EP0437705B1 - Verfahren und Vorrichtung zur kontinuierlichen elektrolytischen Ausbringung von Metall in Form eines Bandes aus einer Lösung sowie Verwendung der Vorrichtung - Google Patents

Verfahren und Vorrichtung zur kontinuierlichen elektrolytischen Ausbringung von Metall in Form eines Bandes aus einer Lösung sowie Verwendung der Vorrichtung Download PDF

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Publication number
EP0437705B1
EP0437705B1 EP90122495A EP90122495A EP0437705B1 EP 0437705 B1 EP0437705 B1 EP 0437705B1 EP 90122495 A EP90122495 A EP 90122495A EP 90122495 A EP90122495 A EP 90122495A EP 0437705 B1 EP0437705 B1 EP 0437705B1
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EP
European Patent Office
Prior art keywords
cathode roller
anode
cathode
coolant
roller
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 - Lifetime
Application number
EP90122495A
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German (de)
English (en)
French (fr)
Other versions
EP0437705A1 (de
Inventor
Stephan Dr. Kotowski
Harri Heinke
Wolfgang Blatt
Max Dr. Mayr
Reinhard Bedel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
De Nora Deutschland GmbH
Original Assignee
Heraeus Elektrochemie GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Heraeus Elektrochemie GmbH filed Critical Heraeus Elektrochemie GmbH
Priority to AT90122495T priority Critical patent/ATE100871T1/de
Publication of EP0437705A1 publication Critical patent/EP0437705A1/de
Application granted granted Critical
Publication of EP0437705B1 publication Critical patent/EP0437705B1/de
Priority to US08/374,999 priority patent/US5516411A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils

Definitions

  • the invention relates to a process for the continuous electrolytic application of metal in the form of a tape from a solution containing metal ions, the metal being deposited on the surface of a rotating cathode roller, the deposited metal being drawn off as a tape, and the solution being passed through at least one located below the cathode roller Opening is fed and the cathode roller is cooled during the deposition.
  • the invention relates to a device for the continuous application of metal in the form of a tape from a solution containing metal ions, which has in a container a cathode roller which can be rotated about an axis and an anode which at least partially surrounds the cathode roller, the cathode roller having internal coolant lines contains, as well as the use of this device.
  • a process for the production of metal foils in which a cathodically connected roller with a passivated coating layer is slowly rotated in an electrolyte and a metal foil deposited on the coating layer of the roller is continuously drawn off and possibly wound on a spool becomes;
  • the roller which is designed as a cylindrical body, has a passivated outer cladding layer, for example made of chrome, aluminum, titanium or similar metals, spiral grooves being introduced into the cladding layer, which enable cooling of the roller during operation by passing a cooling medium through the grooves .
  • the method is particularly based on the deposition of copper from a sulfate-containing solution for the production of copper foils for printed circuits directed with slow roller rotation.
  • an electrolysis cell for the electrolytic application of metals from process ions containing metal ions which contains a large number of planar electrodes spaced parallel to one another in a trough, the cathodes having openings and depending on the distance from the Anode are connected to the current source via connection resistors of different sizes, so that the cathodes are each subjected to the same current density.
  • a problem with such a device is the relatively wage-intensive individual removal of the cathode surface provided with the deposited metal and the relatively labor-intensive removal of the deposited material.
  • US Pat. No. 2,865,830 discloses an electrolytic device for the continuous production of a copper strip from a solution containing copper ions in a tank, the copper being deposited on the lower side of the cathode roller which projects into the solution and rotates about a horizontal axis.
  • This is a relatively large-volume system, since less than half of the outer surface of the cathode roller can be used for the deposition, and the cathode current is also very limited due to the limited cathode current density on the relatively small immersed outer surface.
  • EP-OS 248 118 discloses an electrolytic device for the continuous production of metal foils from a solution containing metal ions in a tank, the cathode, which is partially immersed in the solution, being designed as a drum or continuous endless belt. In its immersed area, it is surrounded by an anode arranged at a distance, which is provided with channels or openings for the electrolyte access. The metal deposited on the cathode is separated from the cathode after leaving the solution.
  • the cathode has a polished surface, for example made of titanium or tantalum, while the anode consists, for example, of a lead-antimony alloy.
  • An acidic metal ion solution for example of copper sulfate and sulfuric acid, is used as the solution.
  • the invention has for its object from a process liquid, ie. H. from a pickling liquid containing metal ions or process waste water containing metal ions, the metal ions are continuously separated and separated from the cathode in the form of a continuous band.
  • the aim is to achieve a compact design and maintenance-friendly operation.
  • the object is achieved according to the process in that a halogen or a sulfur compound containing process liquid is used as the solution and the cathode roller rotates about an axis designed as a hollow shaft, which is connected at one or both ends to connecting lines through which one of one Coolant discharged coolant flows.
  • the device according to the invention is characterized in that at least the surface of the cathode roller consists of aluminum, valve metal, an aluminum or a valve metal base alloy, of electrically conductive plastic or electrically conductive ceramic and that the cathode roller is provided along its axis with a hollow shaft which is attached to one or both of its ends is connected to a cooling device via connecting lines.
  • one end of the hollow shaft serves as a coolant inlet and the opposite end serves as a coolant outlet for the cathode roller.
  • the simple technical structure and the low maintenance expenditure prove to be advantageous.
  • the upper end of the hollow shaft is provided with two hollow cylinders which are coaxial with one another, of which the inner one Hollow cylinder for the coolant inlet and the outer hollow cylinder encasing this for the coolant outlet from the cathode roller is provided.
  • the lower end of the hollow shaft is supported on a rotary bearing.
  • the simple interchangeability of the cathode roller proves to be advantageous here, since it can be removed from its lower bearing by a simple lifting movement.
  • Another advantage can be seen in the fact that drive and contacting elements for the cathode roller are arranged at the upper end of the shaft at a safe distance from the solution containing metal ions without any sealing problems.
  • a separating device in the form of a diaphragm or an ion exchange membrane is arranged between the anode and the cathode roller, the diaphragm having proven particularly useful in the case of chlorine-containing solutions and the ion exchange membrane in the case of sulfate solutions. It has proven to be particularly advantageous here to specifically collect or remove the gases formed at the anode in a side reaction, such as, for. B. Chlorine with a chloride solution and oxygen with a sulfate solution. This gas separation also provides increased security against oxyhydrogen gas explosions or chlorine oxyhydrogen gas explosion due to the hydrogen gas generated in a side reaction from the cathode roller.
  • the quality of the anolyte surrounding the anode in its own anolyte space is not changed in the case of highly contaminated or very aggressive process fluids. It is possible to construct the anode segments and, if appropriate, the separating device in the form of closed anode boxes which contain a planar anode and surround the cathode roller with a distance to several copies.
  • zinc is continuously deposited in the form of a strip from a process liquid containing zinc chloride on the aluminum surface of the cathode roller.
  • the speed of the coolant and the current density can be adjusted to such an extent that rapid application is achieved and redissolution of the zinc within the electrolyte is avoided.
  • a separating device in the form of a diaphragm or an ion exchange membrane is arranged between the anode and the cathode.
  • the extensive automation of the application of metals from a process liquid and the metal depletion of even very aggressive process liquids by dividing the electrolyte space into an anolyte space and a catholyte space for receiving the process liquid have proven to be advantageous; hydrochloric acid is used as the anolyte.
  • FIG. 1 shows in cross section a container 1 provided for holding the process liquid, with a cathode roller 3 which can be rotated about a horizontal axis 2 and an anode 4 which partially surrounds the cathode roller and which is at least partially designed as a segment of a hollow cylinder.
  • a planar separating device 5 provided which divides the electrolyte space into a catholyte space 6 and an anolyte space 7 as an ion exchange membrane or diaphragm.
  • the inlet opening 9 for the anolyte while in the upper part of the side wall 10 of the container 1 there is the outlet opening 11 for the anolyte.
  • the inflow opening 14 of the process liquid acting as a catholyte is arranged, the outlets 15 of the catholyte being located above the cathode roller 3.
  • the lid part 12 of the container 1 there are also one or more gas outlet openings 13.
  • the electrical contacting of the cathode roller 3 takes place via a hollow shaft 18 guided along the axis 2 by means of a symbolically illustrated sliding contact 32, which is connected to the negative pole of a voltage source 16.
  • the anode 4 is connected via connecting line 33 to the positive pole of this voltage source 16.
  • the tape drawn off from the cathode roller is designated by number 34.
  • FIG 2 a partially broken device is shown in perspective.
  • the cathode roller 3 which can be seen in the broken area is in turn broken in the area of its end face in order to remove the internal coolant lines required for the cooling circuit, i.e. to show the connecting lines 19 between the hollow shaft 18 and the temperature control lines 17 and the connecting lines 20 between the temperature control lines 17.
  • the liquid temperature control agent is supplied or removed at the end faces of the hollow shaft 18.
  • the cathode roller 3 is driven via the belt pulley 21 located on the hollow shaft 18 via a belt drive 22 which is connected to a drive pulley 23 of an electric motor 24.
  • the anode 4 and the separating device 5, which is designed as a diaphragm or ion exchange membrane, can be seen.
  • the container 1 consists of a chloride solution-resistant and temperature-resistant plastic, for example of polypropylene. However, it is also possible to use polyvinyl chloride or polytetrafluoroethylene as the material.
  • the surface of the cathode roller 3 exposed to the process liquid consists of aluminum or an aluminum-based alloy; however, it is also possible to use a cathode roller with a surface made of titanium, a titanium-based alloy or electrically conductive ceramic.
  • the anode 4 consists of titanium or a titanium-based alloy and has an active surface.
  • An ion exchange membrane is preferably used as the separation device 5.
  • the hollow shaft 18 is guided out of the container 1 at both ends via a shaft seal 25 and is electrically insulated from the housing 1; it is electrically connected at one end outside the container to the sliding contact to the negative pole of the voltage source.
  • the anolyte consisting of hydrochloric acid
  • the anolyte flows around the areal anode 4 provided with openings and is guided along the separating device 5 to the outlet opening 11.
  • the process liquid is supplied as catholyte via the inflow mouth 14 and is discharged via the outlets 15 after depletion.
  • the process liquid can be supplied in batches or continuously in the bypass process.
  • the layer thickness of the metal deposited as strip 34 increases in the direction of rotation, the strip 34 being pulled off as a continuous film with a thickness in the range from 0.1 to 2.5 mm in the region of the cathode roller 3 facing the cover part 12 of the container 1 and is fed from the cathode roller 3 in the tangential direction at an angle in the range of approximately 45 ° through a slot in the cover part 12 to a support roller 26 and is passed on by train to a tape winding device (not shown) in the form of a reel.
  • the cathode roller 3 is constantly surrounded by the process liquid which acts as a catholyte, the strip 34 also being pulled off below the liquid level.
  • the number of revolutions of the cathode roller 3 is in the range from half to one revolution per hour, the circumference of which is approximately 356 mm, so that the belt is fed at a speed of 0.18 to 0.36 m per hour.
  • the cathodic current density is in the range from 140 to 1200 A / m2. Due to the cooling of the cathode roller 3, it is possible to operate it with a high current density without causing any damage in the region of the cathode roller 3 or the separating device 5. In addition, it is also possible to treat hot process liquid directly, for example in the range from 40 to 80 ° C., without intermediate cooling. The chlorine generated during the electrolysis process emerges from the container 1 through the gas outlet openings 13 and is discharged.
  • Figure 3 shows schematically in longitudinal section the deposition device with its various connections.
  • the voltage source 16 can be seen, which is electrically connected via connecting line 33 to the anode 4 arranged in the container 1 and via sliding contact 32 and hollow shaft 18 to the cathode roller 3.
  • the separating device arranged between the cathode roller 3 and the anode 4 is not shown for a better overview.
  • the inlet mouth 14 located in the catholyte chamber 6 is connected to the access line 27 for the process liquid, while the outlet 15 of the catholyte chamber 6 is connected to the discharge line 28.
  • the anolyte inlet opening 9 is connected to the anolyte access line 35 and the anolyte outlet opening 11 is connected to the discharge line 36.
  • the gas generated during the separation is discharged through the gas outlet opening.
  • From the The end 37 of the hollow shaft 18 exits the cooling medium and flows to the cooling device 31 via the connecting line 29. Water is used as the cooling medium.
  • the cooling device 31 has a heat exchanger system (not shown here in more detail) and a pump device for forcing the coolant circuit.
  • the cooled cooling medium is then fed in a circuit via connecting line 30 to the other end 38 of the hollow shaft 18, from where - as already explained above - it is fed to the coolant lines 19, 17 in the cathode roller 3.
  • the cathode roller 43 shown in longitudinal section is located in a trough-like container 41, the side walls 50 of which protrude above the height of the cathode roller. In this way it is possible, by filling the container 41 appropriately with process liquid, to completely immerse the outer surface 87 of the cathode roller 43 provided for deposition in the solution 82.
  • the cathode roller 43 has a shaft 58 which runs along the vertical roller axis 42 and is held in two upper bearings 83, 84 which are coaxial with one another.
  • a bearing 85 for centering the shaft 58 is also provided on the bottom 48 of the trough 41.
  • a drive rotating device with a belt pulley 61, belt drive 62, drive pulley 63 and a contacting device 96, which consists of slip ring 86 and slip contact 72, are also provided.
  • the cathode roller 43 has a circumferential outer surface 87 for deposition, which is held by a support frame 88 which contains spokes 89, 90 connected to the shaft 58.
  • the support frame 88 which is rigid per se, has heat exchangers 57 in the area below the lateral surface 87, which are connected to a cooling unit 71 via connecting lines 59, 60 via shaft 58 are, which is shown here only schematically.
  • the drive takes place via a drive motor 64, also shown schematically here, which is connected to shaft 58 via drive pulley 63, belt drive 62 and belt pulley 61 and sets the cathode roller 43 in rotation.
  • the cathode roller 43 is surrounded by anode elements 92 arranged approximately concentrically to the axis 42, which are arranged at a distance from one another and allow a sufficiently large gap for the passage of the strip 74 drawn off the cathode roller 43.
  • the anode elements 92 contain anodes 44, which are each housed in a housing 79 with an opening 80 which is aligned with the cathode roller and are covered by a separating device 5 in the form of an ion exchange membrane or a diaphragm.
  • a seal is arranged along the edge of the opening 80, so that there is a closed anolyte space in the housing 79, which separates the possibly aggressive solution 82 containing the metal ions and one largely unaffected by it Anolyte allows.
  • the anolyte is introduced into the housing 79 via the anolyte access line 75 and discharged via the outlet opening 51.
  • An anolyte overflow is also provided.
  • the housings 79 for the anodes 44 are each connected to a gas discharge line 81 for discharging the gas generated at the anode 44.
  • the tape 74 still drawn off within the solution 82 is led out through the space between the anode elements 92 and leaves the solution 82 by means of a deflection roller 93 on a 90 ° turning distance, this 90 ° turning distance being the winding of the tape 74 on a roll 94 with a horizontal Allows axis of rotation.
  • the position of the roller 94 and its tensile force and speed can be adjusted and regulated depending on the speed of the deposition. It has proven to be particularly expedient to provide a holder 95 which is mechanically firmly connected to the container for receiving the roller 94 and the bearings 83, 84 and the drive device and the contacting device 96 with sliding contact 72.
  • the Contacting device 96 is connected via connecting line 97 to the negative pole of a voltage source 56, while the anodes 44 are connected to the positive pole of this voltage source.
  • the temperature control lines 57 are connected via connecting lines 59, 60 to the coolant inflow and coolant outflow lines 98, 99 arranged coaxially in the shaft 58. All parts of the cathode roller 43, including the spokes 89, 90 and the part of the shaft 58 which is immersed in the solution 83, are provided with an electrically non-conductive surface apart from the outer circumferential surface 87 of the cathode roller 43, which surface is electrolyte- or catholyte-resistant in solution 82.
  • the cathode roller 43 does not require any sealing measures and is therefore flowed through by the solution 82 in its interior, with cooling of the solution 82 flowing through the roller possibly also being achieved due to the temperature control lines 57 serving as heat exchangers.
  • the periphery of the cathode roller 43 is surrounded by the anode elements 92 in a range from 180 to 270 °.
  • the ion exchange membrane or the diaphragm separates the electrolyte space into an anolyte space 47 and a catholyte space 46 for the solution 82 containing metal ions.
  • the inflow opening 54 of the catholyte is located in the immediate vicinity of the lower edge of the outer surface 87 of the cathode roller 43 and is in the Area of the bottom 48 of the trough arranged.
  • the outlet 55 of the catholyte is arranged in one of the side walls 50 of the trough at the level of the upper edge of the outer surface 87, it being possible, if necessary, to achieve a uniform distribution over the entire outer surface by means of additional flow distribution systems.
  • the anolyte for the anode elements 92 is supplied and discharged from above through separate pipelines.
  • the outer surface 87 of the cathode roller 43 consists of aluminum or titanium or an aluminum or titanium-based alloy.
  • the inside of the cathode roller 43, which is surrounded by the outer surface 87, has a surface made of electrolyte- or catholyte-resistant plastic, the current conductors leading to the outer surface being guided in spokes 89, 90 and being sealed by plastic.
  • the drive shaft 58 points at least to that in the solution immersed part also has a surface made of electrolyte- or catholyte-resistant plastic, with the cathode power supply line and the coolant lines being located in the interior of the tubular plastic covering.
  • the metal shaft 58 itself serves as the cathode current feeder; however, it is also possible to provide the shaft with its own cathode current conductor.
  • the coolant is fed in from a cooler 71 via connecting line 70 and the inner hollow cylinder of a coupling 100 provided with seals into the coolant inflow line 98 designed as the inner tube of the shaft 58.
  • the coolant outflow is via the coolant outflow line coaxially surrounding the line 98 99, the outer hollow cylinder of the coupling 100 and the connecting line 69 to the cooler 71.
  • FIG. 5 shows from above the cathode roller 43 inserted in a trough-like container 41, which rotates about the vertical axis 42 by means of shaft 58; this figure is not to scale to figure 4 for a better overview.
  • the inside of the cathode 43 contains a support frame 88 provided with spokes 89, which contains the coolant lines and heat exchangers which are not visible here;
  • the support frame 88 of the cathode roller 43 which is provided with an electrically insulating surface, is provided on its outer circumference with the circumferential surface 87 provided for metal deposition; the deposited metal is drawn off as a band 74 within the solution 82 in an approximately tangential direction and is wound on the band reel 94 via a deflection roller 93 after passing through a turning section for the purpose of rotating the band plane by 90 °.
  • further guide rollers 101, 102 can also be provided, which can optionally also be mechanically driven.
  • the cathode roller 43 is surrounded in a circumferential region of approximately 270 ° by anode elements 92 arranged at a distance from one another; the anode elements 92 each have a flat anode 44, which is arranged in a housing 79 with an opening 80 facing the cathode roller, the opening in each case closing off the interior of the housing from the solution 82 by a separating device 5.
  • the housings 79 are closed at the top and have a gas discharge for the gases developing at the anode.
  • Power connections and anolyte supply and discharge lines 75, 51 are shown schematically using the anode elements 92.
  • the drain 55 for the solution 82 is located in the upper part of the side wall 50 of the container 41.
  • zinc was deposited from a solution containing zinc ions onto an outer surface 87 made of aluminum.
  • the number of revolutions of the cathode roller 43 is in the range of 0.5 to 2 revolutions per hour, the circumference of the cathode roller 43 being approximately 300 mm.
  • the feed speed is in the range of 0.3 to 0.6 meters per hour.
  • the cathodic current density is in the range of 300 to 6,000 amperes / m2, with optimal deposition conditions being achieved with a cathodic current density of 4,000 amperes / m2.
  • a chloride-containing solution was added. The chlorine generated during the separation process emerges from the trough through gas outlet openings and gas discharges and is removed and, if necessary, collected for further use.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
EP90122495A 1989-12-23 1990-11-26 Verfahren und Vorrichtung zur kontinuierlichen elektrolytischen Ausbringung von Metall in Form eines Bandes aus einer Lösung sowie Verwendung der Vorrichtung Expired - Lifetime EP0437705B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AT90122495T ATE100871T1 (de) 1989-12-23 1990-11-26 Verfahren und vorrichtung zur kontinuierlichen elektrolytischen ausbringung von metall in form eines bandes aus einer loesung sowie verwendung der vorrichtung.
US08/374,999 US5516411A (en) 1989-12-23 1995-01-18 Method and apparatus for continuous electrolytic recovery of metal in ribbon form from a metal containing solution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3942876 1989-12-23
DE3942876 1989-12-23

Publications (2)

Publication Number Publication Date
EP0437705A1 EP0437705A1 (de) 1991-07-24
EP0437705B1 true EP0437705B1 (de) 1994-01-26

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EP90122495A Expired - Lifetime EP0437705B1 (de) 1989-12-23 1990-11-26 Verfahren und Vorrichtung zur kontinuierlichen elektrolytischen Ausbringung von Metall in Form eines Bandes aus einer Lösung sowie Verwendung der Vorrichtung

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US (1) US5516411A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0437705B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AT (1) ATE100871T1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (2) DE59004422D1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

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Publication number Priority date Publication date Assignee Title
US7097747B1 (en) * 2003-08-05 2006-08-29 Herceg Joseph E Continuous process electrorefiner
KR100747937B1 (ko) 2006-03-20 2007-08-08 엘에스전선 주식회사 수평형 드럼 제박기
TW200829726A (en) * 2006-11-28 2008-07-16 Basf Ag Method and device for electrolytic coating
US11686012B2 (en) * 2017-10-26 2023-06-27 Unison Industries, Llc Mandrel for electroforming
CN110904472B (zh) * 2019-11-21 2021-06-08 湖北中一科技股份有限公司 一种防电解铜箔断裂阴极辊及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2844529A (en) * 1955-01-17 1958-07-22 Reynolds Metals Co Process and apparatus for rapidly anodizing aluminum
BE573093A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1956-05-14
DE2024112A1 (de) * 1970-05-16 1971-12-02 Kabel Metallwerke Ghh Verfahren zum Herstellen von Metallfolien
US3901785A (en) * 1972-05-09 1975-08-26 Antonina Vladimiro Buzhinskaya Apparatus for producing a metal band
SU619550A1 (ru) * 1976-11-29 1978-08-15 Всесоюзный Научно-Исследовательский И Проектный Институт Вторичных Цветных Металлов "Вниипивторцветмет" Барабанный электролизер
US4279711A (en) * 1980-01-21 1981-07-21 Vining Paul H Aqueous electrowinning of metals
US4647345A (en) * 1986-06-05 1987-03-03 Olin Corporation Metallurgical structure control of electrodeposits using ultrasonic agitation
DE3640020C1 (de) * 1986-11-24 1988-02-18 Heraeus Elektroden Elektrolysezelle zur elektrolytischen Abscheidung von Metallen

Also Published As

Publication number Publication date
ATE100871T1 (de) 1994-02-15
DE4037664C2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1993-09-02
EP0437705A1 (de) 1991-07-24
DE59004422D1 (de) 1994-03-10
DE4037664A1 (de) 1991-06-27
US5516411A (en) 1996-05-14

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