminum Layers have become insufficient due to their Purity, high porosity and inevitable oxide inclusions and thus low corrosion resistance is not proven. Other disadvantages are that the coating is not decorative looks like and one for the fire aluminizing necessary temperatures strong mechanical influences of the material to be coated.

Gemäß dem Stand der Technik kann die Feuerverzinkung auch mit der Feueraluminierung kombiniert werden. Dies führt zu einer etwas verbesserten Korrosionsschicht durch die aktive kathodische Schutzwirkung des Aluminiums. Nachteilig wirkt sich jedoch der fehlende dekorative Charakter aus. Hinzu kommen weitere Nachteile, die allein aufgrund der Beschichtung bei hohen Temperaturen auftreten.According to the prior art, hot-dip galvanizing can also be carried out with the fire aluminum can be combined. This leads to a somewhat improved corrosion layer through the active cathodic Protective effect of aluminum. It has a disadvantageous effect however, the lack of decorative character. Add to that other disadvantages due to the coating alone high temperatures occur.

Als weiterer Stand der Technik sind galvanische Abscheideverfahren von Aluminium bekannt, die in aprotischen wasser- und sauerstofffreien Elektrolyten erfolgen. Dabei erfolgt die Abscheidung des Aluminiums aus Bädern, die Aluminiumalkylkomplexe aus Alkalimetallhalogeniden und Aluminiumalkylen enthalten. Als Lösungsmittel werden im allgemeinen aromatische oder aliphatische Kohlenwasserstoffe eingesetzt. Derartige Elektrolytlösungen werden beispielsweise in der EP 0 402 761 A und der EP 0 084 816 A beschrieben.Galvanic deposition processes are another state of the art of aluminum known in aprotic water and oxygen-free electrolytes. The separation takes place here of aluminum from baths, the aluminum alkyl complexes from alkali metal halides and aluminum alkyls contain. Aromatic solvents are generally used as solvents or aliphatic hydrocarbons used. such Electrolyte solutions are used, for example, in the EP 0 402 761 A and EP 0 084 816 A.

Die DE 3023827 C2 beschreibt eine Anlage, die sich dieses Verfahren zunutze macht. Sie besteht aus einer nach außen abgeschlossenen Rohrzelle, durch die das zu behandelnde, kathodisch kontaktierte Gut in Achsrichtung vorzugsweise kontinuierlich entlang von Anoden bewegbar ist. Um sowohl das ungewollte Austreten des Elektrolyten aus der Rohrzelle als auch das Eindringen von Luftatmosphäre zu verhindern, ist die Rohrzelle mit einem Schutzgas beaufschlagbar. Weiterhin wird der Rohrzelle an beiden Seiten je ein T-förmiges Verbindungsstück angeschlossen, das eine den Längsdurchgang des Elektrolyten verhindernde, den Elektrolytstrom senkrecht ablenkende Blende aufweist. Den T-förmigen Verbindungsstücken folgt je eine aus mehreren Kammern bestehende Schleusenanordnung, in die zum gegenseitigen Abdichten der einzelnen Kammern als Dichtmedium Inertgas und/oder Inertflüssigkeit eingeleitet werden kann. DE 3023827 C2 describes a system that addresses this Benefits from the process. It consists of a closed off to the outside Tube cell through which to be treated, cathodic Contacted material in the axial direction, preferably continuously is movable along anodes. To both the unwanted Leak of the electrolyte from the tubular cell as well Preventing the entry of air is the A protective gas can be applied to the tube cell. Will continue a tubular connector on both sides of the tube cell connected, the one the longitudinal passage of the electrolyte preventing, vertically deflecting the electrolyte current Has aperture. The T-shaped connectors follow each a lock arrangement consisting of several chambers, in the for the mutual sealing of the individual chambers as Sealant inert gas and / or inert liquid introduced can be.

Bei den herkömmlichen Verfahren des Standes der Technik erfolgt die vor der elektrolytischen Beschichtung in wässrigen Lösungen durchgeführte notwendige Aktivierung des Endlosproduktes in einem getrennten Verfahrensschritt. Da sich die A-luminium-organischen Bestandteile des Elektrolyten in Feuchtigkeit zersetzen, sind Spül- und Trocknungsvorgänge angeschlossen, die die Reste der wässrigen Lösungen entfernen. Erst nach Abschluss der Spülvorgänge wird das Endlosprodukt in eine gekapselte Beschichtungsanlage zur galvanischen Metallabscheidung eingebracht.In the conventional methods of the prior art those before electrolytic coating in aqueous Solutions carried out necessary activation of the continuous product in a separate process step. Since the A-aluminum-organic Components of the electrolyte in moisture decompose, rinsing and drying processes are connected, which remove the remains of the aqueous solutions. The continuous product is only after the rinsing process has been completed in an encapsulated coating system for galvanic metal deposition brought in.

In JP 63227797 werden zur Aktivierung eines Metallblechs vor einer elektrolytischen Beschichtung mit Aluminium auch nichtwässrige Lösungsmittel verwendet.JP 63227797 describes the activation of a metal sheet an electrolytic coating with aluminum also non-aqueous Solvent used.

Die technische Aufgabe der Erfindung ist es, ein Verfahren zur Verfügung zu stellen, das die oben erwähnten Nachteile der bisher bekannten Beschichtungsverfahren für Endlosprodukte vermeidet, kostengünstig ist und zu einer besseren Beschichtung führt. Das Verfahren soll weiterhin ohne Veränderung des Grundwerkstoffes durchgeführt werden können, insbesondere bei niedrigen Temperaturen. The technical object of the invention is a method to provide the disadvantages mentioned above the previously known coating processes for continuous products avoids, is inexpensive and for a better coating leads. The process should continue without change of the base material can be carried out, in particular at low temperatures.

Diese technische Aufgabe wird gelöst durch ein Verfahren zum elektrolytischen Beschichten von metallischen oder nichtmetallischen Endlosprodukten mit Metallen oder Legierungen im Durchlaufverfahren aus aprotischen wasser- und sauerstofffreien Elektrolyten, wobei das Endlosprodukt über ein Schleusensystem in eine unter Inertgasatmosphäre befindliche gekapselte Beschichtungsanlage geführt wird und dort die nachfolgenden Schritte bei Temperaturen ≤ 120°C in dieser Reihenfolge durchgeführt werden.

  • Aktivierung des zu beschichtenden Endlosproduktes
  • Spülen des zu beschichtenden Endlosproduktes
  • Kontaktierung des zu beschichtenden Endlosproduktes
  • elektrolytische Beschichtung des zu beschichtenden Endlosproduktes mit Metall oder einer Metalllegierung
  • Trocknung des beschichteten Endlosproduktes
  • Austritt des beschichteten Endlosproduktes über ein Schleusensystem aus der Anlage
This technical problem is solved by a process for the electrolytic coating of metallic or non-metallic continuous products with metals or alloys in a continuous process from aprotic water- and oxygen-free electrolytes, the continuous product being passed via a lock system into an encapsulated coating system located under an inert gas atmosphere and the subsequent steps there at temperatures ≤ 120 ° C in this order.
  • Activation of the continuous product to be coated
  • Rinsing the continuous product to be coated
  • Contacting the continuous product to be coated
  • electrolytic coating of the continuous product to be coated with metal or a metal alloy
  • Drying the coated continuous product
  • The coated continuous product emerges from the system via a lock system

Unter Endlosprodukt im Sinne der Erfindung werden metallische oder nichtmetallische Werkstoffe verstanden, die in aufgerollter oder zusammengelegter Form hergestellt werden und bei der Beschichtung in einem kontinuierlichen Prozeß endlos durch die Anlage bewegt werden. Hierzu gehören beispielsweise Drähte jeglicher Dicken, Bänder und Langprofile, Röhren und ähnliche Produkte.Continuous product in the sense of the invention are metallic or understood non-metallic materials that are rolled up in or folded form and are manufactured at the coating is endless in a continuous process be moved through the plant. These include, for example Wires of all thicknesses, strips and long profiles, tubes and similar products.

Als Elektrolyt im Sinne der Erfindung werden nichtwässrige Systeme bezeichnet, die eine gesteuerte reine Abscheidung des Metalls oder der Metalllegierung, insbesondere von Aluminium und Aluminiumlegierungen über das Elektrolyseverfahren ohne Zwischen- oder Trägerschicht, erlauben.Non-aqueous electrolytes in the sense of the invention Systems called, the controlled pure separation of the Metal or the metal alloy, in particular aluminum and aluminum alloys via the electrolysis process without Intermediate or carrier layer, allow.

In einer bevorzugten Ausführungsform werden als Endlosprodukte Draht, Bänder, Langprofile oder Röhren aus metallischen oder nichtmetallischen Werkstoffen eingesetzt. Es ist bevorzugt, daß diese Werkstoffe mit Aluminium oder Aluminiumlegierungen beschichtet werden.In a preferred embodiment, as continuous products Wire, strips, long profiles or tubes made of metallic or non-metallic materials. It is preferred that these materials with aluminum or aluminum alloys be coated.

Figur 1 zeigt ein Verfahrensschema des erfindungsgemäßen Verfahrens.Figure 1 shows a process diagram of the inventive method.

Figur 2 zeigt eine Abbildung des Schleusensystems, Figur 3 zeigt eine Beschichtungszelle.FIG. 2 shows an illustration of the lock system, FIG. 3 shows a coating cell.

Figur 4 zeigt die Kontaktierungszelle.Figure 4 shows the contacting cell.

Figur 5 zeigt ein Schaubild des Gesamtverfahrens.FIG. 5 shows a diagram of the overall process.

Figur 1 zeigt die einzelnen Verfahrensschritte des erfindungsgemäßen Verfahrens. Dabei wird das Endlosprodukt beispielsweise von einer Haspel abgewickelt und zunächst über eine Schleuse in die Beschichtungsanlage eingeschleust. Bereits beim Einleiten in das Schleusensystem kann ein Reinigungsprozeß durchgeführt werden, indem das Endlosprodukt über eine Gasabstreif- oder Sprühdüse geführt wird (s. auch Figur 2, Ziffer 11). Als zweiter Verfahrensschritt erfolgt dann eine Aktivierung des zu beschichtenden Werkstoffes. Mit der Ziffer 3 ist eine Spüleinheit bezeichnet, in der der Werkstoff nach der Aktivierung gespült wird. Ziffer 4 beschreibt eine Umlenkeinheit mit einer oder mehrerer Rollen. Diese wird verwendet, um die Gesamtgröße der Anlage zu verkleinern und ist insbesondere bei Endlosprodukten von geringem Durchmesser sinnvoll. Die nachfolgenden Ziffern 5 beschreiben einzelne Kontaktierungszellen, die Ziffern 6 die Beschichtungszellen und die Ziffern 7 die Nachbehandlung. Das beschichtete Produkt wird dann am Ende des Prozesses auf eine entsprechende Haspel aufgerollt.Figure 1 shows the individual process steps of the invention Process. The continuous product, for example unwound from a reel and initially over a lock sluiced into the coating system. Already when entering the lock system, a cleaning process can be carried out by using the continuous product a gas wiping or spray nozzle is guided (see also figure 2, paragraph 11). Then, as a second process step Activation of the material to be coated. With the Number 3 is a flushing unit in which the material rinsed after activation. Section 4 describes a deflection unit with one or more rollers. This will used to reduce the overall size of the facility and is particularly useful for small diameter continuous products meaningful. The following paragraphs 5 describe individual ones Contacting cells, the numbers 6 the coating cells and the numbers 7 the aftercare. The coated product is then at the end of the process on an appropriate Reel rolled up.

In einer bevorzugten Ausführungsform kann nach der elektrolytischen Beschichtung in der Anlage eine chemische oder elekttrochemische Nachbehandlung durchgeführt werden. Diese kann auch verbunden sein mit einer gleichzeitigen oder nachfolgenden farblichen Gestaltung innerhalb der Oberflächenstruktur. Bei der Nachbehandlung erfolgt eine mechanische Oberflächenverdichtung, die zu einer sehr glänzenden Oberfläche führt, wobei diese bei der Nachbehandlung nicht beeinflußt wird.In a preferred embodiment, the electrolytic Coating in the plant a chemical or electrochemical Post-treatment can be carried out. This can also be associated with a simultaneous or subsequent color design within the surface structure. During the after-treatment, mechanical surface compaction takes place, which results in a very shiny surface whereby this is not influenced in the aftertreatment.

In einer weiteren bevorzugten Ausführungsform ist die gesamte Anlage über Regenerierungskreisläufe geschlossen gestaltet, und alle verwendeten Flüssigkeiten werden im Umlaufverfahren aufbereitet, gereinigt und rückgeführt. Dies erfolgt insbesondere für die Spüllösungen, die Elektrolytlösungen und die Aktivierungslösung, die je nach Bedarf filtriert und/oder destilliert werden können.In a further preferred embodiment, the entire System designed with closed regeneration cycles, and all liquids used are circulating processed, cleaned and returned. This is particularly the case for the rinsing solutions, the electrolyte solutions and the Activation solution that filters and / or distils as needed can be.

In einer weiteren bevorzugten Ausführungsform wird das Endlosprodukt durch das Schleusensystem und das Spülsystem aus jeweils mindestens drei Kammern geführt, wobei die mittlere Kammer B mit einer Sperrflüssigkeit gefüllt ist und die äußere Kammer A Luft enthält und die innere Kammer C ein Inertgas enthält (s. auch Figur 2). In einer weiteren bevorzugten Ausführungsform werden die Endlosprodukte über nicht gas- und flüssigkeitsdichte Führungen in die Kammern geführt, so daß die in den Kammern befindliche Flüssigkeit teilweise in die Nachbarkammern läuft.In a further preferred embodiment, the continuous product through the lock system and the flushing system each led to at least three chambers, the middle Chamber B is filled with a barrier liquid and the outer Chamber A contains air and the inner chamber C contains an inert gas contains (see also Figure 2). In a further preferred embodiment the continuous products are not gas and liquid-tight guides into the chambers, so that the liquid in the chambers partially into the Neighboring chambers are running.

Durch diese Maßnahmen wird beispielsweise bei der Schleusenkammer erreicht, daß keine Feuchtigkeit oder Sauerstoff bei der Einführung des Endlosproduktes in die Anlage gelangt. Die in der mittleren Kammer B befindliche Sperrflüssigkeit stellt eine Sperre für die in der äußeren Kammer A enthaltene Luft dar. Aufgrund der Auslegung der Führungen zwischen den Kammern in nicht flüssigkeitsdichter Form läuft ein Teil der Sperrflüssigkeit aus der mittleren Kammer B in die Kammern A und C. Es kommt somit an diesen Stellen zu einer Spülung des eingeführten Endlosproduktes. Die in den Kammern A und C gesammelte Flüssigkeit gelangt über ein Ablaufsystem in einen Vorratstank und wird über eine entsprechenden Pumpe und Filtriereinrichtung in die mittlere Kammer B zurückgeführt.These measures, for example, in the lock chamber achieved that no moisture or oxygen the introduction of the continuous product into the system. The barrier liquid located in the middle chamber B. a lock on the air contained in the outer chamber A Due to the design of the guides between the chambers a part of the Barrier liquid from the middle chamber B into the chambers A and C. There is therefore a flushing of the imported continuous product. The collected in chambers A and C. Liquid enters a through a drain system Storage tank and is via a corresponding pump and filtering device returned to the middle chamber B.

In ähnlicher Weise sind auch die in der Figur 5 bezeichneten Spülkammern konstruiert, so daß auch hier aus den davor befindlichen Bädern keinerlei Flüssigkeit oder Gas in die nachfolgenden Kammern gelangen kann.The ones designated in FIG. 5 are similar Rinsing chambers constructed, so that here, too, from those in front Do not bath any liquid or gas in the following Can reach chambers.

In einer weiteren bevorzugten Ausführungsform wird die aus den Kammern durch den Überlauf oder die Führungen ablaufende Flüssigkeit über ein Umlaufsystem gereinigt und in die jeweilige Kammer zurückgeführt. Als Führungen zwischen den Kammern werden bevorzugt Buchsen oder Rollen verwendet. Die Kontaktierung erfolgt bevorzugt in einer mit flüssigen Elektrolyten gefüllten Kammer, die keine Anode enthält, wobei das Endlosprodukt über einen kathodisch geschalteten Metallkontakt geführt wird. Der Flüssigkeitspegel dieser Kontaktierungszelle liegt bevorzugt niedriger, als der der benachbarten Beschichtungszelle, so daß Elektrolytlösung durch die Führungen aus der Beschichtungskammer in die Kontaktierungskammer gelangen kann und so die Reinheit der Elektrolytlösung durch aus der Kontaktierungskammer eingeschleppte Verunreinigungen nicht verringert werden kannIn a further preferred embodiment, the is the chambers through the overflow or through the guides Liquid cleaned via a circulation system and into the respective Chamber returned. As guides between the chambers bushes or rollers are preferred. The contacting is preferably carried out in a liquid electrolyte filled chamber that contains no anode, being the continuous product via a cathodically connected metal contact to be led. The liquid level of this contacting cell is preferably lower than that of the neighboring coating cell, so that electrolyte solution through the guides get from the coating chamber into the contacting chamber can and so by the purity of the electrolytic solution impurities carried in from the contacting chamber cannot be reduced

In einer weiteren bevorzugten Ausführungsform erfolgt die elektrolytische Beschichtung in einer Beschichtungskammer, die mit Elektrolytlösung gefüllt ist, wobei das Endlosprodukt durch eine Buchse geführt wird, die isoliert ist.In a further preferred embodiment, the electrolytic coating in a coating chamber, which is filled with electrolytic solution, the continuous product is passed through a socket that is insulated.

Durch diese Maßnahmen in der Beschichtungszelle wird erreicht, daß die Stromzuführung für das Endlosprodukt in Kammern erfolgt, in denen keine Anode vorhanden ist, so daß es in diesen Kontaktierungszellen nicht zum Anwachsen von abgeschiedenem Metall, beispielsweise auf den Spannung führenden Kathodenführungen, kommt. In den Beschichtungskammern selbst ist keine Stromführung vorhanden, so daß hier die Metallabscheidung nur auf dem Endlosprodukt selbst erfolgt. Die Anordnung der Kontaktierungs- und Beschichtungszellen kann in beliebiger Häufigkeit erfolgen, je nach Länge und Größe der Anlage.These measures in the coating cell achieve that the power supply for the continuous product in chambers takes place in which there is no anode, so that it in these contacting cells not for the growth of the deposited Metal, for example on the voltage leading Cathode guides, coming. In the coating chambers themselves there is no current supply, so here the metal deposition only done on the continuous product itself. The order the contacting and coating cells can be in any frequency, depending on the length and size of the Investment.

Das Einleiten des Drahtes in die erfindungsgemäße Vorrichtung erfolgt über besonders zweckmäßig gestaltete Vakuum- oder Flüssigkeitsschleusensysteme, wobei letztere ähnlich gestaltet sind, wie die Kontaktierungszellen zwischen den Beschichtungszellen. Dies ist sowohl für Ein- als auch für Mehrdrahtsysteme möglich. Das dichtende Medium kann gleichzeitig der Reinigung der Drahtoberfläche dienen. Zwischen den Schleusensystemen laufen die Prozesse stets vollkommen unter inerter Atmosphäre ab. In den Spüleinheiten, Kontaktierungs- und Beschichtungszellen sind die Drahtführungen zielgerichtet so gestaltet, daß der Draht in gleichmäßigem Abstand zu den als Beschichtungsmaterial dienenden Anoden durch die Beschichtungszelle bewegt wird, ohne elektrischen Kontakt zu benachbarten Drähten oder zur Anode zu bekommen.Introducing the wire into the device according to the invention takes place via particularly expediently designed vacuum or Liquid lock systems, the latter designed similarly are like the contacting cells between the coating cells. This is for both single and multi-wire systems possible. The sealing medium can at the same time Serve cleaning the wire surface. Between the lock systems the processes are always completely inert Atmosphere. In the flushing units, contacting and coating cells the wire guides are targeted like this designed that the wire is evenly spaced from the Coating material serving anodes through the coating cell is moved without electrical contact to neighboring Wires or to get to the anode.

Zwischen den Beschichtungszellen befindet sich ein Überflutungssystem, in dem in Kontaktierungszellen die elektrische Kontaktierung des Drahtes erfolgt, um über die gesamte Anlagenlänge gleichmäßige stabile Bedingungen zu schaffen.There is a flooding system between the coating cells, in which the electrical Contacting of the wire takes place over the entire length of the system to create even, stable conditions.

Die Besonderheit der Erfindung besteht darin, daß sich auch in diesem Bereich der Draht innerhalb der Elektrolytflüssigkeit befinden muß, aber die Kontaktierung außerhalb der direkten Beschichtungsbereiche liegt. Der Abschluß von der Umgebung erfolgt neben der inerten Atmosphäre über Überflutungssysteme, ähnlich der erwähnten Schleusensysteme. Die Kontaktierung kann erfindungsgemäß über federnd gelagerte Kontaktelemente schleifend oder rollend erfolgen, wobei eine flexible Durchmesseranpassung möglich ist. Durch die gemäß der Erfindung gestaltete in Bezug auf das Beschichtungsfeld ausgelagerte Kontaktierung, kommt es nicht zu einem Aufwachsen der Kontaktrollen oder Kontaktelemente.The special feature of the invention is that also in this area the wire inside the electrolyte fluid must be located, but the contact outside of the direct Coating areas is. The closure of the environment takes place in addition to the inert atmosphere via flood systems, similar to the lock systems mentioned. The Contacting can be carried out according to the invention via spring-loaded Contact elements are made by grinding or rolling, one flexible diameter adjustment is possible. By the according of the invention designed with respect to the coating field outsourced contact, there is no growing up the contact rollers or contact elements.

Erfindungsgemäß kann insbesondere bei dünnen Abmessungen der Draht über speziell ausgelegte Umlenksysteme mehrmals durch Beschichtungseinheiten geführt werden, so daß eine auf geringe Länge begrenzte hocheffektive Anlage möglich ist. In besonders zweckmäßiger Ausgestaltung der Anlagentechnik und des Verfahrens ist vorgesehen durch Speicherbehälter bei einem Stillstand der Anlage, das Endlosprodukt in seiner ursprünglichen Position zu belassen, um im Gegensatz zu klassischen Verfahren keine Anlaufverluste zu bekommen.According to the invention, the Wire through specially designed deflection systems several times Coating units are guided, so that a low Length limited highly effective facility is possible. Especially appropriate design of the system technology and The method is provided by a storage container Plant shutdown, the continuous product in its original Leave position to unlike classic Procedure to get no start-up losses.

Durch die Erfindung wird gewährleistet, daß mechanische oder physikalisch-chemische Abstreifvorgänge nicht die Gleichmäßigkeit oder Homogenität der aufgebrachten Oberflächenschicht beeinflussen. Bei dem erfindungsgemäßen Verfahren ist es möglich, die Aluminiumelektroden in den Beschichtungszellen problemlos auszutauschen und den Betrieb sofort wieder aufzunehmen.The invention ensures that mechanical or physico-chemical stripping processes not uniformity or homogeneity of the applied surface layer influence. In the method according to the invention, it is possible to the aluminum electrodes in the coating cells without any problems exchange and resume operation immediately.

Die Nebenaggregate, wie Filter und Speichersysteme für Schleusenflüssigkeit, Reinigungsmedien und Elektrolyte, sind entsprechend der Erfindung so gestaltet, daß ein geschlossener umweltunabhängiger Betrieb möglich ist. Abfallprodukte werden in konzentrierter Form recyclingfähig ausgeschieden. Das geschilderte Verfahren bietet über die erfindungsgemäß beschriebenen Komponenten die Möglichkeit einer chemischen Passivierung der Beschichtung, die eine wesentliche Erhöhung der Korrosionsbeständigkeit darstellt. Eine gemäß der Erfindung mögliche farbliche Nuancierung der Beschichtung selbst, nicht als Auftrag, erhöht die mechanische Beständigkeit dieser Farbgebung im Vergleich zu Lacken erheblich. Die dem Verfahren erfindungsgemäß zugrundeliegende Auswahl der Beschichtungsmaterialien und Elektrolyten erhöht gegenüber den dargestellten klassischen Verfahren die Korrosionsbeständigkeit sowohl im sauren als auch im alkalischen Bereich erheblich. Durch eine entsprechend der Erfindung erfolgte Ausgestaltung der Austrittsbereiche des Drahtes aus dem Beschichtungs- und Spültrakt wird es möglich, den Draht in trockner bzw. sogar in oberflächenverdickter Form in den gewünschten Farben und entsprechenden Beschichtungsauflagen zu erhalten.The auxiliary units, such as filters and storage systems for Lock fluid, cleaning media and electrolytes are designed according to the invention so that a closed environmentally independent operation is possible. waste products are recyclable in a concentrated form. The described method offers the invention described components the possibility of a chemical Passivation of the coating, which is a significant increase which represents corrosion resistance. One according to the invention possible color nuances of the coating itself, not as an order, increases the mechanical resistance of this Coloring significantly compared to paints. The procedure Selection of the coating materials on which the invention is based and electrolytes increased over those shown classical methods of corrosion resistance considerable both in the acidic and in the alkaline range. By an embodiment made in accordance with the invention the exit areas of the wire from the coating and Rinsing tract it becomes possible to dry the wire in dryer or even in thickened form in the desired colors and to receive appropriate coating requirements.

Ein weiterer Gegenstand der Erfindung ist eine Vorrichtung zum elektrolytischen Beschichten von metallischen oder nichtmetallischen Endlosprodukten mit Metallen oder Metalllegierungen im Durchlaufverfahren aus aprotischen wasser- und sauerstofffreien Elektrolyten, bestehend aus einer Beschichtungsanlage mit mindestens einem Schleusensystem 1, mindestens einer Kontaktierungszelle 5, mindestens einer Beschichtungszelle 6, wobei diese Baugruppen in beliebiger Anzahl hintereinander geschaltet sind und die gesamte Vorrichtung luftdicht verkapselt ist. Die Beschichtungsanlage zeichnet sich dadurch aus, daß sie eine Aktivierungseinheit 2 und eine Spüleinheit 3 in dieser Reihenfolge umfasst und eine Abspuleinheit für das unbeschichtete Endlosprodukt außerhalb der gekapselten Beschichtungsanlage angeordnet ist. Eine solche Vorrichtung dient auch zur Durchführung des erfindungsgemäßen Verfahrens.Another object of the invention is a device for electrolytic coating of metallic or non-metallic Continuous products with metals or metal alloys in a continuous process from aprotic water and oxygen free Electrolytes, consisting of a coating system with at least one lock system 1, at least a contacting cell 5, at least one coating cell 6, these assemblies in any number are connected in series and the entire device is encapsulated airtight. The coating system draws are characterized in that they have an activation unit 2 and a Rinsing unit 3 includes in this order and an unwinding unit for the uncoated continuous product outside of encapsulated coating system is arranged. Such Device also serves to carry out the invention Process.

Figur 2 zeigt eine Ansicht des Schleusensystems 1. Es besteht bevorzugt aus mindestens drei Kammern A, B und C, 17, 18, 19, wobei die mittlere Kammer B einen Flüssigkeitsüberlauf 16 besitzt und die Kammern A und C als Überlaufkammern ausgebildet sind. Besonders bevorzugt besitzen die Kammern A, B und C einen Ablauf 20, 22 und 23, wobei die mittlere Kammer zusätzlich einen Zulauf 21 besitzt, durch die die in den Kammern A und C gesammelte Sperrflüssigkeit in die mittlere Kammer B zurückgeführt werden kann. Die Ziffer 14 bezeichnet einen Vorratstank, die Ziffer 15 eine entsprechende Pumpe. Mit der Ziffer 9 ist die Drahtführung bezeichnet, Ziffer 17 bezeichnet die Kammer A, Ziffer 18 die Kammer B und Ziffer 19 die Kammer C. Mit der Ziffer 12 ist das Endlosprodukt bezeichnet, das durch die Kammer geführt wird und Ziffer 11 ist eine bevorzugt eingesetzte Gasabstreif- oder Sprühdüse zur zusätzlichen Reinigung der Oberfläche des durch die Anlage geführten Endlosproduktes 12. Mit den Ziffern 24 und 25 sind die inneren Kammerwände bezeichnet, die Ziffer 13 bezeichnet eine Wechselplatte für Buchsen. Hierdurch ist es möglich, Endlosprodukte verschiedenen Durchmessers einzusetzen, wobei dann jeweils auch die entsprechende Buchse eingesetzt werden muß. Ziffer 10 bezeichnet den Flüssigkeitsspiegel.Figure 2 shows a view of the lock system 1. There is preferably from at least three chambers A, B and C, 17, 18, 19, the middle chamber B has a liquid overflow 16 and chambers A and C are designed as overflow chambers are. Chambers A, B and C particularly preferably have one Drain 20, 22 and 23, with the middle chamber in addition has an inlet 21 through which the in the chambers A and C collected barrier liquid into the middle chamber B can be traced back. The number 14 designates one Storage tank, the number 15 a corresponding pump. With the Number 9 denotes the wire guide, number 17 denotes Chamber A, Section 18 Chamber B and Section 19 Chamber C. Numeral 12 denotes the continuous product, that is passed through the chamber and number 11 is preferred used gas wiping or spray nozzle for additional Cleaning the surface of the through the plant led continuous product 12. With the numbers 24 and 25 are designated the inner chamber walls, number 13 a removable plate for sockets. This makes it possible To use continuous products of different diameters, whereby then the corresponding socket can also be used got to. Numeral 10 denotes the liquid level.

Figur 3 zeigt eine Beschichtungszelle. Die Figuren 3a, 3b und 3d zeigen verschiedene Ansichten des in der Zelle befindlichen Trägers 28 für das Endlosprodukt 12. Figur 3a zeigt eine Vorderansicht, Figur 3b eine Seitenansicht und Figur 3d eine Aufsicht. Die Figur 3c ist eine perspektivische Ansicht der gesamten Beschichtungszelle 6. In den Figuren 3a, 3b und 3d ist mit der Ziffer 28 der Träger aus Isoliermaterial bezeichnet. Ziffer 27 zeigt die in zwei Teile geteilte Keramikbuchse. Diese ist entgegen der Laufrichtung des eingeführten Endlosproduktes aus dem Isoliermaterial entfernbar angeordnet und kann beispielsweise gegen Buchsen mit einem veränderten Durchmesser ausgetauscht werden.Figure 3 shows a coating cell. Figures 3a, 3b and 3d show different views of the one in the cell Carrier 28 for the continuous product 12. Figure 3a shows one Front view, Figure 3b is a side view and Figure 3d a At sight. Figure 3c is a perspective view of the entire coating cell 6. In Figures 3a, 3b and 3d is designated by the number 28 of the carrier made of insulating material. Section 27 shows the ceramic bushing divided into two parts. This is opposite to the direction of the imported continuous product arranged removably from the insulating material and can, for example, against sockets with a modified Diameter can be exchanged.

Figur 3c zeigt die gesamte Beschichtungszelle 6 mit den Anodenplatten 26 und dem in der Mitte angeordneten Träger 28 und der Buchse 27.Figure 3c shows the entire coating cell 6 with the anode plates 26 and the carrier 28 arranged in the middle and the socket 27.

Die Beschichtungszelle 6 besitzt bevorzugt Führungen zur Führung des Endlosproduktes 12, die so gestaltet sind, daß ein gleichmäßiger Abstand zwischen den in der Beschichtungszelle angeordneten Anoden 26 und dem zu beschichtenden Endlosprodukt 12 gewährleistet ist. In einer weiteren bevorzugten Ausführungsform besitzt die Beschichtungszelle einen Überlauf und einen Zulauf für Elektrolyt. The coating cell 6 preferably has guides for guidance of the continuous product 12, which are designed so that a uniform distance between those in the coating cell arranged anodes 26 and the continuous product to be coated 12 is guaranteed. In a further preferred embodiment the coating cell has an overflow and an inlet for electrolyte.

Die Führungen in den Beschichtungszellen bestehen aus einem Träger 28 aus Isoliermaterial, der in der Mitte durchbohrt ist, wobei in der Durchbohrung Buchsen 27 angeordnet sind, die nur einseitig einsteckbar sind und in bevorzugter Weise aus keramischem Material bestehen und zur leichteren Auswechselbarkeit für Endlosprodukte von verschiedenem Durchmesser geteilt sind.The guides in the coating cells consist of a Carrier 28 made of insulating material which pierces in the middle is, bushings 27 are arranged in the through bore, which can only be inserted on one side and in a preferred manner Made of ceramic material and for easy interchangeability for continuous products of different diameters are divided.

Figur 4 zeigt eine Abbildung der Kontaktierungszelle 5. Figur 4a stellt eine Vergrößerung des Kontaktierungsbereiches als Seitenansicht dar. Figur 4b zeigt eine perspektivische Ansicht der Kontaktierungszelle 5. In der Figur 4b ist mit der Ziffer 12 das Endlosprodukt bezeichnet. Dieses wird zwischen einer unter kathodischer Spannung befindlichen Metallrolle 29 und einer nicht leitenden Keramikspannrolle 30 hindurchgeführt, wobei mit der Ziffer 32 die Kerben in den Metallrollen bezeichnet sind zur besseren Führung des Endlosproduktes 12. Mit der Ziffer 33 sind die Halteelemente für die Metallrollen und die Keramikspannrollen bezeichnet. Figur 4a zeigt einen vergrößerten Ausschnitt des Kontaktierungsbereiches. Die Ziffer 29 zeigt die Metallrolle, Ziffer 31 eine Bronzebuchse zur Stromzuführung, Ziffer 12 das Endlosprodukt und Ziffer 30 sind die Keramikspannrollen. Mit diesen wird die Vorspannung über Federn oder Stellschrauben für das Endlosprodukt eingestellt.Figure 4 shows an image of the contacting cell 5. Figure 4a represents an enlargement of the contact area as Side view. Figure 4b shows a perspective view the contacting cell 5. In FIG. 4b, the Section 12 designates the continuous product. This is between a metal roller 29 which is under cathodic voltage and passed through a non-conductive ceramic tension roller 30, with the number 32 the notches in the metal rollers are designated for better guidance of the continuous product 12. With the number 33 are the holding elements for the metal rollers and the ceramic tension rollers. Figure 4a shows one enlarged section of the contact area. The digit 29 shows the metal roller, number 31 a bronze bushing Power supply, section 12 the continuous product and section 30 are the ceramic tensioners. With these the preload set via springs or set screws for the continuous product.

Die Kontaktierungszelle 5 ist in bevorzugter Weise so ausgebildet, daß in ihr eine Metallrolle oder ein Schleifkontakt angeordnet ist, über den das Endlosprodukt kathodisch geschaltet wird. Zusätzlich können eine oder mehrere Keramikspannrollen zur Einstellung der Vorspannung in der Kontaktierungszelle angeordnet sein. In einer bevorzugten Ausführungsform weist die Metallrolle eine Kerbung auf, über die das Endlosprodukt geführt wird. In der Kontaktierungszelle ist weiterhin bevorzugt ein Überlauf angeordnet, so daß aus der Elektrolysezelle dringende Elektrolyte in ein Sammelsystem abgeführt werden können.The contacting cell 5 is preferably designed such that that in it a metal roller or a sliding contact is arranged, via which the continuous product is connected cathodically becomes. In addition, one or more ceramic tensioners can be used for setting the preload in the contacting cell be arranged. In a preferred embodiment the metal roller has a notch over which the continuous product is led. In the contacting cell an overflow is preferably arranged so that from the electrolysis cell urgent electrolytes in a collection system can be dissipated.

Die Figur 5 zeigt eine Ansicht der Beschichtungszelle 6, der Kontaktierungszelle 5 und der Spüleinheiten 3. Figur 5a zeigt die Aufsicht auf diese Zellen und Figur 5b eine Seitenansicht. Es ist zu erkennen, daß die Spüleinheiten 3 in ähnlicher Weise gestaltet sind, wie die zuvor beschriebenen Schleusensysteme in Figur 2. Sie besitzen ebenfalls einen Überlauf, sowie benachbarte Überlaufkammmern, wobei die mittlere Kammer jeweils mit Flüssigkeit gefüllt ist. Diese kann durch die nicht dichten Führungen in die Nachbarkammern laufen und wird durch entsprechenden Abläufe gesammelt und in die Spülkammern zurückgeführt. Mit der Ziffer 5 sind die Kontaktierungszellen beschrieben. Diese sind bevorzugt den Beschichtungszellen 6 benachbart und mit Elektrolyt gefüllt. Die Ziffer 6 zeigt die Beschichtungszellen mit den Anoden 26 und den Trägern 28 aus Isoliermaterial mit den darin befindlichen Keramikbuchsen 29 zur Führung der Endlosprodukte 12 in den Beschichtungszellen. Auch die Beschichtungszellen sind mit Elektrolyt gefüllt und verfügen über einen Überlauf, einen Ablauf und einen Zulauf, durch den die jeweiligen Elektrolytflüssigkeiten umgewälzt, gereinigt und rückgeführt werden können.FIG. 5 shows a view of the coating cell 6 Contacting cell 5 and the rinsing units 3. Figure 5a shows the supervision of these cells and Figure 5b is a side view. It can be seen that the rinsing units 3 in a similar way Are designed like the ones described above Lock systems in Figure 2. They also have one Overflow, as well as neighboring overflow chambers, the middle Chamber is filled with liquid. This can run through the impervious guides into the neighboring chambers and is collected through appropriate processes and in the rinsing chambers returned. With the number 5 are the contacting cells described. These are preferably the coating cells 6 adjacent and filled with electrolyte. The number 6 shows the coating cells with the anodes 26 and the carriers 28 made of insulating material with those therein Ceramic bushings 29 for guiding the continuous products 12 in the coating cells. The coating cells are too filled with electrolyte and have an overflow, one Drain and an inlet through which the respective electrolyte liquids circulated, cleaned and returned can.

Die erfindungsgemäße Vorrichtung weist erhebliche Vorteile auf gegenüber bisher bekannten Vorrichtungen zur Metallisierung von Endlosprodukten. So ist der Draht über nicht leitende Rohre und Rollenführungen innerhalb der Vorrichtung, speziell aber im elektrischen Feld der Beschichtungszelle 6, stabil positionierbar. Durch diese stabile Führung ist es möglich, mehrere parallele Stränge von Endlosprodukten, beispielsweise mehrere Drähte, auch in senkrechter Anordnung durch die Vorrichtung zu führen, ohne daß es zu unerwünschten elektrischen Kontakten kommt und ein gleichmäßiger Abstand zur Anode gewährleistet ist. Durch die als Überflutungskammern konstruierten Schleusensysteme 1, Spüleinheiten 3 und Kontaktierungszellen 5 ist eine elektrische Zwischenkontaktierung außerhalb des Wirkungsbereiches des Anodenmaterials möglich, wobei das Endlosprodukt stetig im Elektrolyten verbleibt. Die Übertragung der elektrischen Energie in den Kontaktierungszellen 5 kann sowohl über Schleifkontakte in Form von flexiblen Kontaktstiften, die federnd gelagert sind, erfolgen, als auch über federnde Kontaktrollen.The device according to the invention has considerable advantages on previously known devices for metallization of continuous products. So the wire is over non-conductive Pipes and roller guides inside the device, specifically but in the electric field of the coating cell 6, stable positioning. It is through this stable guidance possible, several parallel strands of continuous products, for example several wires, also in a vertical arrangement to lead through the device without causing undesirable electrical contacts and an even distance to the anode is guaranteed. Through the as flood chambers constructed lock systems 1, rinsing units 3 and Contacting cells 5 is an electrical intermediate contact outside the area of effect of the anode material possible, with the continuous product remaining in the electrolyte. The transmission of electrical energy in the contacting cells 5 can both form sliding contacts of flexible contact pins, which are spring-loaded, as well as via resilient contact rollers.

Durch die besondere Lagerung des Endlosproduktes in der Kontaktierungszelle 5, wie auch durch die Führungen in der Beschichtungszelle 6, ist es möglich, unterschiedliche Durchmesser von Endlosprodukten zu fahren. Durch die bevorzugten Umlenkeinheiten 4 ist es möglich, die Endlosprodukte durch mehrere parallele Beschichtungszellen zu führen und damit bei relativ kurzen Anlagen hohe Durchlaufgeschwindigkeiten zu ermöglichen.Due to the special storage of the continuous product in the contacting cell 5, as well as through the guides in the coating cell 6, it is possible to have different diameters of endless products. By the preferred Deflection units 4, it is possible to pass through the continuous products to lead several parallel coating cells and thus relatively short systems to enable high throughput speeds.

Selbst bei einem Stillstand der Anlage kann das Endlosprodukt in den Kammern verbleiben, ohne daß eine Überreaktion an der Oberfläche, wie Überbeizen oder einseitige Überbeschichtung, erfolgen kann, da unter Beibehaltung der inerten Atmosphäre in der Anlage die Reaktionsmedien in den Zwischenbehältnissen außerhalb der Reaktionsräume gespeichert werden. Weiterhin ist es vorteilhaft, daß ein Austausch des Anodenmaterials im Stillstand erfolgen kann, ohne das zu beschichtende Material aus der Anlage zu entfernen.Even if the system is at a standstill, the continuous product can remain in the chambers without an overreaction on the Surface, such as over-pickling or one-sided over-coating, can take place, while maintaining the inert atmosphere in the system the reaction media in the intermediate containers be stored outside the reaction spaces. Farther it is advantageous that an exchange of the anode material in the Standstill can take place without the material to be coated to remove from the system.

Mit dem erfindungsgemäßen Verfahren und der erfindungsgemäßen Vorrichtung ist es möglich, Endlosprodukte in einem industriell durchzuführenden Verfahren und einer entsprechenden Vorrichtung mit Metallen, insbesnndere Aluminium, zu beschichten. Das erfindungsgemäße Verfahren und die erfindungsgemäße Vorrichtung ersetzen somit die bisher angewendeten Verfahren der Feueraluminierung, Feuerverzinkung und elektrolytischen Beschichtung in wässrigen Medien.With the inventive method and the inventive It is possible to manufacture continuous products in an industrial device procedure to be carried out and a corresponding Coating device with metals, in particular aluminum. The inventive method and the inventive Device thus replace the previously used Process of hot-dip aluminizing, hot-dip galvanizing and electrolytic Coating in aqueous media.

Claims (28)

  1. A process for electroplating metallic or non-metallic continuous products with metals or alloys in a continuous process from aprotic electrolytes free of water and oxygen, wherein the continuous product is passed through a lock system (1) into an encapsulated coating plant under inert gas atmosphere, and the following steps are performed therein at temperatures of ≤120°C in the order below:
    activating the continuous product to be coated;
    rinsing the continuous product to be coated;
    contacting the continuous product to be coated;
    electroplating the continuous product to be coated using a metal or metal alloy;
    drying the coated continuous product;
    discharging the coated continuous product from the plant through a lock system,
    characterized in that the non-coated continuous product is fed from the outside via a lock system (1) into the encapsulated coating plant, and that activating and rinsing of the continuous product to be coated is effected in the encapsulated plant as well.
  2. The process according to claim 1, characterized in that wire, tapes, long-profiles or pipes made of metallic or non-metallic materials are employed as continuous products.
  3. The process according to claim 1 or 2, characterized in that coating is effected using aluminum or aluminum alloys.
  4. The process according to claims 1 to 3, characterized in that during introduction into the lock system (1), a cleaning procedure is performed by passing the continuous product (12) over a gas stripping nozzle or spray nozzle (11).
  5. The process according to claims 1 to 4, characterized in that electroplating in the plant is followed by a chemical or electrochemical secondary treatment.
  6. The process according to claims 1 to 5, characterized in that the entire plant is of a closed design using regeneration cycles, and that all of the liquids used are treated, purified and recirculated in a circulation process.
  7. The process according to claim 6, characterized in that the liquids are rinsing solutions, electrolyte solution and activation solution.
  8. The process according to claims 1 to 7, characterized in that the continuous product (12) is passed through deflector units (4) in order to permit high passage rates in short plants.
  9. The process according to claims 1 to 8, characterized in that the continuous product (12) is passed through the lock system (1) and the rinsing unit (3), each consisting of at least three chambers (17, 18 and 19), the middle chamber B (18) being filled with a sealing fluid, the outer chamber A (17) containing air, and the inner chamber C (19) containing an inert gas.
  10. The process according to claims 1 to 9, characterized in that the continuous products are introduced into the chambers through guides (9) which are not air-tight and liquid-tight, so that part of the liquid in the chambers runs into the adjacent chambers.
  11. The process according to claims 1 to 10, characterized in that the liquids discharging from the chambers through the overflow (16) or the guides (9) are purified via a circulation system and re-circulated into the chambers.
  12. The process according to claims 1 to 11, characterized in that the guides (9) are bushings or pulleys.
  13. The process according to claims 1 to 12, characterized in that contacting is effected in a contacting cell (5) filled with liquid electrolyte, which cell does not include an anode, the continuous product (12) being passed over a metal contact (29) connected as cathode.
  14. The process according to claims 1 to 13, characterized in that electroplating is performed in a coating chamber (6) filled with electrolyte solution, the continuous product (12) being passed through a bushing (27) which is insulated.
  15. A device for electroplating metallic or non-metallic continuous products (12) with metals or metal alloys in a continuous process from aprotic electrolytes free of water and oxygen, which device is comprised of a coating plant having at least one lock system (1), at least one contacting cell (5), at least one coating cell (6), said assemblies being arranged in series, and the entire device being encapsulated so as to be air-tight, characterized in that the coating plant comprises an activation unit (2) and a rinsing unit (3) in this order, and that a wind-off unit for the non-coated continuous product is arranged outside the encapsulated coating plant.
  16. The device according to claim 15, characterized in that the lock system (1) consists of at least three chambers A, B and C (17, 18, 19), the middle chamber B (18) having a liquid overflow, and the chambers A and C (17, 19) being designed as overflow chambers.
  17. The device according to claim 15 or 16, characterized in that the chambers A, B and C (17, 18, 19) have outlets (20, 22, 23), the middle chamber B (18) additionally having an inlet (21) through which the sealing fluid collected in chambers A, C (17, 19) can be recirculated into the middle chamber B (18).
  18. The device according to claims 15 to 17, characterized in that a gas stripping nozzle or spray nozzle (11) is arranged in chamber C (19).
  19. The device according to claims 15 to 18, characterized in that the middle chamber B (18) of the lock system (1) has an overflow (16).
  20. The device according to claims 15 to 19, characterized in that the contacting cell (5) has a metal pulley (29) or a wiping contact arranged therein, through which the continuous product (12) is connected as cathode.
  21. The device according to claims 14 to 20, characterized in that one or more ceramic tension pulleys (30) are arranged to adjust the bias voltage in the contacting cell (5).
  22. The device according to claims 15 to 21, characterized in that the metal pulley (29) has a groove (32) for guiding the continuous product (12).
  23. The device according to claims 15 to 22, characterized in that an overflow (16) is arranged in the contacting cell (5), so that electrolyte discharging from the coating cell (6) can be drained off into a collector system.
  24. The device according to claims 15 to 23, characterized in that guides (27) to guide the continuous product (12) are arranged in the coating cell (6).
  25. The device according to claims 15 to 24, characterized in that anodes (26) are arranged in the coating cell (6).
  26. The device according to claims 15 to 25, characterized in that the coating cell (6) has an overflow (16) and an inlet (21).
  27. The device according to claims 15 to 26, characterized in that the guides (9) in the coating cell (6) consist of a support (28) made of an insulating material having a through-bore in the center, with bushings (27) being arranged in the through-bore which are penetrable from one side only.
  28. The device according to claims 15 to 27, characterized in that the bushings (27) consist of a ceramic material and are split in order to make replacement easier.
EP98922715A 1997-04-19 1998-04-15 Method for electroplating metallic and non-metallic endless products and device for carrying out said method Expired - Lifetime EP0975826B1 (en)

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DE19716493A DE19716493C2 (en) 1997-04-19 1997-04-19 Process for the electrolytic coating of metallic or non-metallic continuous products and device for carrying out the process
DE19716493 1997-04-19
PCT/EP1998/002196 WO1998048081A2 (en) 1997-04-19 1998-04-15 Method for electroplating metallic and non-metallic endless products and device for carrying out said method

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US7204918B2 (en) * 2003-03-10 2007-04-17 Modular Components National, Inc. High efficiency plating apparatus and method
US9149990B2 (en) * 2007-03-30 2015-10-06 Airbus Operations Gmbh Apparatus for the forming of a lay-up of fibre composite material
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BE761101A (en) * 1970-03-25 1971-05-27 Nisshin Steel Co Ltd DEVICE FOR GALVANO-PLASTIC METALLIZATION OF METALS
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DE3023827C2 (en) * 1980-06-25 1985-11-21 Siemens AG, 1000 Berlin und 8000 München Plant for the galvanic deposition of aluminum
US4401522A (en) * 1980-09-29 1983-08-30 Micro-Plate, Inc. Plating method and apparatus
DE3137908A1 (en) * 1981-09-23 1983-04-07 Siemens AG, 1000 Berlin und 8000 München SYSTEM FOR GALVANIC DEPOSITION OF METALS, ESPECIALLY ALUMINUM
DE3202265A1 (en) * 1982-01-25 1983-07-28 Siemens AG, 1000 Berlin und 8000 München ELECTROLYTE FOR GALVANIC DEPOSITION OF ALUMINUM
US5082747A (en) * 1985-11-12 1992-01-21 Hedgcoth Virgle L Magnetic recording disk and sputtering process and apparatus for producing same
JPS63227797A (en) * 1987-03-16 1988-09-22 Nisshin Steel Co Ltd Activation treatment of metallic sheet before al electroplating and treating solution
DE3919069A1 (en) * 1989-06-10 1990-12-13 Studiengesellschaft Kohle Mbh ALUMINUM ORGANIC ELECTROLYTE AND METHOD FOR ELECTROLYTICALLY DEPOSITING ALUMINUM
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DE19716493A1 (en) 1998-10-22
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WO1998048081A2 (en) 1998-10-29
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AU7525798A (en) 1998-11-13
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