EP0043440B1 - Apparatus for the electroplating of aluminium - Google Patents

Apparatus for the electroplating of aluminium Download PDF

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Publication number
EP0043440B1
EP0043440B1 EP81104184A EP81104184A EP0043440B1 EP 0043440 B1 EP0043440 B1 EP 0043440B1 EP 81104184 A EP81104184 A EP 81104184A EP 81104184 A EP81104184 A EP 81104184A EP 0043440 B1 EP0043440 B1 EP 0043440B1
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EP
European Patent Office
Prior art keywords
installation according
electrolyte
tubular cell
inert
chambers
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.)
Expired
Application number
EP81104184A
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German (de)
French (fr)
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EP0043440A1 (en
Inventor
Richard Dr. Dipl.-Chem. Dötzer
Klaus Stöger
Paul Hini
Johann Gehring
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Siemens AG
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Siemens AG
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Priority to AT81104184T priority Critical patent/ATE6874T1/en
Publication of EP0043440A1 publication Critical patent/EP0043440A1/en
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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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • 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
    • C25D3/44—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires

Definitions

  • the invention relates to a system for the galvanic deposition of aluminum from aprotic, oxygen-free and water-free aluminum-organic electrolytes, on wire, tube or tape-shaped material with a tube cell closed to the outside, through which the material to be treated, cathodically contacted, runs along in the axial direction is movable by anodes and through which the electrolyte can be pumped with the aid of a closed electrolyte circulation system against the direction of movement of the material, a lock arrangement being provided at each end of the tubular cell, which arrangement prevents the electrolyte from flowing out of the tubular cell and consists of several chambers.
  • Electrolysis systems for plating wire and strip-shaped materials are known, in which the material to be treated is passed through an electrolysis bath in vertical loops.
  • DE-OS No. 1521076 discloses a device for plating a strand of plastic, in which the conductively precoated plastic strand is passed through an electrolysis bath in a plurality of loops with the aid of drive and contacting rollers arranged at the top and deflection rollers arranged at the bottom vertical anode plates are provided in the electrolysis bath parallel to the course of the strand.
  • the invention is therefore based on the object of designing a system of the type described at the outset in such a way that not only the undesired escape of the electrolyte from the tubular cell, but also the penetration of air atmosphere is reliably prevented.
  • a protective gas inert gas
  • T-shaped connecting pieces are arranged which have a diaphragm which prevents the longitudinal passage of the electrolyte and vertically deflects the electrolyte flow and which has an opening which is closely matched to the shape of the cross section of the material to be treated.
  • At least one disk-shaped chamber wall of the lock arrangements has a radial bore leading to the opening for the passage of the material to be treated, which is connected via a connecting piece to an inert liquid circuit for mutual sealing of the chambers and washing of the material to be treated.
  • the opening in the chamber wall is supplied with inert liquid via the bore in such a way that one can speak of a liquid lock that is practically airtight.
  • the inert liquid for washing the treated material prefferably obtained from the electrolyte by distillation using an evaporator and fed through a bore in the chamber wall. Then the other inert liquids for pure sealing are not contaminated.
  • the opening in the panel is formed by a channel that extends over the entire length of the connecting piece, the clear width of which is adapted to the cross section of the material to be treated and the front of which is in front of the panel extending part has only a wall thickness required for strength, while the part extending behind the panel is adapted to the clear width of the connecting piece.
  • the tubular cell with the T-shaped connecting pieces for the vertical passage of the material to be aluminized is arranged vertically.
  • Band-shaped anodes 7 are arranged inside the tube cell 1 on both sides of the band 2, as shown in particular in FIG. 2a.
  • the band-shaped anodes 7 are contacted by means of contacting pins 8, which are arranged in ring-shaped anode holders 9, as can be seen in more detail in FIG. 2g.
  • FIG. 1 In the exemplary embodiment shown in FIG.
  • the anode holders 9 are arranged at both ends of the tubular cell 1 and close tightly with the flange of the tubular cell 1. In the case of longer tubular cells 1, it is expedient that at least one further anode holder 9 with contacting pins 8 is provided in the course of the tubular cell 1.
  • T-shaped connecting pieces 10 are flanged, with the aid of which electrolyte 11 from an electrolyte reservoir 12 through the tubular cell 1 opposite the direction of movement of the strip 2 with the aid of a pump 13 and pipes 14 and 15 can be pumped. With the help of a flow meter 16, the electrolyte speed can be recorded.
  • the T-shaped connecting pieces 10 are provided with an oblique diaphragm 17 in order to deflect the electrolyte entering or exiting via the connecting piece 18 by 90 ° as aerodynamically as possible, so that a closed electrolyte circuit is formed, which, however, is interrupted by means of the valves 19 and 20 can, for example when the tube cell 1 is put into operation.
  • inert liquid 26 can be pumped from an inert liquid storage container 27 through the pipe cell 1 and connecting pieces 10, once in order to supply the atmospheric air from the pipe cell 1 remove before the electrolyte 11 is pumped through under a protective gas atmosphere N 2 , and secondly to be able to clean the tube cell with inert liquid after the Al electrolytes have been drained.
  • the electrolyte flowing through the line 15 in the direction of the arrow is not introduced directly into the electrolyte reservoir 12, but via a filter 28 in order to separate contaminants from the electrolyte 11 in the form of solid particles.
  • the electrolyte reservoir 12 is of course sealed airtight with the help of a lid 29.
  • the electrolyte reservoir 12 is also equipped with a pressure relief valve 30 and corresponding, airtight openings for introducing the pipelines 14 and 15.
  • the electrolyte reservoir 12 is also under a protective gas atmosphere.
  • the diaphragms 17 of the T-shaped connecting pieces are provided with corresponding openings for the passage of the band 2, and these openings are adapted as closely as possible to the cross section of the band 2 in order to avoid as far as possible that electrolyte from the tube cell 1 or from the T -shaped connecting pieces come out or atmospheric air penetrates.
  • lock arrangements 31 and 32 are arranged at both ends of the tube cell 1 and the connecting pieces 10 connected thereto, whereby according to FIG. 1 the lock arrangement 31 has three chambers 33 to 35, while the lock arrangement 32 even has five chambers 36 to 40. In the chambers 35 and 36 of the lock arrangements 31 and 32, the electrolyte escaping through the openings in the diaphragms 17 is collected and returned to the electrolyte reservoir 12 via pipes 41 and 42, specifically in front of the filter 28.
  • lock arrangements 31 and 32 have liquid locks which are particularly tight and which even prevent atmospheric air from diffusing into the tube cell 1.
  • An effective liquid lock can be formed, for example, by partially flooding the chambers of the lock arrangements 31 and 32, which are preferably composed of pipe pieces and partitions, with inert liquids, which will be explained in more detail with reference to FIG. 2.
  • a disk-shaped intermediate wall 43 which is provided with a breakthrough for the passage of the strip 2 is provided with a bore leading to this breakthrough, to which a line 44 is connected, which leads to a via a valve 45
  • Inert liquid container 46 leads.
  • the inert liquid is fed to the opening in the intermediate wall 43 in such a way that the space between the band 2 and the opening is completely filled.
  • the inert liquid emerging from the gap between the strip and the breakthrough is collected in the chambers 33 and 34 and fed back to the inert liquid container 46 via pipes 48 and 49.
  • the intermediate walls 50 and 51 of the lock chambers 37 and 38 or 39 and 40 are also formed, the connecting bore of the disk-shaped intermediate wall 50 being connected via a pipeline 52 and valve 53 an evaporator 54 is connected.
  • a feed pump 55 is provided, with which the inert liquid obtained by distillation from the electrolyte 11 can be pumped through the radial bore of the intermediate wall 50 into the space between band 2 and the breakthrough.
  • the inert liquid that accumulates in the chambers 37 and 38 of the lock arrangement 32 is returned to the electrolyte reservoir 12 via pipes 56.
  • the main task of this inert liquid circuit is to clean the aluminized goods from adhering Al electrolytes with inert liquid.
  • composition and The amount of electrolyte in the reservoir 12 is practically constant and at the same time the amount of electrolyte discharge through the band 2 to be coated is reduced to a minimum (rinsing the surface of the band 2 with pure inert liquid is a highly effective cleaning of the adhering electrolyte).
  • the disk-shaped intermediate wall 51 is connected to a pipeline 57, which is connected to a further inert liquid container 60 via a valve 58 and pump 59.
  • the return flow of the inert liquid from the chambers 39 and 40 takes place via a pipeline 61.
  • the roll 3 of the unwinding unit 4 is also located in a closed container 62 which is charged with inert gas N 2 and is partially filled with inert liquid.
  • the container 62 is connected to an inert liquid container 66 via a pipeline 63, a valve 64 and a feed pump 65.
  • An overflow 67 for the inert liquid is provided in the container 62. Behind the overflow 67, a discharge pipe line 68 is attached, which leads the overflowing inert liquid back into the inert liquid container 66.
  • the container 62 is also still sealingly connected to the lock arrangement 31 via a tubular connecting piece 69.
  • the connecting piece 69 also has a longitudinal opening for the band 2 to be aluminized and can be connected to the pipe 44 of the inert liquid circuit of the lock arrangement 31 by means of a pipe 70.
  • the tape 2 is contacted via contacting rollers 71 and 72 arranged on both sides of the tape 2. For the sake of clarity, only one contacting roller is drawn, which is connected to the negative pole of the power source.
  • the contacting rollers 71 are arranged within the container 62 and separated by an intermediate wall 73. With the help of a pipeline 74 which is connected to the pipeline 49, excess inert liquid can be discharged into the inert liquid container 46.
  • Connection pieces 75 and 76 or 77 and 78 of the lock arrangements 31 and 32 are used for connection to an inert gas storage container, which is not shown in the drawing for the sake of clarity. Of course, the connection is made via appropriate valves.
  • FIG. 2 shows a section through the lock arrangement 31, the T-shaped connecting piece 10, the anode holder 9 and part of the tubular cell 1.
  • FIGS. 2a to 2g show different sectional views in FIG. 2, the same parts being provided with the same reference numerals are.
  • anodes 7 are arranged on both sides of the strip to be aluminized, which anodes 7 are larger than the width of the strip 2.
  • the inside of the pipe is completely filled with electrolyte.
  • the band 2 is completely aluminized on both sides. If any parts of the strip are not to be covered with an aluminum layer, these parts must be covered, for example by inserting a corresponding shaped body into the interior of the tubular cell 1, so that only the parts of the strip released by the corresponding cover are aluminized.
  • the anode holder 9 is annular and is arranged between the connecting flanges of the tubular cell 1 and the T-shaped connecting piece 10 with the interposition of sealing rings 79.
  • the contacting pins 8 are guided to the anodes 7 via insulating bushings and press them against an appropriately designed anode carrier 81 made of insulating material.
  • the anode carrier 81 has a corresponding recess 82 for the band 2 and serves to guide the same.
  • the internally insulated T-shaped connecting piece 10 can be a normal tube with a T-shape, which has the same diameter as the tube cell 1.
  • the inclined surface forming the actual panel.
  • a curved surface can also be used.
  • the part of the insert part 83 lying behind the inclined surface completely fills the intermediate piece 10 and has only one opening 85, which is closely adapted to the strip cross section, for the strip 2 to pass through.
  • this opening 85 extends over the entire length of the insert part 83 and is surrounded in front of the cover 17 by a tubular part 86, as shown in FIG. 2f.
  • the wall thickness of the part 86 is so small that the electrolyte can flow freely, but the part is given the required strength.
  • the insert part 83 is pushed tightly into the connecting piece 10, a disk-shaped wall part 87 of the lock arrangement 31 being arranged between the flange 84 of the insert part 83 and the flange of the connecting piece 10 and having the connecting piece 76 for the inert gas N 2 .
  • the connecting piece 76 is connected to the chamber 35 via a bore, not shown, which is formed by a further disk-shaped wall part 88 and a pipe section 89.
  • the disk-shaped wall part 87 also has a connecting piece 90 for connecting the pipeline 42 according to FIG. 1.
  • the electrolyte emerging from the connecting piece 10 through the gap between the band 2 and the opening 85 can collect, which then passes through the connecting piece 90 and piping 41 and 42 is supplied to the electrolyte reservoir.
  • the chamber 34 of the lock arrangement 31 is formed by the wall parts 43 and 88 and the chamber 33 by the wall part 43 and a wall part 92.
  • the two chambers 33 and 34 serve to collect the inert liquid, which has an opening 95 through a connecting piece 93 and a radial bore 94 a non-conductive disc-shaped molded part 96 is supplied.
  • the line 44 according to FIG. 1 is connected to the connecting piece 93, via which the inert liquid is fed with the help of the pump 47 via the channel 94 into the gap between the band 2 carried out and the opening 95 in such a way that it is completely filled with inert liquid is. This creates a 100% seal against atmospheric air.
  • the inert liquid collecting at the bottom of the chambers 34 and 33 is drained into the inert liquid container 46 via connecting pieces 97 and 98, to which the pipes 48 are connected, via pipe 49.
  • the connecting pieces 97 and 98 are connected to the chambers 33 and 34 via bores.
  • the connection piece 75 is provided, which can be charged with inert gas N 2 , so that in the chambers 33, 34 and 35 there is only inert gas apart from the inert liquid and the electrolyte.
  • the non-conductive, disk-shaped molded part 96 can be arranged interchangeably in the disk-shaped intermediate wall 43 in order to be able to replace it with another disk-shaped part if necessary. In order to achieve longer gap paths between band 2 and breakthrough 85, the disk-shaped molded part 96 can be replaced by a cylindrical part which has a channel adapted to the cross section of the band 2. This creates a wider fluid lock.
  • the wall part 92 is also provided with a disk-shaped molded part 99, in which an opening 95 is provided for the band 2.
  • the lock arrangement 32 is constructed in the same way from disk-shaped wall parts and pipe pieces as the lock arrangement 31 shown in FIG. 2. From this it can be seen that more than three chambers can be used if necessary. The more chambers, the better the protection against diffusion of atmospheric air.
  • the tubular cell 1 and the electrolyte reservoir 12 can expediently be surrounded by a heating jacket in order to obtain higher deposition rates by using a heated electrolyte.
  • Thermometers are preferably attached to both ends of the tubular cell in order to measure temperature differences occurring in the direction of flow and to be able to compensate for them by heating the heating jacket accordingly.
  • the electrolyte can be circulated at any high flow rate via the two T-shaped connecting pieces, so that the current density can be selected to be significantly higher than when the electrolyte is at a standstill, as a result of which higher deposition rates can be achieved.
  • the two T-shaped connecting pieces can advantageously be used for flooding or flushing the tubular cell with a suitable solvent. This takes place with the aid of the inert liquid 26 in the inert storage container 27 after the valves 19 and 20 have been closed and the valves 21 and 22 have been opened with the aid of the circulating pump 25. Since this leads to the chambers 35 and 36, the inert liquid has to be closed via lines 41 and 102 of valve 100 and opening of valve 101 are returned to container 27.
  • Bores can be provided in the cover of the electrolyte reservoir 12 for introducing appropriate devices for measuring the temperature and conductivity and for attaching a level indicator.
  • the electrolyte storage container 12 is surrounded by an oil heating jacket container in which heating coils are located, thereby enabling indirect heating of the electrolytes which is gentle on the electrolyte liquid.
  • Toluene is preferably used as the inert liquid, which can be obtained by distillation from the electrolyte, which consists of toluene dissolved aluminum alkyl complex salt.
  • the disgusting trolyte preferably consists of 3 to 4 mol of inert liquid and 1 mol of aluminum alkyl complex salt, so that the inert liquid toluene can be relatively easily distilled off from the aluminum alkyl complex salt at a boiling point of 110 ° C., with completely oxygen-free and water-free toluene (inert liquid) being obtained as Inert liquid for the preparation of a new electrolyte as well as for use in the container 60 is very well suited.
  • the principle according to the invention can also be used if, for manufacturing reasons, the galvanization does not have to be carried out horizontally but vertically. This is necessary, for example, for the galvanic aluminizing of optical fibers, because on the one hand they can only be drawn using the vertical process and on the other hand they have to be protected immediately after manufacture. It is not possible to deflect or wind up the optical waveguide and then paint or galvanize it in a horizontal position because of its high sensitivity with regard to its mechanical strength.
  • Fig. 3 shows an embodiment of a system for aluminizing in the vertical method in principle.
  • the actual aluminizing cell which is designed as a tubular cell in accordance with FIG. 1, is designated by 103.
  • the strand-like material 105 is guided through the tubular cell 103.
  • T-shaped connecting pieces 106 and 107 are flanged on both sides of the aluminizing cell 103 in order to feed and discharge and redirect the aluminum electrolyte, as indicated by arrows 104.
  • the connecting pieces 106 and 107 are followed by lock arrangements 108 and 109.
  • the lock arrangement 108 contains an inert gas chamber 110, to which an inert gas, for example N 2 , is fed via a feed line 111.
  • the electrolyte 113 and possibly the inert liquid, which may still emerge at the top, can be drained off via a discharge nozzle 112 and fed to the electrolyte reservoir, in accordance with the exemplary embodiment according to FIG. 1 and a drain 117 can be flooded. These two chambers prevent air and moisture from entering the electroplating cell 103.
  • the inert liquid is conducted from bottom to top, as arrows 118 show. They work on the overflow principle.
  • the T-shaped connecting piece 107 is specially designed to prevent the electrolyte 113 from escaping downward through the insertion openings of the strand 105 to be aluminized. This is achieved in that the electrolyte 113 is fed to the aluminizing cell 103 at high speed, the flow being controlled in such a way that a certain negative pressure is created in a tube 119 and is compensated for with inert gas. For this reason, the T-shaped connecting piece 107 is followed by an inert gas chamber 127 of the lock arrangement 109, the inert gas being supplied via a connecting piece 121.
  • the electrolyte 113 which may possibly still escape through the pipe 119 can be discharged via a drainage connection 122 and fed to the electrolyte storage container.
  • the inert gas chamber 120 is adjoined by the two inert liquid chambers 123 and 124, the inflow via a connecting piece 125 and the outflow via a connecting piece 126. These two chambers also work on the overflow principle. Furthermore, a pipe section 127 (for sealing with inert gas) can be under an inert gas pressure via a connecting piece 128.
  • Fig. 4 shows a sluice head in the vertical mode of operation of the galvano-aluminizing system and passage of the material to be treated 129 from top to bottom, as indicated by a broken line.
  • 130 denotes a tubular cell in which there is an electrolyte 131.
  • the tube cell 130 is followed by a lock arrangement 132 which consists of at least three lamellar chambers 133 to 135. These chambers are under an inert gas overpressure which is low compared to the outside atmosphere or 129, depending on the inflow rate of the material to be coated.
  • the chambers 133 to 135 are supplied with inert gas, for example N 2 , via connecting pieces 136 to 141.
  • the chambers 133 to 135 and the inert gas space 142 can be under the same inert gas pressure or advantageously also under an increasing inert gas pressure from the inside out (ie from bottom to top), which results in a Inert gas purging action is created which blows the surface of the product 129 to be coated free of adhering air or contaminant atmosphere and at the same time closes off the galvano-aluminizing system from the outside atmosphere.
  • the inert rinse jet effect can be increased by more than three chambers. However, irrespective of the number of compartments, it can also be reinforced by the fact that the mouths of the compartments are positioned closer to each other towards the outside (still above), so that the flushing jet effect is enhanced. Furthermore, the blowing angle of the rinsing jet can also be changed by a different geometrical design of the chamber walls and its effect can thereby be optimized depending on the coating object surface structure.
  • FIG. 5 shows a discharge head corresponding to the feed head shown in FIG. 4.
  • the same parts are provided with the same reference numerals.
  • At the lower end of the tubular cell 130 there is a narrowing 143 adapted to the cross section of the material 129 to be treated, to which an inert gas lock arrangement 144 is connected.
  • the inert gas lock arrangement 144 like the infeed head according to FIG. 4, consists of at least three lamella-like central chambers 145 to 147, which supply inert gas via connecting pieces (not shown) be hit, as Fig. 5 shows.
  • FIG. 6 shows an embodiment of a discharge head in which the bubbling of inert gas into the tubular cell 130 can be excluded with certainty, the same parts being provided with the same reference numerals as in FIGS. 4 and 5.
  • a space 149 is formed above the constriction 143 by appropriately designing the lower end of the tubular cell 130, and is filled with liquid metal, for example. Gallium, for example, can be used as the liquid metal.
  • the space 149 is shielded from the tubular cell 130 by screens 150.
  • the liquid metal is expediently used for the electrical contacting of the coating object 129.
  • the basic principle of the discharge heads shown in FIGS. 5 and 6 is that the inert gas pressure of the chambers 145 to 147 keeps the electrolyte liquid column in equilibrium so that it cannot run out. This is tied to the narrowest possible outlet orifices for the coating object and requires manometric control of the discharge head.
  • the embodiment according to FIG. 6 has the advantage that electrolyte 131 still adhering to the glavanized material 129 is squeezed out.

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Abstract

A system for the galvanic deposition of aluminum incorporating a tubular cell through which goods to be treated can be moved in the axial direction. An electrolyte is pumped through the tubular cell preferably with the aid of an electrolyte circulating system which is self-contained. The electrolyte is gated out by means of T-shaped connecting components which are adjoined by airlock arrangements associated with the tubular cell.

Description

Die Erfindung bezieht sich auf eine Anlage zum galvanischen Abscheiden von Aluminium aus aprotischen, sauerstoff- und wasserfreien aluminiumorganischen Elektrolyten, auf draht-, rohr-oder bandförmigem Gut mit einer nach aussen abgeschlossenen Rohrzelle, durch die das zu behandelnde, kathodisch kontaktierte Gut in Achsrichtung entlang von Anoden bewegbar ist und durch die der Elektrolyt mit Hilfe eines geschlossenen Elektrolytumlaufsystems entgegen der Bewegungsrichtung des Gutes pumpbar ist, wobei an jedem Ende der Rohrzelle eine an das Ausströmen des Elektrolyten aus der Rohrzelle verhindernde Schleusenanordnung vorgesehen ist, welche aus mehreren Kammern besteht.The invention relates to a system for the galvanic deposition of aluminum from aprotic, oxygen-free and water-free aluminum-organic electrolytes, on wire, tube or tape-shaped material with a tube cell closed to the outside, through which the material to be treated, cathodically contacted, runs along in the axial direction is movable by anodes and through which the electrolyte can be pumped with the aid of a closed electrolyte circulation system against the direction of movement of the material, a lock arrangement being provided at each end of the tubular cell, which arrangement prevents the electrolyte from flowing out of the tubular cell and consists of several chambers.

Es sind Elektrolyseanlagen zum Plattieren von draht- und bandförmigen Materialien bekannt, bei denen das zu behandelnde Gut in senkrechten Schleifen durch ein Elektrolysebad geführt wird. Beispielsweise ist durch die DE-OS Nr. 1521076 eine Vorrichtung zum Plattieren eines Stranges aus Kunststoff bekannt, bei der der leitend vorbeschichtete Kunststoffstrang in einer Vielzahl von Schleifen mit Hilfe oben angeordneter Antriebs-und Kontaktierungsrollen und unten angeordneten Umlenkrollen durch ein Elektrolysebad geleitet wird, wobei im Elektrolysebad parallel zum Strangverlauf angeordnete senkrechte Anodenplatten vorgesehen sind.Electrolysis systems for plating wire and strip-shaped materials are known, in which the material to be treated is passed through an electrolysis bath in vertical loops. For example, DE-OS No. 1521076 discloses a device for plating a strand of plastic, in which the conductively precoated plastic strand is passed through an electrolysis bath in a plurality of loops with the aid of drive and contacting rollers arranged at the top and deflection rollers arranged at the bottom vertical anode plates are provided in the electrolysis bath parallel to the course of the strand.

Durch die US-PS Nr. 3865701 ist eine Anlage der eingangs beschriebenen Art zum Abscheiden von Metallen, insbesondere Edelmetallen, bekanntgeworden. Bei dieser bekannten Anlage ist zwar die Rohrzelle an beiden Enden durch Schleusenanordnungen abgeschlossen, doch kann nicht verhindert werden, dass Luftsauerstoff und Luftfeuchtigkeit mit dem Elektrolyten in Berührung kommen. Eine solche Anlage ist zum galvanischen Abscheiden von Aluminium weder vorgesehen noch dafür geeignet, da zum Aluminieren ein Elektrolyt verwendet werden muss, der unter sauerstoff- und wasserfreien Bedingungen hergestellt ist und soweit als praktisch möglich gehalten werden muss. Da der Zutritt von Luftsauerstoff und Luftfeuchtigkeit in zunehmenden grösseren Mengen eine erhebliche Verringerung der Leitfähigkeit und der Lebensdauer dieser Elektrolyten bewirkt, muss das Elektrolytbad bei der galvanischen Aluminierung unter Luftausschluss gehalten werden.A system of the type described at the outset for the deposition of metals, in particular precious metals, has become known from US Pat. No. 3,865,701. In this known system, the tube cell is closed at both ends by lock arrangements, but it cannot be prevented that atmospheric oxygen and air humidity come into contact with the electrolyte. Such a system is neither intended nor suitable for the galvanic deposition of aluminum, since an electrolyte must be used for aluminizing, which is produced under oxygen- and water-free conditions and must be kept as far as practically possible. Since the access of atmospheric oxygen and air humidity in larger and larger quantities causes a considerable reduction in the conductivity and the service life of these electrolytes, the electrolytic bath must be kept away from air during galvanic aluminizing.

Der Erfindung liegt daher die Aufgabe zugrunde, eine Anlage der eingangs beschriebenen Art derart auszubilden, dass nicht nur das ungewollte Austreten des Elektrolyten aus der Rohrzelle, sondern auch das Eindringen von Luftatmosphäre mit Sicherheit verhindert wird. Diese Aufgabe wird gemäss der Erfindung dadurch gelöst, dass die nach aussen abgeschlossene Rohrzelle mit einem Schutzgas (Inertgas) beaufschlagbar ist, dass die einzelnen Kammern der Schleusenanordnungen gegeneinander durch Inertgas und/oder Inertflüssigkeit abgedichtet sind und dass zum Ein- und Ausblenden sowie zum Umlenken der Bewegungsrichtung des strömenden Elektrolyten zwischen Rohrzelle und den Schleusenanordnungen T-förmige Verbindungsstücke angeordnet sind, die eine den Längsdurchgang des Elektrolyten verhindernde, den Elektrolytstrom senkrecht ablenkende Blende aufweisen, welche einen der Form des Querschnitts des zu behandelnden Gutes eng angepassten Durchbruch aufweist.The invention is therefore based on the object of designing a system of the type described at the outset in such a way that not only the undesired escape of the electrolyte from the tubular cell, but also the penetration of air atmosphere is reliably prevented. This object is achieved according to the invention in that a protective gas (inert gas) can be applied to the tubular cell, which is sealed off from the outside, that the individual chambers of the lock arrangements are sealed against one another by inert gas and / or inert liquid and that for fading in and out as well as for deflecting the Direction of movement of the flowing electrolyte between the tube cell and the lock arrangements T-shaped connecting pieces are arranged which have a diaphragm which prevents the longitudinal passage of the electrolyte and vertically deflects the electrolyte flow and which has an opening which is closely matched to the shape of the cross section of the material to be treated.

Vorzugsweise weist zumindest eine scheibenförmige Kammerwand der Schleusenanordnungen eine radiale, zu dem Durchbruch für den Durchgang des zu behandelnden Gutes führende Bohrung auf, die über einen Anschlussstutzen an einen Inertflüssigkeitskreislauf zum gegenseitigen Abdichten der Kammern und Waschen des behandelten Gutes angeschlossen ist. Überdie Bohrung wird der Durchbruch in- der Kammerwand so mit Inertflüssigkeit versorgt, dass man von einer Flüssigkeitsschleuse sprechen kann, die praktisch luftdicht ist.At least one disk-shaped chamber wall of the lock arrangements has a radial bore leading to the opening for the passage of the material to be treated, which is connected via a connecting piece to an inert liquid circuit for mutual sealing of the chambers and washing of the material to be treated. The opening in the chamber wall is supplied with inert liquid via the bore in such a way that one can speak of a liquid lock that is practically airtight.

Ferner ist es zweckmässig, dass die Inertflüssigkeitzum Waschen des behandelten Gutes aus dem Elektrolyten durch Destillation mit Hilfe eines Verdampfers gewonnen und über eine Bohrung der Kammerwand zugeführt wird. Dann werden die anderen Inertflüssigkeiten zum reinen Abdichten nicht verschmutzt.It is furthermore expedient for the inert liquid for washing the treated material to be obtained from the electrolyte by distillation using an evaporator and fed through a bore in the chamber wall. Then the other inert liquids for pure sealing are not contaminated.

Um eine weitere gute Abdichtung zu erhalten, ist es vorteilhaft, dass der Durchbruch in der Blende durch einen sich über die gesamte Länge des Verbindungsstückes erstreckenden Kanal gebildet ist, dessen lichte Weite-dem Querschnitt des zu behandelnden Gutes angepasst ist und dessen sich vor die Blende erstreckendes Teil nur eine für die Festigkeit erforderliche Wandstärke aufweist, während der sich hinter die Blende erstreckende Teil der lichten Weite des Verbindungsstückes angepasst ist.In order to obtain a further good seal, it is advantageous that the opening in the panel is formed by a channel that extends over the entire length of the connecting piece, the clear width of which is adapted to the cross section of the material to be treated and the front of which is in front of the panel extending part has only a wall thickness required for strength, while the part extending behind the panel is adapted to the clear width of the connecting piece.

Gemäss einer Weiterbildung der Erfindung ist die Rohrzelle mit den T-förmigen Verbindungsstücken zum senkrechten Durchgang des zu aluminierenden Gutes senkrecht angeordnet.According to a further development of the invention, the tubular cell with the T-shaped connecting pieces for the vertical passage of the material to be aluminized is arranged vertically.

In der Zeichnung ist ein Ausführungsbeispiel der Anlage näher erläutert. Es zeigen:

  • Fig. 1 eine Anlage zum galvanischen Abscheiden im Prinzip;
  • Fig. 2 einen Schnitt durch eine Rohrzelle mit T-förmigem Verbindungsstück und Schleusenanordnung;
  • Fig. 2a eine Schnittansicht nach der Linie Ila-Ila der Fig. 2;
  • Fig. 2b eine Ansicht auf eine Schleusenanordnung in Pfeilrichtung Ilb;
  • Fig. 2c eine Schnittansicht nach der Linie IIcllc;
  • Fig. 2d eine Schnittansicht nach der Linie lld-Ild;
  • Fig. 2e eine Schnittansicht nach der Linie llelle;
  • Fig. 2f eine Schnittansicht nach der Linie Ilf-Ilf;
  • Fig. 2g eine Schnittansicht nach der Linie IIg-Ilg;
  • Fig. 3 eine vertikale Durchlauf-Aluminierzelle;
  • Fig. 4 einen Einschleuskopf einer vertikalen Durchlauf-Aluminierzelle;
  • Fig. 5 einen Ausschleuskopf einer vertikalen Durchlauf-Aluminierzelle, und
  • Fig. 6 einen anderen Ausschleuskopf einer vertikalen Durchlauf-Aluminierzelle.
In the drawing, an embodiment of the system is explained in more detail. Show it:
  • 1 shows a system for galvanic deposition in principle;
  • 2 shows a section through a tubular cell with a T-shaped connecting piece and lock arrangement;
  • Fig. 2a is a sectional view along the line Ila-Ila of Fig. 2;
  • 2b shows a view of a lock arrangement in the direction of arrow Ilb;
  • 2c is a sectional view along the line IIcllc;
  • 2d is a sectional view along the line lld-Ild;
  • 2e shows a sectional view along the line IIelle;
  • 2f shows a sectional view along the line Ilf-Ilf;
  • 2g shows a sectional view along the line IIg-Ilg;
  • 3 shows a vertical continuous aluminizing cell;
  • 4 shows a feed head of a vertical continuous aluminizing cell;
  • 5 shows a discharge head of a vertical continuous aluminizing cell, and
  • Fig. 6 shows another discharge head of a vertical continuous aluminizing cell.

Die in Fig. 1 dargestellte Bandaluminieranlage weist als Aluminierzelle eine innen isolierte Rohrzelle 1 auf, durch die ein zu aluminierendes Band 2 gezogen wird, welches von einer Rolle 3 einer Abspuleinheit 4 abgezogen und auf eine Rolle 5 einer Aufspuleinheit 6 nach der Aiuminierungaufgewickelt wird. Innerhalb der Rohrzelle 1 sind zu beiden Seiten des Bandes 2 bandförmige Anoden 7 angeordnet, wie insbesondere Fig. 2a zeigt. Die bandförmigen Anoden 7 werden mit Hilfe von Kontaktierungsstiften 8 kontaktiert, welche in ringförmigen Anodenhaltern 9 angeordnet sind, wie näher aus Fig. 2g zu ersehen ist. Die Anodenhalter 9 sind bei dem in Fig. 1 dargestellten Ausführungsbeispiel, an beiden Enden der Rohrzelle 1 angeordnet und schliessen mit dem Flansch der Rohrzelle 1 dicht ab. Bei längeren Rohrzellen 1 ist es zweckmässig, dass im Verlauf der Rohrzelle 1 zumindest noch ein weiterer Anodenhalter 9 mit Kontaktierungsstiften 8 vorgesehen wird.The Bandaluminieranlage shown in FIG. 1, as Aluminierzelle an internally insulated tubular cell 1, through which a drawn to aluminierendes band 2, which drawn from a roll 3 of an unreeling unit 4 and a roll 5 an A UFS p MISS h eit 6 after the Aiumination is wound up. Band-shaped anodes 7 are arranged inside the tube cell 1 on both sides of the band 2, as shown in particular in FIG. 2a. The band-shaped anodes 7 are contacted by means of contacting pins 8, which are arranged in ring-shaped anode holders 9, as can be seen in more detail in FIG. 2g. In the exemplary embodiment shown in FIG. 1, the anode holders 9 are arranged at both ends of the tubular cell 1 and close tightly with the flange of the tubular cell 1. In the case of longer tubular cells 1, it is expedient that at least one further anode holder 9 with contacting pins 8 is provided in the course of the tubular cell 1.

An beiden Enden der Rohrzelle 1, und zwar nach den Anodenhaltern 9, sind T-förmige Verbindungsstücke 10 angeflanscht, mit deren Hilfe Elektrolyt 11 aus einem Elektrolytvorratsbehälter 12 durch die Rohrzelle 1 entgegengesetzt der Bewegungsrichtung des Bandes 2 mit Hilfe einer Pumpe 13 sowie Rohrleitungen 14 und 15 gepumpt werden kann. Mit Hilfe eines Strömungsmessers 16 kann die Elektrolytgeschwindigkeit erfasst werden.At both ends of the tubular cell 1, namely after the anode holders 9, T-shaped connecting pieces 10 are flanged, with the aid of which electrolyte 11 from an electrolyte reservoir 12 through the tubular cell 1 opposite the direction of movement of the strip 2 with the aid of a pump 13 and pipes 14 and 15 can be pumped. With the help of a flow meter 16, the electrolyte speed can be recorded.

Die T-förmigen Verbindungsstücke 10 sind mit einer schrägen Blende 17 versehen, um den über Stutzen 18 ein- bzw. austretenden Elektrolyten um 90° möglichst strömungsgünstig umzulenken, so dass ein geschlossener Elektrolytkreislauf entsteht, welcher jedoch mit Hilfe der Ventile 19 und 20 unterbrochen werden kann, beispielsweise wenn die Rohrzelle 1 in Betrieb genommen wird. In diesem Falle kann über einen parallelen Kreislauf über geöffnete Ventile 21 und 22 und Rohrleitungen 23 und 24 mit Hilfe einer Förderpumpe 25 Inertflüssigkeit 26 aus einem Inertflüssigkeitsvorratsbehälter 27 durch die Rohrzelle 1 sowie Verbindungsstücke 10 gepumpt werden, einmal um die atmosphärische Luft aus der Rohrzelle 1 zu entfernen, bevor der Elektrolyt 11 unter Schutzgasatmosphäre N2 durchgepumpt wird, und zum anderen um - nach abgelassenen AI-Elektrolyten -die Rohrzelle mit Inertflüssigkeit reinigen zu können. Vorteilhafterweise wird der durch die Leitung 15 in Pfeilrichtung strömende Elektrolyt nicht unmittelbar in den Elektrolytvorratsbehälter 12 eingeleitet, sondern über ein Filter 28, um Verunreinigungen des Elektrolyten 11 in Form von Feststoffpartikeln abzutrennen.The T-shaped connecting pieces 10 are provided with an oblique diaphragm 17 in order to deflect the electrolyte entering or exiting via the connecting piece 18 by 90 ° as aerodynamically as possible, so that a closed electrolyte circuit is formed, which, however, is interrupted by means of the valves 19 and 20 can, for example when the tube cell 1 is put into operation. In this case, via a parallel circuit via open valves 21 and 22 and pipes 23 and 24 with the aid of a feed pump 25, inert liquid 26 can be pumped from an inert liquid storage container 27 through the pipe cell 1 and connecting pieces 10, once in order to supply the atmospheric air from the pipe cell 1 remove before the electrolyte 11 is pumped through under a protective gas atmosphere N 2 , and secondly to be able to clean the tube cell with inert liquid after the Al electrolytes have been drained. Advantageously, the electrolyte flowing through the line 15 in the direction of the arrow is not introduced directly into the electrolyte reservoir 12, but via a filter 28 in order to separate contaminants from the electrolyte 11 in the form of solid particles.

Der Elektrolytvorratsbehälter 12 ist selbstverständlich luftdicht mit Hilfe eines Deckels 29 abgeschlossen. Der Elektrolytvorratsbehälter 12 ist ferner mit einem Überdruckventil 30 ausgestattet sowie entsprechenden, luftdicht abgeschlossenen Öffnungen zum Einführen der Rohrleitungen 14 und 15. Selbstverständlich steht auch der Elektrolytvorratsbehälter 12 unter Schutzgasatmosphäre.The electrolyte reservoir 12 is of course sealed airtight with the help of a lid 29. The electrolyte reservoir 12 is also equipped with a pressure relief valve 30 and corresponding, airtight openings for introducing the pipelines 14 and 15. Of course, the electrolyte reservoir 12 is also under a protective gas atmosphere.

Die Blenden 17 der T-förmigen Verbindungsstücke sind zum Durchgang des Bandes 2 mit entsprechenden Durchbrüchen versehen, und zwar sind diese Durchbrüche möglichst eng dem Querschnitt des Bandes 2 angepasst, um möglichst zu vermeiden, dass einerseits Elektrolyt aus der Rohrzelle 1 bzw. aus den T-förmigen Verbindungsstükken nach aussen tritt bzw. atmosphärische Luft eindringt. Da dies jedoch nur zum Teil möglich ist, sind an beiden Enden der Rohrzelle 1 bzw. der sich daran anschliessenden Verbindungsstücke 10 Schleusenanordnungen 31 bzw. 32 angeordnet, wobei gemäss Fig. 1 die Schleusenanordnung 31 drei Kammern 33 bis 35 aufweist, während die Schleusenanordnung 32 sogar fünf Kammern 36 bis 40 aufweist. In den Kammern 35 und 36 der Schleusenanordnungen 31 und 32 wird der durch die Durchbrüche in den Blenden 17 austretende Elektrolyt aufgefangen und über Rohrleitungen 41 und 42 dem Elektrolytvorratsbehälter 12 wieder zugeführt, und zwar vor dem Filter 28.The diaphragms 17 of the T-shaped connecting pieces are provided with corresponding openings for the passage of the band 2, and these openings are adapted as closely as possible to the cross section of the band 2 in order to avoid as far as possible that electrolyte from the tube cell 1 or from the T -shaped connecting pieces come out or atmospheric air penetrates. However, since this is only possible in part, lock arrangements 31 and 32 are arranged at both ends of the tube cell 1 and the connecting pieces 10 connected thereto, whereby according to FIG. 1 the lock arrangement 31 has three chambers 33 to 35, while the lock arrangement 32 even has five chambers 36 to 40. In the chambers 35 and 36 of the lock arrangements 31 and 32, the electrolyte escaping through the openings in the diaphragms 17 is collected and returned to the electrolyte reservoir 12 via pipes 41 and 42, specifically in front of the filter 28.

Als besonders vorteilhaft hat sich erwiesen, wenn die Schleusenanordnungen 31 und 32 Flüssigkeitsschleusen aufweisen, die besonders dicht sind und die sogar das Eindiffundieren von atmosphärischer Luft in die Rohrzelle 1 verhindern.It has proven to be particularly advantageous if the lock arrangements 31 and 32 have liquid locks which are particularly tight and which even prevent atmospheric air from diffusing into the tube cell 1.

Eine wirksame Flüssigkeitsschleuse kann beispielsweise dadurch gebildet werden, dass die vorzugsweise aus Rohrstücken und Trennwänden zusammengesetzten Kammern der Schleusenanordnungen 31 und 32teilweise mit Inertflüssigkeiten geflutet werden, was anhand der Fig. 2 noch näher erläutert werden wird. Bei dem Ausführungsbeispiel nach Fig. 1 ist beispielsweise eine scheibenförmige Zwischenwand 43, welche mit einem Durchbruch zum Durchgang des Bandes 2 versehen ist, mit einer zu diesem Durchbruch führenden Bohrung versehen, an die eine Leitung 44 angeschlossen ist, welche über ein Ventil 45 zu einem Inertflüssigkeitsbehälter 46 führt. Mit Hilfe einer Pumpe 47 wird die Inertflüssigkeit dem Durchbruch in der Zwischenwand 43 so zugeführt, dass der Zwischenraum zwischen Band 2 und Durchbruch vollständig ausgefüllt wird. Die aus dem Spalt zwischen Band und Durchbruch austretende Inertflüssigkeit wird in den Kammern 33 und 34 gesammelt und über Rohrleitungen 48 und 49 dem Inertflüssigkeitsbehälter 46 wieder zugeführt.An effective liquid lock can be formed, for example, by partially flooding the chambers of the lock arrangements 31 and 32, which are preferably composed of pipe pieces and partitions, with inert liquids, which will be explained in more detail with reference to FIG. 2. In the embodiment according to FIG. 1, for example, a disk-shaped intermediate wall 43, which is provided with a breakthrough for the passage of the strip 2, is provided with a bore leading to this breakthrough, to which a line 44 is connected, which leads to a via a valve 45 Inert liquid container 46 leads. With the help of a pump 47, the inert liquid is fed to the opening in the intermediate wall 43 in such a way that the space between the band 2 and the opening is completely filled. The inert liquid emerging from the gap between the strip and the breakthrough is collected in the chambers 33 and 34 and fed back to the inert liquid container 46 via pipes 48 and 49.

In gleicher Weise wie die Zwischenwand 43 der beiden Kammern 33 und 34 der Schleusenanordnung 31 sind auch die Zwischenwände 50 und 51 der Schleusenkammern 37 und 38 bzw. 39 und 40 ausgebildet, wobei die Anschlussbohrung der scheibenförmigen Zwischenwand 50 über eine Rohrleitung 52 und Ventil 53 mit einem Verdampfer 54 in Verbindung steht. In diesem Kreislauf ist eine Förderpumpe 55 vorgesehen, mit der die aus dem Elektrolyten 11 durch Destillation gewonnene Inertflüssigkeit über die Radialbohrung der Zwischenwand 50 in den Zwischenraum zwischen Band 2 und Durchbruch gepumpt werden kann. Über Rohrleitungen 56 wird die sich in den Kammern 37 und 38 der Schleusenanordnung 32 ansammelnde Inertflüssigkeit in den Elektrolytvorratsbehälter 12 zurückgeführt. Dieser Inertflüssigkeitskreislauf hat hauptsächlich die Aufgabe, das aluminierte Warengut mit Inertflüssigkeit von anhaftenden AI-Elektrolyten zu reinigen.In the same way as the intermediate wall 43 of the two chambers 33 and 34 of the lock arrangement 31, the intermediate walls 50 and 51 of the lock chambers 37 and 38 or 39 and 40 are also formed, the connecting bore of the disk-shaped intermediate wall 50 being connected via a pipeline 52 and valve 53 an evaporator 54 is connected. In this circuit, a feed pump 55 is provided, with which the inert liquid obtained by distillation from the electrolyte 11 can be pumped through the radial bore of the intermediate wall 50 into the space between band 2 and the breakthrough. The inert liquid that accumulates in the chambers 37 and 38 of the lock arrangement 32 is returned to the electrolyte reservoir 12 via pipes 56. The main task of this inert liquid circuit is to clean the aluminized goods from adhering Al electrolytes with inert liquid.

Das ist sehr wichtig für einen ungestörten und möglichst langen Betrieb der Anlage. Konstanz des Elektrolyten in Zusammensetzung und Qualität sowie Minimum an Elektrolytverlust durch Austrag mit der beschichteten Ware sind hierbei sehr wesentliche und wichtige Faktoren. Beiden trägt das den Verdampfer 54 enthaltene System Rechnung.This is very important for an undisturbed and as long as possible operation of the plant. Constancy of the electrolyte in composition and quality as well as minimum loss of electrolyte due to discharge with the coated goods are very important and important factors. The system containing the evaporator 54 takes both into account.

Dadurch, dass stets nur eine kleine Volumenmenge an Inertflüssigkeit von wenigen Litern mittels Kondensation oder Destillation aus der grossen Elektrolytvorratsmenge für diesen Spül- bzw. Waschvorgang ausgekreist und mit verhältnismässig kleine Mengen an abgespülten Originalelektrolyten beladen in den Elektrolytvorratsbehälter 12 wieder zurückgeführt werden kann, bleiben Zusammensetzung und Menge des Elektrolyten im Vorratsbehälter 12 praktisch konstant und gleichzeitig wird die Menge an Elektrolytaustrag durch das zu beschichtende Band 2 auf ein Minimum herabgesetzt (das Spülen der Oberfläche des Bandes 2 mit reiner Inertflüssigkeit stellt eine hochwirksame Reinigung derselben von anhaftendem Elektrolyten dar).Because only a small volume of inert liquid of a few liters is removed from the large electrolyte supply for this rinsing or washing process by means of condensation or distillation and loaded with relatively small amounts of rinsed original electrolyte can be returned to the electrolyte storage container 12, composition and The amount of electrolyte in the reservoir 12 is practically constant and at the same time the amount of electrolyte discharge through the band 2 to be coated is reduced to a minimum (rinsing the surface of the band 2 with pure inert liquid is a highly effective cleaning of the adhering electrolyte).

Die minimalen Reste hochverdünnten Elektrolyten, die eventuell beim Verlassen der Kammer 38 noch an der Oberfläche des Bandes 2 anhaften, werden dann in den Kammern 39 und 40 mittels der Zwischenwand- 51 -Düse mit Inertflüssigkeit aus dem Vorratsbehälter 60 noch ganz entfernt.The minimal residues of highly diluted electrolytes, which may still adhere to the surface of the band 2 when leaving the chamber 38, are then completely removed from the storage container 60 in the chambers 39 and 40 by means of the intermediate wall 51 nozzle with inert liquid.

Das Auskreisen eines kleinen Volumenteiles Inertflüssigkeit aus dem grossen Elektrolytvorrat zum Zwecke des Rückspülens von Originalelektrolyt von der Oberfläche des beschichteten Objekts in den Elektrolytvorratsbehälter 12 stellt ein sehr wesentliches und wirksames Moment der erfindungsgemässen Anlage dar.The removal of a small volume of inert liquid from the large electrolyte reservoir for the purpose of backwashing the original electrolyte from the surface of the coated object into the electrolyte reservoir 12 represents a very essential and effective moment of the system according to the invention.

In entsprechender Weise ist auch die scheibenförmigeZwischenwand 51 an eine Rohrleitung 57 angeschlossen, die über ein Ventil 58 und Pumpe 59 mit einem weiteren Inertflüssigkeitsbehälter 60 in Verbindung steht. Der Rücklauf der Inertflüssigkeit aus den Kammern 39 und 40 erfolgt über eine Rohrleitung 61.In a corresponding manner, the disk-shaped intermediate wall 51 is connected to a pipeline 57, which is connected to a further inert liquid container 60 via a valve 58 and pump 59. The return flow of the inert liquid from the chambers 39 and 40 takes place via a pipeline 61.

Die Rolle 3 der Abspuleinheit 4 befindet sich ebenfalls in einem abgeschlossenen Behälter 62, der von Inertgas N2 beaufschlagt und teilweise mit Inertflüssigkeit gefüllt ist. Der Behälter 62 steht über eine Rohrleitung 63, ein Ventil 64 sowie eine Förderpumpe 65 mit einem Inertflüssigkeitsbehälter 66 in Verbindung. Im Behälter 62 ist ein Überlauf 67 für die Inertflüssigkeit vorgesehen. Hinter dem Überlauf 67 ist eine Abftussrohrteitung 68 angebracht, die die überlaufende Inertflüssigkeit in den Inertflüssigkeitsbehälter 66 zurückführt.The roll 3 of the unwinding unit 4 is also located in a closed container 62 which is charged with inert gas N 2 and is partially filled with inert liquid. The container 62 is connected to an inert liquid container 66 via a pipeline 63, a valve 64 and a feed pump 65. An overflow 67 for the inert liquid is provided in the container 62. Behind the overflow 67, a discharge pipe line 68 is attached, which leads the overflowing inert liquid back into the inert liquid container 66.

Der Behälter 62 ist ferner noch über ein rohrförmiges Verbindungsstück 69 mit der Schleusenanordnung 31 dichtend verbunden. Auch das Verbindungsstück 69 hat einen Längsdurchbruch für das zu aluminierende Band 2 und kann mit Hilfe einer Rohrleitung 70 an die Rohrleitung 44 des Inertflüssigkeitskreislaufes der Schleusenanordnung 31 angeschlossen werden.The container 62 is also still sealingly connected to the lock arrangement 31 via a tubular connecting piece 69. The connecting piece 69 also has a longitudinal opening for the band 2 to be aluminized and can be connected to the pipe 44 of the inert liquid circuit of the lock arrangement 31 by means of a pipe 70.

Überzu beiden Seiten des Bandes 2 angeordnete Kontaktierungsrollen 71 und 72 wird das Band 2 kontaktiert. Der Übersicht halber ist nur eine Kontaktierungsrolle gezeichnet, welche mit dem negativen Pol der Stromquelle verbunden ist.The tape 2 is contacted via contacting rollers 71 and 72 arranged on both sides of the tape 2. For the sake of clarity, only one contacting roller is drawn, which is connected to the negative pole of the power source.

Wie Fig. 1 zeigt, sind die Kontaktierungsrollen 71 innerhalb des Behälters 62 angeordnet und durch eine Zwischenwand 73 abgesondert. Mit Hilfe einer Rohrleitung 74, die an die Rohrleitung 49 angeschlossen ist, kann überschüssige Inertflüssigkeit in den Inertflüssigkeitsbehälter 46 abgeleitet werden.1 shows, the contacting rollers 71 are arranged within the container 62 and separated by an intermediate wall 73. With the help of a pipeline 74 which is connected to the pipeline 49, excess inert liquid can be discharged into the inert liquid container 46.

Anschlussstutzen 75 und 76 bzw. 77 und 78 der Schleusenanordnungen 31 und 32 dienen zum Anschluss an einen Inertgasvorratsbehälter, was in der Zeichnung der Übersicht halber nicht dargestellt ist. Selbstverständlich erfolgt der Anschluss über entsprechende Ventile.Connection pieces 75 and 76 or 77 and 78 of the lock arrangements 31 and 32 are used for connection to an inert gas storage container, which is not shown in the drawing for the sake of clarity. Of course, the connection is made via appropriate valves.

Fig. 2 zeigt einen Schnitt durch die Schleusenanordnung 31, das T-förmige Verbindungsstück 10, den Anodenhalter 9 und einen Teil der Rohrzelle 1. Fig. 2a bis Fig. 2g zeigen verschiedene Schnittansichten der Fig. 2, wobei gleiche Teile mit gleichen Bezugszeichen versehen sind.2 shows a section through the lock arrangement 31, the T-shaped connecting piece 10, the anode holder 9 and part of the tubular cell 1. FIGS. 2a to 2g show different sectional views in FIG. 2, the same parts being provided with the same reference numerals are.

Wie Fig. 2a zeigt, sind bei dem gewählten Ausführungsbeispiel zu beiden Seiten des zu aluminierenden Bandes 2 Anoden 7 angeordnet, die höher als die Breite des Bandes 2 sind. Das Rohrinnere ist vollständig mit Elektrolyt gefüllt. Bei dem gewählten Ausführungsbeispiel wird das Band 2 an beiden Seiten vollständig aluminiert. Sollen irgendwelche Teile des Bandes nicht mit einer Aluminiumschicht bedeckt werden, so müssen diese Teile abgedeckt werden, beispielsweise durch Einschieben eines entsprechenden Formkörpers in das Innere der Rohrzelle 1, so dass nur die von der entsprechenden Abdeckung freigegebenen Teile des Bandes aluminiert werden.As shown in FIG. 2a, in the selected embodiment, anodes 7 are arranged on both sides of the strip to be aluminized, which anodes 7 are larger than the width of the strip 2. The inside of the pipe is completely filled with electrolyte. In the selected embodiment, the band 2 is completely aluminized on both sides. If any parts of the strip are not to be covered with an aluminum layer, these parts must be covered, for example by inserting a corresponding shaped body into the interior of the tubular cell 1, so that only the parts of the strip released by the corresponding cover are aluminized.

Wie Fig. 2 und 2g zeigen, ist der Anodenhalter 9 kreisringförmig ausgebildet und zwischen den Anschlussflanschen der Rohrzelle 1 und des T-förmigen Verbindungsstückes 10 unter Zwischenschaltung von Dichtungsringen 79 angeordnet. Wie Fig. 2g zeigt, sind die Kontaktierungsstifte 8 über isolierende Durchführungen zu den Anoden 7 geführt und drücken diese gegen einen entsprechend ausgebildeten Anodenträger 81 aus Isolierstoff. Der Anodenträger 81 weist eine entsprechende Aussparung 82 für das Band 2 auf und dient zur Führung desselben.As shown in FIGS. 2 and 2g, the anode holder 9 is annular and is arranged between the connecting flanges of the tubular cell 1 and the T-shaped connecting piece 10 with the interposition of sealing rings 79. As FIG. 2g shows, the contacting pins 8 are guided to the anodes 7 via insulating bushings and press them against an appropriately designed anode carrier 81 made of insulating material. The anode carrier 81 has a corresponding recess 82 for the band 2 and serves to guide the same.

Wie Fig. 2 zeigt, kann das innen isolierte T-förmige Verbindungsstück 10 ein normales Rohr mit T- Form sein, welches den gleichen Durchmesser wie die Rohrzelle 1 aufweist. Zur Bildung der Blende 17 ist in das Verbindungsstück 10 ein nichtleitendes Einsatzteil 83 mit einem Flansch 84 eingeschoben, wobei die schräge Fläche die eigentliche Blende bildet. Anstelle einer schrägen Fläche kann auch eine gekrümmte Fläche verwendet sein. Der hinter der schrägen Fläche liegende Teil des Einsatzteiles 83 füllt das Zwischenstück 10 voll aus und weist nur einen dem Bandquerschnitt eng angepassten Durchbruch 85 zum Durchtritt des Bandes 2 auf. Dieser Durchbruch 85 erstreckt sich jedoch über die gesamte Länge des Einsatzteiles 83 und ist vor der Blende 17 von einem rohrförmigen Teil 86 umgeben, wie Fig. 2f zeigt. Die Wandstärke des Teiles 86 ist so knapp bemessen, dass der Elektrolyt zwar frei strömen kann, jedoch das Teil die erforderliche Festigkeit erhält.As shown in FIG. 2, the internally insulated T-shaped connecting piece 10 can be a normal tube with a T-shape, which has the same diameter as the tube cell 1. To form the aperture 17 is in the connector 10 non-conductive insert 83 inserted with a flange 84, the inclined surface forming the actual panel. Instead of an inclined surface, a curved surface can also be used. The part of the insert part 83 lying behind the inclined surface completely fills the intermediate piece 10 and has only one opening 85, which is closely adapted to the strip cross section, for the strip 2 to pass through. However, this opening 85 extends over the entire length of the insert part 83 and is surrounded in front of the cover 17 by a tubular part 86, as shown in FIG. 2f. The wall thickness of the part 86 is so small that the electrolyte can flow freely, but the part is given the required strength.

Der Einsatzteil 83 ist dicht im Verbindungsstück 10 eingeschoben, wobei zwischen dem Flansch 84 des Einsatzteiles 83 und dem Flansch des Verbindungsstückes 10 ein scheibenförmiger Wandteil 87 der Schleusenanordnung 31 angeordnet ist, der den Anschlussstutzen 76 für das Inertgas N2 aufweist.The insert part 83 is pushed tightly into the connecting piece 10, a disk-shaped wall part 87 of the lock arrangement 31 being arranged between the flange 84 of the insert part 83 and the flange of the connecting piece 10 and having the connecting piece 76 for the inert gas N 2 .

Der Anschlussstutzen 76 ist über eine nichtbezeichnete Bohrung mit der Kammer 35 verbunden, die durch ein weiteres scheibenförmiges Wandteil 88 und ein Rohrstück 89 gebildet ist. Der scheibenförmige Wandteil 87 besitzt ferner noch einen Anschlussstutzen 90 zum Anschluss der Rohrleitung 42 gemäss Fig. 1. In der Kammer 35 kann sich der aus dem Verbindungsstück 10 durch den Spalt zwischen Band 2 und Durchbruch 85 austretende Elektrolyt sammeln, der dann über den Anschlussstutzen 90 und Rohrleitungen 41 und 42 dem Elektrolytvorratsbehälter zugeführt wird.The connecting piece 76 is connected to the chamber 35 via a bore, not shown, which is formed by a further disk-shaped wall part 88 and a pipe section 89. The disk-shaped wall part 87 also has a connecting piece 90 for connecting the pipeline 42 according to FIG. 1. In the chamber 35, the electrolyte emerging from the connecting piece 10 through the gap between the band 2 and the opening 85 can collect, which then passes through the connecting piece 90 and piping 41 and 42 is supplied to the electrolyte reservoir.

Die Kammer 34 der Schleusenanordnung 31 wird durch die Wandteile 43 und 88 gebildet und die Kammer33 durch den Wandteil 43 sowie einen Wandteil 92. Die beiden Kammern 33 und 34 dienen zum Sammeln der Inertflüssigkeit, die über einem Anschlussstutzen 93 und eine Radialbohrung 94 einem Durchbruch 95 eines nichtleitenden scheibenförmigen Formteiles 96 zugeführt wird. An dem Anschlussstutzen 93 ist die Leitung 44 gemäss Fig. 1 angeschlossen, über die mit Hilfe der Pumpe 47 Inertflüssigkeit über den Kanal 94 in den Spalt zwischen dem durchgeführten Band 2 und dem Durchbruch 95 zugeführt wird und zwar so, dass dieser vollständig mit Inertflüssigkeit ausgefüllt ist. Auf diese Weise ergibt sich eine 100%ige Dichtung gegen die atmosphärische Luft. Die sich am Grunde der Kammern 34 und 33 sammelnde Inertflüssigkeit wird über Anschlussstutzen 97 und 98, an denen die Rohrleitungen 48 angeschlossen sind, über Rohrleitung 49 in den Inertflüssigkeitsbehälter 46 abgelassen. Wie aus Fig. 2 zu ersehen ist, stehen die Anschlussstutzen 97 und 98 mit den Kammern 33 und 34 über Bohrungen in Verbindung. In dem Wandteil 92 ist der Anschlussstutzen 75 vorgesehen, der mit Inertgas N2 beaufschlagt werden kann, so dass sich in den Kammern 33,34 und 35 ausser der Inertflüssigkeit und dem Elektrolyten nur Inertgas befindet. Das nichtleitende scheibenförmige Formteil 96 kann auswechselbar in der scheibenförmigen Zwischenwand 43 angeordnet sein, um es durch ein anderes scheibenförmiges Teil im Bedarfsfalle ersetzen zu können. Um längere Spaltwege zwischen Band 2 und Durchbruch 85 zu erzielen, kann das scheibenförmige Formteil 96 durch ein zylindrisches Teil ersetzt werden, das einen dem Querschnitt des Bandes 2 angepassten Kanal aufweist. Auf diese Weise ergibt sich eine breitere Flüssigkeitsschleuse.The chamber 34 of the lock arrangement 31 is formed by the wall parts 43 and 88 and the chamber 33 by the wall part 43 and a wall part 92. The two chambers 33 and 34 serve to collect the inert liquid, which has an opening 95 through a connecting piece 93 and a radial bore 94 a non-conductive disc-shaped molded part 96 is supplied. The line 44 according to FIG. 1 is connected to the connecting piece 93, via which the inert liquid is fed with the help of the pump 47 via the channel 94 into the gap between the band 2 carried out and the opening 95 in such a way that it is completely filled with inert liquid is. This creates a 100% seal against atmospheric air. The inert liquid collecting at the bottom of the chambers 34 and 33 is drained into the inert liquid container 46 via connecting pieces 97 and 98, to which the pipes 48 are connected, via pipe 49. As can be seen from FIG. 2, the connecting pieces 97 and 98 are connected to the chambers 33 and 34 via bores. In the wall part 92, the connection piece 75 is provided, which can be charged with inert gas N 2 , so that in the chambers 33, 34 and 35 there is only inert gas apart from the inert liquid and the electrolyte. The non-conductive, disk-shaped molded part 96 can be arranged interchangeably in the disk-shaped intermediate wall 43 in order to be able to replace it with another disk-shaped part if necessary. In order to achieve longer gap paths between band 2 and breakthrough 85, the disk-shaped molded part 96 can be replaced by a cylindrical part which has a channel adapted to the cross section of the band 2. This creates a wider fluid lock.

Wie insbesondere Fig. 2b zeigt, ist auch das Wandteil 92 mit einem scheibenförmigen Formteil 99 versehen, in dem ein Durchbruch 95 für das Band 2 vorgesehen ist.As shown in FIG. 2b in particular, the wall part 92 is also provided with a disk-shaped molded part 99, in which an opening 95 is provided for the band 2.

Die Schleusenariordnung 32 ist in gleicher Weise aus scheibenförmigen Wandteilen und Rohrstücken aufgebaut, wie die in Fig. 2 dargestellte Schleusenanordnung 31. Daraus ist zu ersehen, dass im Bedarfsfalle mehr als drei Kammern verwendet werden können. Je mehr Kammern, um so besser ist der Schutz gegen Eindiffundieren von atmosphärischer Luft.The lock arrangement 32 is constructed in the same way from disk-shaped wall parts and pipe pieces as the lock arrangement 31 shown in FIG. 2. From this it can be seen that more than three chambers can be used if necessary. The more chambers, the better the protection against diffusion of atmospheric air.

Die Rohrzelle 1 und der Elektrolytvorratsbehälter 12 können zweckmässigerweise mit einem Heizmantel umgeben sein, um höhere Abscheidungsraten durch Verwendung eines aufgeheizten Elektrolyten zu erhalten. Vorzugsweise sind an beiden Enden der Rohrzelle 1 Thermometer angebracht, um in Strömungsrichtung eintretende Temperaturunterschiede messen und durch entsprechende Beheizung des Heizmantels ausgleichen zu können.The tubular cell 1 and the electrolyte reservoir 12 can expediently be surrounded by a heating jacket in order to obtain higher deposition rates by using a heated electrolyte. Thermometers are preferably attached to both ends of the tubular cell in order to measure temperature differences occurring in the direction of flow and to be able to compensate for them by heating the heating jacket accordingly.

Wie bereits bemerkt, kann über die beiden T-förmigen Verbindungsstücke der Elektrolyt mit beliebig hoher Strömungsgeschwindigkeit umgewälzt werden, so dass die Stromdichte wesentlich höher gewählt werden kann als bei stehendem Elektrolyten, wodurch sich höhere Abscheidungsraten erzielen lassen. Ausserdem können die beiden T-förmigen Verbindungsstücke zum Fluten oder Spülen der Rohrzelle mit einem geeigneten Lösungsmittel vorteilhaft benutzt werden. Dies erfolgt mit Hilfe der Inertflüssigkeit 26 im Inertvorratsbehälter 27 nach Schliessen der Ventile 19 und 20 und Öffnen der Ventile 21 und 22 mit Hilfe der Umwälzpumpe 25. Da hierbei in die Kammern 35 und 36 Inertflüssigkeit gelangt, muss diese über Leitung 41 und 102 durch Schliessen des Ventils 100 und Öffnen des Ventils 101 in den Behälter 27 zurückgeführt werden.As already noted, the electrolyte can be circulated at any high flow rate via the two T-shaped connecting pieces, so that the current density can be selected to be significantly higher than when the electrolyte is at a standstill, as a result of which higher deposition rates can be achieved. In addition, the two T-shaped connecting pieces can advantageously be used for flooding or flushing the tubular cell with a suitable solvent. This takes place with the aid of the inert liquid 26 in the inert storage container 27 after the valves 19 and 20 have been closed and the valves 21 and 22 have been opened with the aid of the circulating pump 25. Since this leads to the chambers 35 and 36, the inert liquid has to be closed via lines 41 and 102 of valve 100 and opening of valve 101 are returned to container 27.

Im Deckel des Elektrolytvorratsbehälters 12 können Bohrungen vorgesehen sein zum Einführen entsprechender Geräte zur Messung der Temperatur und Leitfähigkeit sowie zum Anbringen einer Füllstandshöhenanzeige.Bores can be provided in the cover of the electrolyte reservoir 12 for introducing appropriate devices for measuring the temperature and conductivity and for attaching a level indicator.

Damit der Elektrolyt zur Leitfähigkeitsverbesserung gefahrlos aufgeheizt werden kann, ist es zweckmässig, dass der Elektrolytvorratsbehälter 12 von einem Ölheizmantelbehälter umgeben ist, in dem sich Heizspiralen befinden und dadurch eine indirekte und die Elektrolytflüssigkeit schonende Aufheizung der Elektrolyten ermöglicht wird.So that the electrolyte can be safely heated to improve the conductivity, it is expedient that the electrolyte storage container 12 is surrounded by an oil heating jacket container in which heating coils are located, thereby enabling indirect heating of the electrolytes which is gentle on the electrolyte liquid.

Als Inertflüssigkeit wird vorzugsweise Toluol verwendet, das sich durch Destillation aus dem Elektrolyten gewinnen lässt, der aus in Toluol gelösten Aluminiumalkylkomplexsalz besteht.Toluene is preferably used as the inert liquid, which can be obtained by distillation from the electrolyte, which consists of toluene dissolved aluminum alkyl complex salt.

Der Ekeltrolyt besteht vorzugsweise aus 3 bis 4 mol Inertflüssigkeit und 1 mol Aluminiumalkylkomplexsalz, so dass die InertflüssigkeitToluol bei einem Siedepunkt von 110°C verhältnismässig leicht vom Aluminiumalkylkomplexsalz abdestilliert werden kann, wobei völlig sauerstoff- und wasserfreies Toluol (Inertflüssigkeit) erhalten wird, das sich als Inertflüssigkeit für das Ansetzen eines neuen Elektrolyten wie auch zum Einsatz in den Behälter 60 sehr gut eignet.The disgusting trolyte preferably consists of 3 to 4 mol of inert liquid and 1 mol of aluminum alkyl complex salt, so that the inert liquid toluene can be relatively easily distilled off from the aluminum alkyl complex salt at a boiling point of 110 ° C., with completely oxygen-free and water-free toluene (inert liquid) being obtained as Inert liquid for the preparation of a new electrolyte as well as for use in the container 60 is very well suited.

Das erfindungsgemässe Prinzip lässt sich auch dann anwenden, wenn aus fertigungstechnischen Gründen die Galvanisierung nicht waagrecht, sondern senkrecht vorgenommen werden muss. Dies ist beispielsweise erforderlich für die galvanische Aluminierung von Lichtwellenleitern, da diese zum einen nur im Senkrechtverfahren gezogen werden können und zum anderen diese unmittelbar nach der Herstellung geschützt werden müssen. Es ist nicht möglich, die Lichtwellenleiter umzulenken oder aufzuwickeln und anschliessend in horizontaler Lage zu lackieren oder zu galvanisieren wegen der hohen Empfindlichkeit hinsichtlich ihrer mechanischen Festigkeit.The principle according to the invention can also be used if, for manufacturing reasons, the galvanization does not have to be carried out horizontally but vertically. This is necessary, for example, for the galvanic aluminizing of optical fibers, because on the one hand they can only be drawn using the vertical process and on the other hand they have to be protected immediately after manufacture. It is not possible to deflect or wind up the optical waveguide and then paint or galvanize it in a horizontal position because of its high sensitivity with regard to its mechanical strength.

Fig. 3 zeigt ein Ausführungsbeispiel einer Anlage zum Aluminieren im Senkrechtverfahren im Prinzip. Mit 103 ist die eigentliche Aluminierzelle bezeichnet, die entsprechend Fig. 1 als Rohrzelle ausgebildet ist. Durch die Rohrzelle 103 ist das strangförmige Gut 105 geführt. Zu beiden Seiten der Aluminierzelle 103 sind T-förmige Verbindungsstücke 106 und 107 angeflanscht, um den Aluminiumelektrolyten zu- und abzuführen und umzulenken, wie durch Pfeile 104 angedeutet ist. Den Verbindungsstücken 106 und 107 folgen Schleusenanordnungen 108 und 109. Die Schleusenanordnung 108 enthält eine Inertgaskammer 110, der über eine Zuleitung 111 ein I nertgas, beispielsweise N2, zugeführt wird. Über einem Ablaufstutzen 112 kann der eventuell noch oben austretende Elektrolyt 113 und ggf. Inertflüssigkeit abgeleitet und dem Elektrolytvorratsbehälter zugeführt werden, entsprechend dem Ausführungsbeispiel nach Fig. 1. Anschliessend an die Inertgaskammer 110 befinden sich Kammern 114 und 115, die mit Inertflüssigkeit über einen Zulauf 116 und einem Ablauf 117 geflutet werden können. Diese beiden Kammern verhindern, dass Luft und Feuchtigkeit in die Galvanisierzelle 103 dringen kann. Die Inertflüssigkeitwird hierbei von unten nach oben geführt, wie die Pfeile 118 zeigen. Sie arbeiten nach dem Überlaufprinzip.Fig. 3 shows an embodiment of a system for aluminizing in the vertical method in principle. The actual aluminizing cell, which is designed as a tubular cell in accordance with FIG. 1, is designated by 103. The strand-like material 105 is guided through the tubular cell 103. T-shaped connecting pieces 106 and 107 are flanged on both sides of the aluminizing cell 103 in order to feed and discharge and redirect the aluminum electrolyte, as indicated by arrows 104. The connecting pieces 106 and 107 are followed by lock arrangements 108 and 109. The lock arrangement 108 contains an inert gas chamber 110, to which an inert gas, for example N 2 , is fed via a feed line 111. The electrolyte 113 and possibly the inert liquid, which may still emerge at the top, can be drained off via a discharge nozzle 112 and fed to the electrolyte reservoir, in accordance with the exemplary embodiment according to FIG. 1 and a drain 117 can be flooded. These two chambers prevent air and moisture from entering the electroplating cell 103. The inert liquid is conducted from bottom to top, as arrows 118 show. They work on the overflow principle.

Das T-förmige Verbindungsstück 107 ist besonders gestaltet, um zu verhindern, dass der Elektrolyt 113 durch die Einführöffnungen des zu aluminierenden Stranges 105 nach unten austreten kann. Dies wird dadurch erreicht, dass der Elektrolyt 113 mit hoher Geschwindigkeit der Aluminierzelle 103 zugeführt wird, wobei die Strömung so gesteuert wird, dass in einem Rohr 119 ein gewisser Unterdruck entsteht, der mit Inertgas ausgeglichen wird. Aus diesem Grunde schliesst sich dem T-förmigen Verbindungsstück 107 eine Inertgaskammer 127 der Schleusenanordnung 109 an, wobei das Inertgas über einen Anschlussstutzen 121 zugeführt wird. Über einen Ablaufstutzen 122 kann der durch das Rohr 119 eventuell noch austretende Elektrolyt 113 abgeführt und dem Elektrolytvorratsbehälter zugeführt werden. Der Inertgaskammer 120 schliessen sich die beiden Inertflüssigkeitskammern 123 und 124 an, wobei der Zulauf über einen Anschlussstutzen 125 und der Ablauf über einen Anschlussstutzen 126 erfolgt. Auch diese beiden Kammern arbeiten nach dem Überlaufprinzip. Ferner kann ein Rohrstück 127 (zur Dichtung mit Inertgas) über einen Anschlussstutzen 128 unter Inertgasdruck stehen.The T-shaped connecting piece 107 is specially designed to prevent the electrolyte 113 from escaping downward through the insertion openings of the strand 105 to be aluminized. This is achieved in that the electrolyte 113 is fed to the aluminizing cell 103 at high speed, the flow being controlled in such a way that a certain negative pressure is created in a tube 119 and is compensated for with inert gas. For this reason, the T-shaped connecting piece 107 is followed by an inert gas chamber 127 of the lock arrangement 109, the inert gas being supplied via a connecting piece 121. The electrolyte 113 which may possibly still escape through the pipe 119 can be discharged via a drainage connection 122 and fed to the electrolyte storage container. The inert gas chamber 120 is adjoined by the two inert liquid chambers 123 and 124, the inflow via a connecting piece 125 and the outflow via a connecting piece 126. These two chambers also work on the overflow principle. Furthermore, a pipe section 127 (for sealing with inert gas) can be under an inert gas pressure via a connecting piece 128.

Fig. 4 zeigt einen Einschleuskopf bei senkrechter Betriebsweise der Galvanoaluminieranlage und Durchlauf des zu behandelnden Gutes 129 von oben nach unten, wie mit einer gestrichelten Linie angedeutet ist. Mit 130 ist eine Rohrzelle bezeichnet, in der sich ein Elektrolyt 131 befindet. An die Rohrzelle 130 schliesst sich eine Schleusenanordnung 132 an, die aus mindestens drei lamellenartig aufgebauten zentrischen Kammern 133 bis 135 besteht. Diese Kammern stehen unter einem gegenüber der Aussenatmosphäre geringen oder je nach Einlaufgeschwindigkeit des zu beschichtenden Gutes 129 grösseren Inertgasüberdruck. Wie aus der Figur ersichtlich, wird den Kammern 133 bis 135 über Anschlussstutzen 136 bis 141 Inert- gas, zum Beispiel N2, zugeführt. In der Rohrzelle 130 über dem Elektrolyten 131 befindet sich ein Inertgasraum 142. Dabei können die Kammern 133 bis 135 und der Inertgasraum 142 unter demselben Inertgasüberdruck oder vorteilhafterweise auch unter einem von innen nach aussen (d.h. von unten nach oben) zunehmenden Inertgasüberdruck stehen, wodurch eine Inertgasspülstrahlwirkung entsteht, die die Oberfläche des zu beschichtenden Gutes 129 von anhaftender Luft oder Verunreinigungsatmosphäre freibläst und gleichzeitig die Galvanoaluminieranlage gegen die Aussenatmosphäre abschliesst.Fig. 4 shows a sluice head in the vertical mode of operation of the galvano-aluminizing system and passage of the material to be treated 129 from top to bottom, as indicated by a broken line. 130 denotes a tubular cell in which there is an electrolyte 131. The tube cell 130 is followed by a lock arrangement 132 which consists of at least three lamellar chambers 133 to 135. These chambers are under an inert gas overpressure which is low compared to the outside atmosphere or 129, depending on the inflow rate of the material to be coated. As can be seen from the figure, the chambers 133 to 135 are supplied with inert gas, for example N 2 , via connecting pieces 136 to 141. There is an inert gas space 142 in the tubular cell 130 above the electrolyte 131. The chambers 133 to 135 and the inert gas space 142 can be under the same inert gas pressure or advantageously also under an increasing inert gas pressure from the inside out (ie from bottom to top), which results in a Inert gas purging action is created which blows the surface of the product 129 to be coated free of adhering air or contaminant atmosphere and at the same time closes off the galvano-aluminizing system from the outside atmosphere.

Die Inertspülstrahlwirkung kann durch mehr als drei Kammern beliebig verstärkt werden. Sie kann jedoch unabhängig von der Kammerzahl auch dadurch verstärkt werden, dass die Kammermündungen nach aussen (noch oben) hin immer dichter aufeinander aufsitzen, so dass sich die Spülstrahlwirkung verstärkt. Ferner kann auch der Anblaswinkel des Spülstrahles durch andere geometrische Gestaltung der Kammerwandungen verändert und dadurch dessen Wirkung je nach Beschichtungsobjektoberflächenstruktur optimiert werden.The inert rinse jet effect can be increased by more than three chambers. However, irrespective of the number of compartments, it can also be reinforced by the fact that the mouths of the compartments are positioned closer to each other towards the outside (still above), so that the flushing jet effect is enhanced. Furthermore, the blowing angle of the rinsing jet can also be changed by a different geometrical design of the chamber walls and its effect can thereby be optimized depending on the coating object surface structure.

Fig. 5 zeigt einen dem in Fig. 4 dargestellten Einschleuskopf entsprechenden Ausschleuskopf. Gleiche Teile sind mit gleichen Bezugszeichen versehen. Am unteren Ende der Rohrzelle 130 ist eine dem Querschnitt des zu behandelnden Gutes 129 angepasste Verengung 143 vorgesehen, an die sich eine Inertgasschleusenanordnung 144 anschliesst. Die Inertgasschleusenanordnung 144 besteht wie der Einschleuskopf gemäss Fig. 4 aus mindestens drei lamellenartig aufgebauten zentrischen Kammern 145 bis 147, die über nicht näher bezeichnete Anschlussstutzen mit Inertgas beaufschlagt werden, wie Fig. 5 zeigt. Unterhalb der Kammern 145 bis 147 befindet sich noch ein Inertgasraum 148.FIG. 5 shows a discharge head corresponding to the feed head shown in FIG. 4. The same parts are provided with the same reference numerals. At the lower end of the tubular cell 130 there is a narrowing 143 adapted to the cross section of the material 129 to be treated, to which an inert gas lock arrangement 144 is connected. The inert gas lock arrangement 144, like the infeed head according to FIG. 4, consists of at least three lamella-like central chambers 145 to 147, which supply inert gas via connecting pieces (not shown) be hit, as Fig. 5 shows. There is also an inert gas space 148 below the chambers 145 to 147.

In Fig. 6 ist eine Ausführungsform eines Ausschleuskopfes dargestellt, bei dem mit Sicherheit ein Einblubbern von Inertgas in die Rohrzelle 130 mit Sicherheit ausgeschlossen werden kann, wobei wirkumgsmässig gleiche Teile mit gleichen Bezugszeichen wie in Fig. 4 und 5 versehen sind. Bei dieser Ausführung ist über der Verengung 143 durch entsprechende Gestaltung des unteren Endes der Rohrzelle 130 ein Raum 149 ausgebildet, der beispielsweise mit Flüssigmetall gefüllt ist. Als Flüssigmetall kann beispielsweise Gallium verwendet sein. Der Raum 149 ist gegen die Rohrzelle 130 durch Blenden 150 abgeschirmt. Hierbei wird das Flüssigmetall zweckmässig zur elektrischen Kontaktierung des Beschichtungsobjektes 129 verwendet.FIG. 6 shows an embodiment of a discharge head in which the bubbling of inert gas into the tubular cell 130 can be excluded with certainty, the same parts being provided with the same reference numerals as in FIGS. 4 and 5. In this embodiment, a space 149 is formed above the constriction 143 by appropriately designing the lower end of the tubular cell 130, and is filled with liquid metal, for example. Gallium, for example, can be used as the liquid metal. The space 149 is shielded from the tubular cell 130 by screens 150. Here, the liquid metal is expediently used for the electrical contacting of the coating object 129.

Grundprinzip der in Fig. 5 und 6 dargestellten Ausschleusköpfe ist, dass durch den Inertgasdruck der Kammern 145 bis 147 die Elektrolytflüssigkeitssäule im Gleichgewicht gehalten wird, damit sie nicht auslaufen kann. Das ist an möglichst enge Auslaufblenden für das Beschichtungsobjekt gebunden und setzt eine manometrische Steuerung des Ausschleuskopfes voraus. Gegenüber der Ausführung nach Fig. 5 hat die Ausführung nach Fig. 6 den Vorteil, dass durch das Flüssigmetall am glavanisierten Gut 129 noch anhaftender Elektrolyt 131 abgequetscht wird.

Figure imgb0001
Figure imgb0002
Figure imgb0003
 The basic principle of the discharge heads shown in FIGS. 5 and 6 is that the inert gas pressure of the chambers 145 to 147 keeps the electrolyte liquid column in equilibrium so that it cannot run out. This is tied to the narrowest possible outlet orifices for the coating object and requires manometric control of the discharge head. Compared to the embodiment according to FIG. 5, the embodiment according to FIG. 6 has the advantage that electrolyte 131 still adhering to the glavanized material 129 is squeezed out.
Figure imgb0001
Figure imgb0002
Figure imgb0003

Claims (19)

1. An installation for the electrolytic deposition of aluminium from aprotic, organoaluminium electrolytes, which are free from oxygen and water, on to material in the form of wire, piping or strips, comprising a tubular cell which is sealed from the outside and through which the cathodically contacted material which is to be treated can be moved in the axial direction alongside of anodes, and through which the electrolyte can be pumped in a direction opposite to that of the movement of the material with the aid of a closed electrolyte- circulating system, wherein, at each end of the tubular cell, there is provided a sluice arrangement which prevents the electrolyte from flowing out of the tubular cell, and which consists of a plurality of chambers, characterised in that the tubular cell (1), which is sealed from the outside, can be supplied with a shielding gas (inert gas); that the individual chambers (33,34,35 and 36,37,38,39, 40) of the sluice arrangements (31, 32) are sealed from one another by inert gas and/or inert liquid; and that, for the inlet and outlet gating of the flowing electrolyte (11) and diverting its direction of movement, between the tubular cell (1) and the sluice arrangements (31, 32), there are arranged T-shaped connecting members (10), each of which has a diaphragm (17) which prevents a longitudinal passage of the electrolyte and which vertically deflects the electrolyte flow, and each of which is provided with an opening (85) closely adapted to the cross-sectional shape of the material (2) to be treated.
2. An installation according to claim 1, characterised in that at least one disc-shaped chamber wall (43, 50, 51) of the sluice arrangements (31, 32) is provided with a radial bore (94) which leads to the opening for the passage of the material (2) to be treated and which is connected by way of a connecting member (93) to an inert-liquid circuit (44, 45, 46, 47, 48; 52, 53, 54, 55; 57, 58, 59, 60, 61) which serves for the common sealing of the chambers (33,34 and 39,40) and for washing the material (2) to be treated.
3. An installation according to claim 2, characterised in that a vaporiser (54) is provided which serves to produce the inert liquid for washing the material (2) to be treated, and which is connected by way of a pipeline (52) to a bore in the chamber wall (50).
4. An installation according to one of claims 1 to 3, characterised in that the individual chambers (33, 34, 35, 36, 37, 38, 39, 40) of the sluice arrangements (31,32) consist of tubular members (89) and disc-shaped chamber walls (43, 50, 51, 87, 88, 92, 94).
5. An installation according to claim 1, characterised in that the opening (85) in the diaphragm (17) is formed by a channel which extends along the entire length of the connecting member (10), in an insert (83), the internal width of which corresponds to the cross-section of the material (2) to be treated, that part (86) of the insert (83) which extends in front of the diaphragm (17) merely having such a wall thickness as is necessary for stability, whilst the portion which extends behind the diaphragm corresponds to the internal width of the connecting member (10).
6. An installation according to one of claims 1 to 5, characterised in that the T-shaped connecting member (10) has a circular cross-section and is attached by means of flanges to the tubular cell (1).
7. An installation according to one of claims 1 to 6, characterised in that in the tubular cell (1), there are arranged anode plates (7) which extend along the entire length, and which surround as fullyas possible those surfaces of the material to be treated which are to be electroplated, and which are maintained in a predetermined position with the aid of current-insulating spacing members (81), the current-insulating spacer members (81 ) being provided with guides (82) for the moving material to be treated.
8. An installation according to claim 7, characterised in that the anode plates (7) can be contacted by way of anode holders (9) which are made of insulating material and which interrupt the tubular cell (1) and/or are arranged at both ends thereof.
9. An installation according to claim 1, characterised in that a thermo-couple is arranged at each ends of the tubular cell (1 ).
10. An installation according to claim 1, characterised in that the tubular cell (1) is surrounded by a heating jacket.
11. An installation according to claim 10, characterised in that the tubular cell (1) is surrounded by a heat-insulating material.
12. An installation according to one of claims 1 to 11, characterised in that an electrolyte-supply container (12) is connected in the electrolyte- circulating system.
13. An installation according to one of claims 1 to 12, characterised in that an inert-liquid circuit (21 to 27) which serves for washing and flushing can be connected to the T-shaped connecting members (10).
14. An installation according to one of claims 1 to 13, characterised in that the tubular cell (103), together with the T-shaped connecting members (106, 107) and the sluice arrangements (108, 109), is arranged vertically for vertical transport of the material (105) to be coated with aluminium.
15. An installation according to claim 14, characterised in that the sluice arrangements (108, 109) each consist of an inert gas chamber (110, 120) and at least two inert-liquid chambers (114, 115 and 123,124).
16. An installation according to claim 15, characterised in that inert-liquid chambers (114, 115 and 123,124) are provided, the flow through which can be upwards.
17. An installation according to claim 14, characterised in that the sluice arrangements (132, 144) are designed as inert-gas sluices which consist of at least three lamella-like concentric chambers (133,134,135 and 145,146,147).
18. An installation according to claim 17, characterised in that a liquid seal is arranged at the lower end of the tubular cell (130).
19. An installation according to claim 18, characterised in that the liquid seal consists of a liquid-metal plug which simultaneously serves to electrically contact the material (129) to be coated with aluminium.
EP81104184A 1980-06-25 1981-06-01 Apparatus for the electroplating of aluminium Expired EP0043440B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81104184T ATE6874T1 (en) 1980-06-25 1981-06-01 PLANT FOR ELECTROPLATING ALUMINUM.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3023827A DE3023827C2 (en) 1980-06-25 1980-06-25 Plant for the galvanic deposition of aluminum
DE3023827 1980-06-25

Publications (2)

Publication Number Publication Date
EP0043440A1 EP0043440A1 (en) 1982-01-13
EP0043440B1 true EP0043440B1 (en) 1984-03-28

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EP81104184A Expired EP0043440B1 (en) 1980-06-25 1981-06-01 Apparatus for the electroplating of aluminium

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US (1) US4444636A (en)
EP (1) EP0043440B1 (en)
JP (1) JPS5739194A (en)
AT (1) ATE6874T1 (en)
BR (1) BR8103972A (en)
CA (1) CA1162516A (en)
DE (1) DE3023827C2 (en)
DK (1) DK152595C (en)
ES (1) ES503382A0 (en)
IE (1) IE51338B1 (en)
NO (1) NO163063C (en)
PT (1) PT73251B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3515629A1 (en) * 1985-05-02 1986-11-06 Held, Kurt, 7218 Trossingen METHOD AND DEVICE FOR PRODUCING COPPER-COATED LAMINATES
DE19716493C2 (en) * 1997-04-19 2001-11-29 Aluminal Oberflaechentechnik Process for the electrolytic coating of metallic or non-metallic continuous products and device for carrying out the process
DE10242772B4 (en) * 2002-09-14 2005-06-09 ITT Manufacturing Enterprises, Inc., Wilmington Electroplating
DE102009060676B4 (en) * 2009-12-28 2015-07-23 Atotech Deutschland Gmbh Process and device for wet-chemical treatment of items to be treated
US20160040292A1 (en) * 2014-08-08 2016-02-11 Gary P. Wainwright Roll-to-roll electroless plating system with low dissolved oxygen content

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1590599A (en) * 1924-06-17 1926-06-29 Taylor Lab Inc Method of making insulated electrical conductors and the like
US2445675A (en) * 1941-11-22 1948-07-20 William C Lang Apparatus for producing coated wire by continuous process
DE813621C (en) * 1949-05-08 1951-09-13 Siemens & Halske A G Device for electrolytic treatment, in particular for the oxidation of wires, tapes or the like.
US3267008A (en) * 1962-10-04 1966-08-16 Nat Steel Corp Method of recovering aluminum halide from metal strip electrodeposited with an aluminum-containing coating from a fused salt bath
US3474009A (en) * 1966-03-07 1969-10-21 Kennecott Copper Corp Process and apparatus for the production of elongated metal articles
US3658680A (en) * 1968-09-04 1972-04-25 Thomson Csf Apparatus for forming silicon carbide filaments
US3778355A (en) * 1968-10-25 1973-12-11 Texas Instruments Inc Metallic covering of continuous metallic core material
US3592746A (en) * 1969-05-15 1971-07-13 Burroughs Corp Electroplating method of fabricating plated wire memory units
US3661752A (en) * 1970-06-23 1972-05-09 Amp Inc Belt plating apparatus
GB1416337A (en) * 1971-11-19 1975-12-03 Angelini S Method and apparatus for electroplating elongated metal elements
US3865701A (en) * 1973-03-06 1975-02-11 American Chem & Refining Co Method for continuous high speed electroplating of strip, wire and the like
AR204283A1 (en) * 1975-01-21 1975-12-10 Uss Eng & Consult APPARATUS FOR THE ELECTROLYTIC TREATMENT OF METAL STRIPS
US4162955A (en) * 1978-10-10 1979-07-31 Midland-Ross Corporation Electrodeposition coating apparatus

Also Published As

Publication number Publication date
US4444636A (en) 1984-04-24
NO812123L (en) 1981-12-28
IE811402L (en) 1981-12-25
PT73251A (en) 1981-07-01
JPS5739194A (en) 1982-03-04
DK152595B (en) 1988-03-21
ES8205022A1 (en) 1982-05-16
DE3023827A1 (en) 1982-02-11
PT73251B (en) 1982-07-06
DK152595C (en) 1988-09-19
JPS6128756B2 (en) 1986-07-02
IE51338B1 (en) 1986-12-10
NO163063B (en) 1989-12-18
EP0043440A1 (en) 1982-01-13
CA1162516A (en) 1984-02-21
NO163063C (en) 1990-03-28
ATE6874T1 (en) 1984-04-15
ES503382A0 (en) 1982-05-16
DK278781A (en) 1981-12-26
BR8103972A (en) 1982-03-09
DE3023827C2 (en) 1985-11-21

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