EP0167790A2 - Electrode en métal-soupape revêtue pour le zingage électrolytique - Google Patents

Electrode en métal-soupape revêtue pour le zingage électrolytique Download PDF

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Publication number
EP0167790A2
EP0167790A2 EP85106733A EP85106733A EP0167790A2 EP 0167790 A2 EP0167790 A2 EP 0167790A2 EP 85106733 A EP85106733 A EP 85106733A EP 85106733 A EP85106733 A EP 85106733A EP 0167790 A2 EP0167790 A2 EP 0167790A2
Authority
EP
European Patent Office
Prior art keywords
lamellae
coated
strip
electrode according
electrode
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.)
Withdrawn
Application number
EP85106733A
Other languages
German (de)
English (en)
Other versions
EP0167790A3 (fr
Inventor
Konrad Dipl.-Chem. Koziol
Erich Wenk
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 Elektroden GmbH
Conradty GmbH and Co Metallelektroden KG
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 Elektroden GmbH, Conradty GmbH and Co Metallelektroden KG filed Critical Heraeus Elektroden GmbH
Publication of EP0167790A2 publication Critical patent/EP0167790A2/fr
Publication of EP0167790A3 publication Critical patent/EP0167790A3/fr
Withdrawn legal-status Critical Current

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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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form

Definitions

  • the invention relates to a coated valve metal electrode for the electrolytic deposition of metals from aqueous solutions of the metal salts onto a metal flat article, in particular a strip, preferably an anode for electrolytic electroplating with zinc, consisting of at least one current feeder, at least one electrically moving Conductively connected current distributor and an active surface arranged thereon, which is aligned with the metal strip.
  • the continuous electrolytic coating of flat metal, ie strips and sheets, in particular electrolytic galvanizing is a relatively old technology (DE-PS 250 403; DE-PS 689 548).
  • This continuous electro Lytic zinc is deposited from the aqueous solution of its salts on cold-rolled strip or sheet made of soft, unalloyed steels, in general structural steels or from high-strength steels suitable for cold forming.
  • the electrode is connected as an anode and the band as a cathode.
  • One-sided or two-sided galvanizing can be carried out in one operation, whereby different layer thicknesses can also be produced in the double-sided coating.
  • the tape guide and thus the electrode arrangement can take place horizontally, vertically or radially, ie with electrodes bent in a circular arc, the radial arrangement of course only permitting a one-sided coating.
  • the technology described has found a new revival.
  • the automotive industry in particular uses electrolytically galvanized flatware in the body area.
  • the zinc coating actively protects the steel sheet from corrosion and is particularly suitable for subsequent painting with relevant surface treatments such as phosphated, chromate rinsed or chromate passivated.
  • a known arrangement for the electrolytic galvanizing of rolled strip (DE-OS 29 17 630) is characterized in that the electrolyte in the bath is guided parallel to the strip surface and against the strip running direction at a relatively high speed. This is to avoid dendritic crystal growth and to improve the current efficiency in a hydrodynamic manner, the mass transfer to the band acting as the cathode can be improved.
  • insoluble anodes are used, which consist either of coal or of lead with a copper core.
  • such anodes are problematic at higher current densities because they are subject to great wear and tear and show an uneven current distribution.
  • these anodes form continuous surfaces, so that, in particular in the case of a horizontal arrangement, the resulting gas, namely oxygen at the anode and hydrogen at the belt, can only be removed insufficiently. This applies in particular to the area below the band. The gas that is not discharged disrupts and slows down the galvanizing process, which results in inadequate system efficiency.
  • lead anodes there is the additional disadvantage that the lead is built into the zinc deposited on the sheet, which means that the corrosion protection deteriorates and the paint adhesion is adversely affected.
  • the electrolyte is guided parallel to the belt surface in the systems described above, it is also possible to apply the electrolyte perpendicularly to the belt surface and in this way to steer it over the belt surface.
  • the electrodes are provided with at least one slot for this purpose, through which the electrolyte is pressed out to the surface of the metal strip, so that a suitable static pressure builds up in the electrolyte is to ensure that the metal strip is kept at a constant distance between two opposite electrodes.
  • an electrode in particular anode, of the presupposed type in that the active surface is formed from lamellae of valve metal with an active surface coating, in that the coated total surface of the lamellae F A and the area Fp (occupied by the overall arrangement of the lamellae) Length x width of the electrode area) an area factor preferably and that the larger portions of the coated surface of the lamellae are oriented perpendicular to the surface of the strip to be coated, that the current feeder consists of a rod with a core of electrically highly conductive metal, in particular copper, and a sheathing of valve metal, that the current distributor through a rod made of valve metal is formed so that the current distributor is mechanically and electrically conductively connected to the current supply via at least one sheet-like connecting element made of valve metal in that the connecting element is welded on the one hand to the casing of the current supply and on the other hand to the current distributor.
  • the first basic idea of the invention is then to dissolve the active surface of the electrode in an open structure of parallel or spaced apart in the case of horizontal and vertical cells and in the case of radial and vertical cells and lamellae or rods or the like arranged on a cylinder surface.
  • These fins can be arranged very simply on flat and also on curved surfaces, so that the anodes according to the invention can be used both in horizontal and vertical cells and in radial cells.
  • An active surface of an electrode formed from lamellae in this way is also suitable for controlling and directing the electrolyte flow through its structure.
  • a specific electrolyte movement is required in an optimum process control to the D iffusions slaughterdicke on the cathode that is, the tape to shrink and at the same time to prevent an unacceptably large metal ion depletion of the electrolyte in the cathode area.
  • the type of gas removal also contributes to this in the electrode according to the invention. The gas can namely escape between the channels formed by the lamellae under acceleration.
  • the described pump effect in the electrode according to the invention is further enhanced by the fact that, according to a further feature of the concept according to the invention, the larger portions of the coated surface of the lamellae are oriented perpendicular to the surface of the strip to be coated.
  • the slats are - seen in cross-section perpendicular to the belt surface - upright, i.e. have a greater height perpendicular to the belt surface with respect to the width parallel to the belt surface.
  • the measure described, according to which the larger portions of the coated surface of the lamellae are oriented perpendicular to the surface of the strip to be coated, also considerably reduces the wear on the electrodes according to the invention. Due to mechanical abrasion between the strip and the electrode, only the smaller portions of the coated surface, which are aligned with the strip and run parallel to the strip surface, can be subject to mechanical wear. However, the larger portions of the active surface of the electrode according to the invention are retained. This ensures the electrode according to the invention a kind of emergency running property, i.e. it is possible to continue working the electrode even with a partially finished surface coating.
  • the active surface of the electrode according to the invention in the form of a lamellar structure, there is the further basic idea of the invention of creating an electrode with a large area factor, which is achieved in that the coated total surface of the lamellae F A and the area Fp (length x width of the electrode area) occupied by the overall arrangement of the lamellae is an area factor preferably having. Let it through extremely high cathodic current densities are achieved with a relatively low current density and uniform current distribution on the active surface of the electrode according to the invention. Because of the acceptable current density at the electrode according to the invention and at the same time high current densities for the electrolytic process, the active surface coating, which is selected appropriately, has a long service life.
  • the "inner surface”, which is also provided with an active surface coating, that is to say those parts of the coated surface of the lamellae which are oriented perpendicular to the surface of the strip to be coated, are not subject to mechanical wear , which also contributes to a long service life and the emergency running properties of the electrode according to the invention.
  • Another feature of the solution according to the invention is to manufacture the current feeder of the electrode from a rod with a core made of electrically highly conductive metal, in particular copper.
  • Such a construction allows a sufficiently large amount of electricity to be transported with the lowest possible voltage drop.
  • a current lead with a flat cross-section it can be bent slightly with respect to the respective wider area, so that this current lead can be very well adapted to the given cell housing.
  • a power supply line can be bent very easily at an angle, so that in a horizontal cell, the then essentially vertical current feeder can be angled at the upper end in the direction of the busbar and at the lower end in the direction of the current distributor of the horizontally oriented active surface.
  • the measure according to the invention that the connection between the current feeder and the current distributor is brought about via a connecting element which is welded on the one hand to the casing of the current feeder and on the other hand to the current distributor contributes to the rapid and cost-effective reactivation of the electrode according to the invention.
  • the power distributor including the fins arranged thereon can be easily removed, so that the active surface can be supplied to the re-coating, while the power supply and all other electrical components for powering the cell remain with the operator .
  • the operator only has to keep active parts in stock for the rapid reuse of the cells, so that relatively little capital is tied up.
  • Each connecting element can consist of one sheet metal strip or several sheet metal strips. In the latter case, a separate sheet metal strip is provided for each power distributor.
  • titanium will be the first choice. If higher breakthrough potentials are required, tantalum, niobium or zircon can also be considered.
  • the invention provides an electrode for high-performance electroplating processes that takes account of the requirements that arise.
  • the experience gained from valve metal electrodes as such in other electrolytic or electrochemical processes is used.
  • the lamellae of the electrode according to the invention can either be designed as solid-wall lamellae or made of expanded metal.
  • the electrolyte can flow directly through them.
  • the electrolyte flow is increased in turbulence, which in addition to the gas bubble effect or the pump effect achieved with the open structure of the electrode according to the invention, on the one hand for rapid gas removal and on the other hand to reduce the cathode-side diffusion layer thickness and to prevent impermissible metal ion depletion of the electrolyte in Contribution near the cathode.
  • the lamellae which are either solid or made of expanded metal, are oriented obliquely to the strip running direction or to the electrolyte flow.
  • the electrolyte flow thereby receives a movement component in the direction of one of the edges of the strip to be coated. This flow of electrolyte, which is directed in this way, also leads part of the gas formed away from the side of the belt.
  • the spacing of the fins from one another in the flow direction of the electrolyte is gradually increased.
  • the gas passage area between the fins in the flow direction of the electrolyte is increased continuously or in steps, which takes into account the increased gas development in the direction of the * electrolyte flow.
  • the slats can also be arranged parallel to the tape running direction with respect to their longitudinal extent.
  • the lamellae form channels in the direction of the flow of the electrolyte, as a result of which the latter can be guided along the strip to be coated at a particularly high flow rate.
  • the electrode arrangement according to the invention can be used with advantage.
  • the dissolution of the active surface in rods, lamellae or the like provides a large total area for the electrolyte to pass through the electrode, so that the strip to be coated can be subjected to the electrolytic solution very intensively and avoiding dead zones in the flow .
  • the fins produce a kind of nozzle effect, which accelerates the electrolyte flow.
  • the height of the connecting elements between the current feeder and the current distributor can prevent the current feeder from causing a flow dead space in the electrolyte flow.
  • the respective power supply is equipped with a connection for the power supply at its opposite ends.
  • the current is thus supplied to the electrode from the two opposite sides. This further lowers the voltage drop in the power supply.
  • a vertically aligned power supply line 10 is mechanically and electrically connected by the fact that the upper end of the power supply line 10 is welded to a head plate 2, which in turn is screw 3 is attached to the busbar 1.
  • the current feeder consists of a core 11 made of electrically highly conductive material, preferably copper, and a jacket 12 Valve metal, preferably made of titanium.
  • the current supply line 10 is connected to current distributors 20 which run vertically, that is to say in the installed position of the anode, and which also preferably consist of titanium, in that two sheet-metal connecting elements 30 to the current supply line 10 are welded parallel to the casing 12 thereof along a weld seam 31 while, on the other hand, the power distributors 20 are welded to the opposite edges of the sheet-like connecting elements 30 along the weld seams 32.
  • the sheet-like connecting elements 30 are also advantageously made of titanium.
  • the active surface 40 of this anode is formed from lamellae 41, which are arranged parallel to one another at a distance from one another and, in the installed position of the anode, run vertically in one plane.
  • the lamellae have a relatively narrow rectangular cross section and are aligned with their (larger) height perpendicular to the current distributors 20 and thus perpendicular to the strip to be coated which is guided along the other side.
  • the fins 41 themselves consist of valve metal, advantageously also titanium, and are equipped with an active surface coating. Due to the arrangement of the fins 41, their dimensions and their spacing from one another, the fins 41 satisfy the relationships that the coated total surface of the fins F A and the area Fp occupied by the overall arrangement of the fins (length x width of the electrode surface 40) have an area factor and that the larger portions of the coated surface of the slats 41 are aligned perpendicular to the surface of the tape to be coated.
  • Fig. 3 shows an anode according to the invention, adapted to a horizontal cell, in which the anodes and the tape guide in the region of the anodes are oriented horizontally.
  • the same components are provided with the same reference numerals.
  • two current feeders 10 are then provided per anode, which are designed as double angles, so that the upper horizontal leg 13 can be connected to a current rail, the vertical leg 14 leads into the cell and the active surface 40 on the horizontal leg 15 the anode is connected.
  • FIG. 3 also exist in the arrangement of FIG. 3 tromzuleiter of a core of highly electrically conductive metal, in particular copper, and a sheath of valve metal, especially titanium.
  • the current feed lines 10 have a flat rectangular cross section, the angular bending taking place around a broad side. It has been found that such bends can be made without much of the composite structure
  • the sheet-like connecting elements 30 do not have to be continuous. Rather, they can be designed as short elements, so that such a connecting element 30 is assigned to a current distributor 20.
  • the fins 41 of the active surface 40 of an anode according to the invention shows an arrangement of the fins 41 of the active surface 40 of an anode according to the invention in such a way that the fins 41 are oriented transversely with respect to their longitudinal extension to the direction of the strip indicated by the arrow.
  • the electrolyte is preferably guided against this direction of tape travel.
  • the fins 41 expediently consist of expanded metal, as a result of which the electrolyte flows through the fin surfaces itself and is thereby set in high turbulence.
  • the fins 41 of the active surface 40 of the anode according to the invention are arranged obliquely to the strip running direction.
  • the electrolyte flow directed parallel to the strip surface receives a movement component in the direction of an edge of the strip to be coated, as a result of which the gas discharge is also promoted in this direction.
  • FIG. 6 serves the same purpose, in which the lamellae 41 of the active surface 40 of the anode according to the invention each consist of two legs 42 oriented at an angle to one another.
  • the apex of these angular lamellae 41 is expediently directed against the electrolyte flow, as a result of which it receives a movement component in the direction of both edges of the band.
  • FIG. 7 shows an arrangement of the fins 41 of the active surface 40 of the anode according to the invention parallel to the tape running direction and to the electrolyte flow. In this case, too, the fins produce a kind of nozzle effect, which accelerates the electrolyte flow.

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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)
  • Electroplating Methods And Accessories (AREA)
EP85106733A 1984-06-08 1985-05-31 Electrode en métal-soupape revêtue pour le zingage électrolytique Withdrawn EP0167790A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3421480 1984-06-08
DE3421480A DE3421480A1 (de) 1984-06-08 1984-06-08 Beschichtete ventilmetall-elektrode zur elektrolytischen galvanisierung

Publications (2)

Publication Number Publication Date
EP0167790A2 true EP0167790A2 (fr) 1986-01-15
EP0167790A3 EP0167790A3 (fr) 1986-05-07

Family

ID=6237989

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85106733A Withdrawn EP0167790A3 (fr) 1984-06-08 1985-05-31 Electrode en métal-soupape revêtue pour le zingage électrolytique

Country Status (4)

Country Link
US (1) US4642173A (fr)
EP (1) EP0167790A3 (fr)
JP (1) JPS613899A (fr)
DE (1) DE3421480A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0713932A1 (fr) 1994-11-29 1996-05-29 Heraeus Elektrochemie GmbH Electrode avec un corps en forme de plaque

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3519272C1 (de) * 1985-05-30 1986-12-18 Heraeus Elektroden GmbH, 6450 Hanau Elektrodenstruktur fuer elektrochemische Zellen
DE3626522A1 (de) * 1986-06-26 1988-02-11 Vepa Ag Stauchkammerkraeuselvorrichtung zum kraeuseln synthetischer fadenscharen
US4936971A (en) * 1988-03-31 1990-06-26 Eltech Systems Corporation Massive anode as a mosaic of modular anodes
US5188721A (en) * 1989-02-10 1993-02-23 Eltech Systems Corporation Plate anode having bias cut edges
US5017275A (en) * 1989-10-23 1991-05-21 Eltech Systems Corporation Electroplating cell anode
US5685970A (en) * 1992-07-01 1997-11-11 Gould Electronics Inc. Method and apparatus for sequentially metalized polymeric films and products made thereby
DE19525360A1 (de) * 1995-07-12 1997-01-16 Metallgesellschaft Ag Anode zur elektrolytischen Gewinnung von Metallen
EP1018568A4 (fr) * 1998-07-10 2006-05-31 Ebara Corp Dispositif de placage
ITMI20022382A1 (it) * 2002-11-11 2004-05-12 De Nora Elettrodi Spa Elettrodi per elettrometallurgia
US20110123822A1 (en) * 2007-08-16 2011-05-26 H.C. Starck Gmbh Nanosize structures composed of valve metals and valve metal suboxides and process for producing them
JP5278789B2 (ja) * 2007-12-28 2013-09-04 スズキ株式会社 陽極酸化処理装置
US8022004B2 (en) * 2008-05-24 2011-09-20 Freeport-Mcmoran Corporation Multi-coated electrode and method of making
US8038855B2 (en) 2009-04-29 2011-10-18 Freeport-Mcmoran Corporation Anode structure for copper electrowinning
US9150974B2 (en) 2011-02-16 2015-10-06 Freeport Minerals Corporation Anode assembly, system including the assembly, and method of using same
ITMI20112136A1 (it) * 2011-11-24 2013-05-25 Industrie De Nora Spa Struttura anodica per celle orizzontali per processi di elettrodeposizione di metalli
TWI655324B (zh) * 2014-02-19 2019-04-01 義大利商第諾拉工業公司 電解槽之陽極結構以及金屬電解場中金屬澱積方法和系統

Citations (1)

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Publication number Priority date Publication date Assignee Title
US4022679A (en) * 1973-05-10 1977-05-10 C. Conradty Coated titanium anode for amalgam heavy duty cells

Family Cites Families (8)

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US3380908A (en) * 1964-03-23 1968-04-30 Asahi Chemical Ind Explosion bonded electrode for electrolysis
GB1290099A (fr) * 1969-06-25 1972-09-20
US3761384A (en) * 1971-06-30 1973-09-25 Hooker Chemical Corp Anode assembly for electrolytic cells
AU509150B2 (en) * 1976-08-04 1980-04-24 Imperial Chemical Industries Limited Baseplate for anodes
US4141814A (en) * 1976-08-04 1979-02-27 Imperial Chemical Industries Limited Diaphragm cell
US4391695A (en) * 1981-02-03 1983-07-05 Conradty Gmbh Metallelektroden Kg Coated metal anode or the electrolytic recovery of metals
US4392937A (en) * 1982-04-26 1983-07-12 Uhde Gmbh Electrolysis cell
US4452685A (en) * 1983-05-02 1984-06-05 Olin Corporation Electrodes for electrolytic cells

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4022679A (en) * 1973-05-10 1977-05-10 C. Conradty Coated titanium anode for amalgam heavy duty cells

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0713932A1 (fr) 1994-11-29 1996-05-29 Heraeus Elektrochemie GmbH Electrode avec un corps en forme de plaque
DE4442388A1 (de) * 1994-11-29 1996-05-30 Heraeus Elektrochemie Elektrode mit plattenförmigem Elektrodenträger
DE4442388C2 (de) * 1994-11-29 1999-01-07 Heraeus Elektrochemie Elektrode mit plattenförmigem Elektrodenträger

Also Published As

Publication number Publication date
DE3421480A1 (de) 1985-12-12
JPS613899A (ja) 1986-01-09
EP0167790A3 (fr) 1986-05-07
US4642173A (en) 1987-02-10

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