WO2004044270A1 - Anode pour des applications electrometallurgiques - Google Patents

Anode pour des applications electrometallurgiques Download PDF

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Publication number
WO2004044270A1
WO2004044270A1 PCT/EP2003/012587 EP0312587W WO2004044270A1 WO 2004044270 A1 WO2004044270 A1 WO 2004044270A1 EP 0312587 W EP0312587 W EP 0312587W WO 2004044270 A1 WO2004044270 A1 WO 2004044270A1
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WO
WIPO (PCT)
Prior art keywords
anode
planar substrate
dimensional structure
sheet
catalytic layer
Prior art date
Application number
PCT/EP2003/012587
Other languages
English (en)
Inventor
Peter Fabian
Original Assignee
De Nora Elettrodi S.P.A.
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 De Nora Elettrodi S.P.A. filed Critical De Nora Elettrodi S.P.A.
Priority to AU2003301914A priority Critical patent/AU2003301914A1/en
Publication of WO2004044270A1 publication Critical patent/WO2004044270A1/fr

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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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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
    • 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
    • C25D7/0642—Anodes

Definitions

  • the automotive industry employs a big amount of carbon steel sheets coated with a thin layer of zinc or zinc alloy, for instance zinc-nickel or zinc-iron, whose purpose is to ensure an effective protection from corrosion: only the use of this kind of sheet allows producing vehicles whose chassis can endure the attack of atmospheric agents for an adequate number of years.
  • the coating was originally applied by dipping the sheet in a fused metal bath: this process is intrinsically slow and therefore inadequate for the production of the big amounts of sheet required by the car industry, the thus obtained sheet being furthermore not particularly suited to those bending and forming operations which are evidently needed for the production of the vehicle bodywork, as it is easily subjected to detachment phenomena with the imaginable consequences on the final product quality.
  • the coating with optimum quality is nowadays obtained by deposition in an electrochemical cell.
  • the sheet connected to the negative pole of a direct current generator, faces an anode (connected to the generator positive pole) and passes with a predetermined speed through the cell which contains a solution of a zinc salt (for example 300 grams/litre of zinc sulphate heptahydrate) and optionally of a nickel or iron salt.
  • the sheet works as cathode and zinc is therefore deposited thereupon, optionally alongside nickel and iron, together with an usually limited amount of hydrogen evolution that represents a loss of electric efficiency.
  • I is the current produced by the generator (amps), t the electrolysis time
  • PA is the atomic weight of the deposited metal
  • M is the amount of electricity (Amperehour) required for depositing one mole of metal
  • E is the yield of deposition (fraction of electric current effectively used for depositing the metal).
  • the anode and the sheet which are kept mutually parallel, can be disposed in a horizontal or vertical position or as coaxial cylinders.
  • the former position allows using a simpler cell design, even though the tendency of the sheet to assess along a catenary under the effect of its own weight must be counteracted with suitable internal devices.
  • the vertical position eliminates this inconvenience and allows using more compact cells, however with the disadvantage of a greater complexity of construction.
  • the anode facing the moving sheet was originally of the soluble type, made of the same metal contained in the electrolytic solution: the advantage of this option, consisting in the capability of the process of keeping the metal concentration in the electrolytic solution virtually constant, could't compensate however the big problem of the anode's own dimensional change and of the associated changes of the gap thereof with the membrane. These changes in their turn would cause an inhomogeneous distribution of the current density with consequent local variations in the thickness of deposited metal. Moreover, particles coming from the disintegration of the soluble anode could remain embedded in the deposit hampering its quality.
  • insoluble anodes made of a substrate, usually of titanium, coated with a catalytic layer for the evolution of oxygen and/or chlorine, comprising at least one metal of the group of platinum or oxides thereof, optionally mixed with at least one oxide of a metal selected between titanium, niobium, zirconium, tantalum, tin, lead, manganese.
  • These anodes are dimensionally stable and solve therefore the problem of the required constancy of the sheet - anode gap: nevertheless, they evolve gas, and to avoid that the bubbles accumulate and adhere to the surface of the anode itself or to the one of the sheet causing irregularities in the coating growth it was necessary to adopt the aforementioned circulation flow-rates of the electrolytic solution.
  • a limitation still characterising the commercial insoluble anodes is given by the relatively reduced lifetime, approximately 1 - 2 years in the above indicated conditions of high current density, and substantially arising from dissolution mechanisms of one or more components of the catalytic layer or of passivation induced by the growth of insulating layers at the interface between the substrate and the catalytic layer.
  • this anode shows a prolonged lifetime, but on the other hand it is subjected to some inconveniences, such as the oxygen bubble entrapment within the package, the perturbation of the solution motion with possible negative repercussions on the quality of the coating deposited on the sheet and a very unsatisfactory behaviour when damages caused by the contact with the sheet during the electrolysis and consequent short-circuiting occur.
  • the latter problem particularly serious with the insoluble anodes, is generated by the oscillations that the sheet experiences in its motion across the cell: these oscillations in some cases, such as in the presence of irregularities in the profile of the sheet or when resonance effects arise, can assume those amplitudes that bring to the contact with the anode.
  • the repairing of these anodes is cumbersome and entails a certain number of steps: the whole anode is first deprived of the catalytic layer through sandblasting and/or etching, the damaged zone is then machined to remove the residues of catalytic layer and of solidified fused metal, the cleaned zone is resurfaced with the base material, for instance titanium, by welding, and then milled to obtained the required planarity and to restore the ribbed pattern. After recovering the structural integrity of the anode, a new catalytic layer is applied, characterised however by a decreased lifetime in correspondence of the repaired zones.
  • the present invention is directed to an anode for a cell suitable for processes of deposition of a metallic coating from a solution containing the ions of the metal or of the metals to be deposited on a sheet or wire or other object in motion across said cell, wherein said anode, of the insoluble type and provided with a catalytic layer for the evolution of oxygen or other gas, is placed in parallel position with respect to the sheet or wire or other object in motion thereby defining a gap.
  • said anode of the insoluble type and provided with a catalytic layer for the evolution of oxygen or other gas
  • the assembly consisting in the moving sheet and the anode of the invention, disposed horizontally, vertically or according to a coaxial cylindrical geometry, is characterised by a prolonged lifetime and by the capability of effectively withstanding the collision with said moving sheet and the consequent short- circuiting followed by an electric arc.
  • the anode of the present invention comprises a generally planar substrate, made of a conducting material which is resistant to corrosion in the cell operating conditions, wherein at least one three-dimensional structure, preferably made of the same material of the planar substrate, is secured to the surface of the planar substrate facing the moving sheet during operation, and wherein said structure is positioned in parallel to the axis of the planar substrate oriented in the direction of the motion, protrudes from the surface of the planar substrate and has a length substantially equal to the one of the planar substrate measured along the axis thereof oriented in the direction of the motion.
  • the structure secured to the planar substrate comprises a U-shaped strip with the base of said U in contact with the planar substrate and the two lateral surfaces oriented toward the moving sheet.
  • the structure secured to the planar substrate comprises at least one strip with a C-, Z- or L-shaped cross section, the minor surface thereof being fixed to the planar substrate, and positioned such that it results generally parallel to the axis of the planar substrate oriented in the direction of the motion of the sheet.
  • Such U-, C-, Z- or L-shaped strip has a length which is substantially equal to that of the planar substrate measured along the axis oriented in the direction of the motion.
  • the structure-planar substrate assembly is produced by means of a spot or continuous welding with Tungsten Inert Gas (TIG) or equivalent arc-welding, or more preferably by laser welding.
  • TAG Tungsten Inert Gas
  • the anode comprises a multiplicity of said structures, parallel to each other, wherein the surfaces of said structures directly facing the moving sheet are preferably equally spaced in order to avoid affecting significantly the flow of the solution containing the gas bubbled formed in operation, to facilitate a homogeneous distribution of the electric current and to offer a uniform mechanical resistance toward the collisions with the moving sheet on the whole anode surface.
  • the latter may also be placed in mutual contact so that the coupling of the lateral walls of the different strips can oppose an increased resistance to the collisions with the moving sheet.
  • the anode of the invention is provided with a catalytic layer for gas evolution, preferably oxygen and/or chlorine evolution, on the whole surface exposed to the solution during operation which comprises the surface of the planar substrate that is not occupied by the structures of the invention and the portion of surface of the structures which is not in direct contact with the surface of the planar substrate.
  • the surface of the structures directly facing the moving sheet during operation consisting in the set of minor surfaces of the strips, is free of catalytic layer so as to increase the contact electric resistance between anode and sheet in case of collisions.
  • the anode is constructed through the steps of degreasing of the planar substrate, preparation of the strips, for example U-shaped strips, and degreasing of the same, insertion of the planar substrate and of the strips in a suitable mould, spot or preferably continuous laser welding, sandblasting and/or etching and application of the catalytic layer for oxygen and/or chlorine evolution as known in the art, preferably with the addition of a mill finishing step that allows to simultaneously achieve the two objectives of obtaining a perfectly planar surface, important for a best quality of the coating, and of removing the catalytic layer from the surfaces of the structures directly facing the moving sheet, with the aforementioned advantages.
  • the above indicated construction procedure can also me employed for the conversion of anodes of the prior art, extracted from the cells after short-circuit induced damages, to anodes of the invention: in this case the above listed steps are preferably preceded by a total removal of the damaged catalytic layer, for instance by sandblasting and/or etching, and by an optional resurfacing of the planar substrate in case the short- circuiting has provoked a consistent loss of material. In this occurrence it is necessary to carry out a grinding of the planar substrate to ensure an acceptable starting planarity.
  • - Fig. 1 is a three-dimensional view of a first embodiment of the anode of the invention.
  • - Fig.2 is a cross section of the anode of fig.1 - Fig. 3 is a sketch of the cell in which the anode of the invention is installed.
  • FIG. 4 is a three-dimensional view of a second embodiment of the anode of the invention.
  • Fig. 5 is a cross section of the anode of fig.4. DETAILED DESCRIPTION OF THE INVENTION
  • Fig.1 represents a three-dimensional view of an anode (1) according to the invention, characterised in that it is made by a substrate (2) whose essentially planar surface (3) comprises a multiplicity of structures (4) in the form of as strips with U-shaped cross section.
  • the strips have substantially the same length as the substrate as measured in the parallel direction with respect to the direction of the motion of the sheet to be coated across the cell (direction represented by the arrow (5)).
  • the strips are disposed on the surface (3) in a reciprocally parallel orientation with the base (6) of the U-shaped section in direct contact with the surface (3) of the planar substrate (2): the securing may be effected with any known method capable of ensuring a good electrical continuity between strips and planar substrate.
  • a suitable procedure is the one based on spot or preferably continuous welding: one technology that can be employed is the TIG type or equivalent, or preferably the laser type, particularly the automated laser type of high productive capacity in which the single pieces are first mechanically pre-set in the desired positions by means of a suitable mould, then subjected to the action of the laser beam and finally set free from the mould as a final product characterised by a low grade of warping caused by the small thermal effect of the welding.
  • Fig. 2 shows a cross section along the line A - A of figure 1 : the U-shaped profile of the strips (4), the weld (7) and the catalytic layer (8) for oxygen and/or chlorine evolution are evidenced.
  • the dimensions of the strips (4) these are characterised by the thickness t, the height of the lateral surfaces h, the base width w and the spacing s.
  • h can be correlated to the value of the gap established between moving sheet and anode surface and that more particularly such value of h is preferably not higher than 50% of such gap and that more preferably such value h should not exceed 33% of the gap.
  • the anode of figs. 1 and 2 can be installed alone or together with other equivalent ones, all facing the same surface of the moving sheet to be coated when the coating is applied to that surface only (case sketched in fig.3) or as an alternative the anodes can be split in two rows placed symmetrically with respect to the moving sheet when both surfaces thereof are to be coated.
  • Figure 3 shows the sketch of a vertical type cell: (9) indicates the cell body, (10) the sheet in motion (guided from the cell inside by means of at least one admission roller (11), one extraction roller (12) and one inversion roller (13)), (14) the row of anodes placed ni parallel with respect to the only surface (15) to be coated of the sheet (10), (16) and (17) respectively the inlet and the outlet of the solution containing the metal to be deposited in ionic form.
  • the inner design of these cells is rather complex as it is necessary to ensure a flow of solution with high linear velocity to guarantee both an effective withdrawal of the gas bubbles from the cell as homogeneous dispersion in the liquid phase, and an adequate mass transport of the ion to be deposited, two conditions that are essential for obtaining good quality deposits.
  • the details of this inner design are not shown in figure 3, and likewise the devices for fastening the anodes within the cells are not shown in the same figure 3 nor in figures 1 and 2.
  • the anodes of the invention are able to withstand the contact with the moving sheets and the relative short-circuit and are able to guarantee a reliable operation continuity to a much greater extent than the equivalent anodes of the prior art simply built out of a substrate with essentially planar surface. Furthermore it has been observed that the loss in the catalytic activity of the layer applied to the anode surface is substantially slowed down and the lifetime of the anodes of the invention is thereby increased with respect to the anodes of the prior art.
  • the enhanced resistance to short-circuits is to be attributed to the presence of surfaces which protrude from the planar surface of the substrate (2): when the sheet, due to the oscillations promoted by its high speed motion, smashes on the anode, the collision does not occur anymore between the two planar surfaces of the moving sheet and of the prior art anode with an extended contact area, but rather between the sheet and the crests of the structures (4) in figs. 1 and 2 with a very limited contact area.
  • the passage of the short-circuit electric current is further reduced by the height h of the U-shaped structure (4) sides: in this regard it would be ideally desirable that the thickness t of the sidewalls of the U-shaped structures be as thin as possible so as to minimise the short-circuit current, nevertheless the sidewalls of the U-shaped structures have also the additional function of opposing a mechanical resistance to the impact with the sheet in order to reduce the damage to the catalytic layer (8) to a minimum, and for this reason it would be apparently advantageous to increase the value of t.
  • the industrial experience has shown that the optimum values of t come from a trade-off between the two mentioned needs and are affected by the values of h, w and s: in particular, the optimum value of t, at a given value of h, increases when w and s increase.
  • w and s respectively equal to 5 ⁇ 0.2, 7 ⁇ 0.2 e 5 - 7 millimetres
  • the optimum value of t is in the range of 1 millimetre, being anyway comprised between 0.8 and 1.2 millimetres.
  • the increased operating life of the anodes of the invention should be also probably attributable to the bigger effective working surface: for example, in the above mentioned case of the U-shaped structures characterised by t, h, w and s respectively equal to 1 ⁇ 0.2, 5 ⁇ 0.2, 7 ⁇ 0.2 and 5 - 7 millimetres, the effective working area results to be about 2.5 times bigger than that of the corresponding prior art anode having the same projected surface. It has to be noted that in the above discussed specific case, the ratio of the surface of the crests to the surface comprised between two adjacent lateral walls of the same U-shaped structure or between two adjacent U-shaped structures results to be 1 :5 - 1 :7, substantially lower that the disclosure of US 4,936,971.
  • the effective area of the anode of the invention mainly depends from the values assumed by h, w and s: in particular, for a given value of h, it is evident that the effective area is increased when the value of w and s is decreased, that is when the lateral walls of the U-shaped strips are closer.
  • This situation is however negative from the standpoint of resistance to short-circuits provoked by the collisions with the moving sheet: in fact, the increase in the population of crests of the U-shapes strips determines also an increase of the contact surface with the sheet and thus of the electric current associated to the short-circuit with a consequent aggravation of the damage.
  • the catalytic layer shows the distribution of the catalytic layer (8) which results to be placed in the area defined within each strip and between each pair of adjacent strips: it can also be observed that in a preferred embodiment the catalytic layer is not present on the crests of the U- shaped strips.
  • the fraction of catalytic layer present on the crests can be removed with a milling or grinding procedure that also allows obtaining anodes with optimum planarity eliminating the profile irregularities generated by small distorsions. The latter are inevitably caused by the welding procedures even though the single components are pre-assembled and fixed in an appropriate mould prior to the beginning of the welding operation.
  • the crests of the three-dimensional structures of the present invention are preferably free from catalytic layer and therefore, as a further difference from the prior art, are absolutely not involved in the evolution of gas (oxygen and/or chlorine), which remains confined in the region of anode delimited by the sidewalls of the U-shaped structures and of the exposed portion of the planar substrate (2).
  • gas oxygen and/or chlorine
  • the ratio of the surface of the crests of the catalytic layer-free U-shaped structures to the total activated surface, on the anodic planar substrate and on the sidewalls of the U- shaped structures is equal to or lower than 0.2.
  • Figures 4 and 5 illustrate a different arrangerhent of the U-shaped strips, which are positioned in parallel to each other as in the anode of figures 1 and 2, however without being mutually spaced: this configuration has the merit of maintaining the advantages of the anode of figures 1 and 2, with an equivalent increase of active surface but with a higher mechanical resistance to the collision with the oscillating sheet in motion imparted by the bigger population of coupled U- shaped structure sidewalls.
  • the solution of figs. 4 and 5 entails higher production costs associated to the greater amount of material employed, to the bigger extent of the welds (6) and to the longer pre-assembling times of the moulds.
  • the anode surface profile according to the two embodiments of the invention presents the additional advantage of not interfering in an appreciable way with the hydrodynamic regime of the solution inside the cell and in particular within the anode-moving sheet gap, said regime having been studied since a long time in the prior art and optimised for the cells equipped with conventional planar anodes: the prior art teachings, an example among the many references being US 4,584,066, indicate in fact that the optimum hydrodynamic regime is the result of a delicate balance of many factors whose slightest perturbation may result in a decay of the coating quality.
  • the structures parallel one to the other may be not parallel to the flow of the solution (and therefore to the main dimension of the planar subtrate) but rather form an angle comprised between 0 and 45° with the latter, however, it is preferable that said angle, in this case, be by far lower than 45° not to face the risk of perturbing the hydrodynamic regime of the process; the structures may be provided with suitable slots parallel to the flow of the solution to avoid the incurrence of undesired turbulence. As far as the fabrication procedures are concerned no difficulties ad thus no particular additional costs are present.
  • the procedure provides the following steps: degreasing of the substantially planar substrate, preparation of the structures of the present invention by cutting and/or bending of metallic band and degreasing of the same, insertion and pre-setting of the structures and of the planar substrate in an appropriate mould, securing by means of a known technique and preferably by TIG welding or equivalent and even more preferably by laser welding, the latter preferably being a continuous welding for a better current distribution, extraction from the mould, sandblasting and/or etching with various reactants and application of the catalytic layer comprising at least one metal of the platinum group or oxides thereof, optionally in admixture with oxides of metals selected from the group of tin, antimony, lead, manganese, titanium, niobium, zirconium, tantalum as known to those skilled in the art, and optional final machining such as milling or grinding to obtain the double advantage of an optimum planarity of the surface formed by the crests of the
  • This procedure also allows the retrofitting of conventional anodes made out of a simple planar substrate to anodes of the invention according to one of the following two preferred embodiments: in the former alternative, the substrate with the residues of the spent catalytic layer is used as such after washing to remove the traces of the solution employed in the coating cell, in the latter alternative the residues of the spent catalytic layer are previously eliminated, for instance by sandblasting and/or etching according to the teachings of the prior art.
  • the latter alternative is generally preferred as it permits to obtain a better fixing of the structures of the invention to the planar substrate, both from the mechanical and from the electrical standpoint.
  • the restoring procedure for putting the same once more in operation comprises, prior to the steps mentioned before for the new anodes, a pre-treatment including the measurement the residual planarity after the several short-circuits that are likely to have occurred during the previous operation and the removal of the parts deemed unacceptable in terms of uniformity of electric current distribution, wherein such removal preferably consists in the elimination by milling of the damaged zones, in the placement of new chunks in the milled zones and in the welding of the chunks to the underlying substrate.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

L'invention concerne une anode pour une cellule destinée à des procédés électrométallurgiques pour un dépôt sur une feuille, sur un fil ou sur un autre objet en déplacement dans la cellule. L'invention concerne un revêtement métallique contenant des ions, du métal ou des métaux à déposer. L'anode est d'un type insoluble, et est dotée d'un revêtement catalytique pour une évolution oxygène et/ou chlore, et est positionnée parallèle à la feuille, au fil ou à l'autre objet en déplacement. L'assemblage comprenant l'anode et la feuille, le fil ou l'autre objet est orienté dans la direction horizontale ou verticale, ou présente une géométrie cylindrique coaxiale. L'anode est caractérisée par une durée de vie de fonctionnement prolongée et peut résister à des collisions avec la feuille, le fil ou l'autre objet maintenu en déplacement, et par le court-circuitage résultant suivi un arc électrique. L'anode de l'invention comprend un substrat sensiblement plane constitué d'une matière conductrice résistant à la corrosion, dans des conditions de fonctionnement de cellule, au moins une structure tridimensionnelle, de préférence constituée de la même matière que le substrat plane étant fixée à la surface du substrat plane faisant face à la feuille, au fil ou à l'autre objet maintenu en déplacement. Ladite structure est positionnée en parallèle à l'axe du substrat plane orienté dans la direction du déplacement de la feuille, du fil ou de l'autre objet, et fait saillie de la surface du substrat plane, vers la feuille, le fil ou l'autre objet en déplacement, et présente une longueur sensiblement égale à celle du substrat plane mesuré le long de l'axe de celui-ci.
PCT/EP2003/012587 2002-11-11 2003-11-11 Anode pour des applications electrometallurgiques WO2004044270A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003301914A AU2003301914A1 (en) 2002-11-11 2003-11-11 Anode for electrometallurgical applications

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2002A002382 2002-11-11
ITMI20022382 ITMI20022382A1 (it) 2002-11-11 2002-11-11 Elettrodi per elettrometallurgia

Publications (1)

Publication Number Publication Date
WO2004044270A1 true WO2004044270A1 (fr) 2004-05-27

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AU (1) AU2003301914A1 (fr)
IT (1) ITMI20022382A1 (fr)
WO (1) WO2004044270A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1580303A2 (fr) * 2004-03-25 2005-09-28 De Nora Deutschland GmbH Moyens hydrodynamiques pour cellules électrochimiques
WO2009145994A1 (fr) * 2008-03-31 2009-12-03 Michael Steven Georgia Anode de protection cathodique polymère non corrosive

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4642173A (en) * 1984-06-08 1987-02-10 Conradty Gmbh & Co. Metallelektroden Kg Cell having coated valve metal electrode for electrolytic galvanizing
US4828653A (en) * 1986-12-19 1989-05-09 Permelec S.P.A. Long lasting anode for high current density galvanization
US4936971A (en) * 1988-03-31 1990-06-26 Eltech Systems Corporation Massive anode as a mosaic of modular anodes
EP0514582A1 (fr) * 1990-09-03 1992-11-25 Heraeus Elektrochemie Gmbh Dispositif pour électrodéposition
JPH08127900A (ja) * 1994-11-01 1996-05-21 Nippon Steel Corp 電気めっき用電極
WO2002077326A2 (fr) * 2001-03-27 2002-10-03 De Nora Elettrodi S.P.A. Structure anodique pour cellules electrolytiques a cathode de mercure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4642173A (en) * 1984-06-08 1987-02-10 Conradty Gmbh & Co. Metallelektroden Kg Cell having coated valve metal electrode for electrolytic galvanizing
US4828653A (en) * 1986-12-19 1989-05-09 Permelec S.P.A. Long lasting anode for high current density galvanization
US4936971A (en) * 1988-03-31 1990-06-26 Eltech Systems Corporation Massive anode as a mosaic of modular anodes
EP0514582A1 (fr) * 1990-09-03 1992-11-25 Heraeus Elektrochemie Gmbh Dispositif pour électrodéposition
JPH08127900A (ja) * 1994-11-01 1996-05-21 Nippon Steel Corp 電気めっき用電極
WO2002077326A2 (fr) * 2001-03-27 2002-10-03 De Nora Elettrodi S.P.A. Structure anodique pour cellules electrolytiques a cathode de mercure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 09 30 September 1996 (1996-09-30) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1580303A2 (fr) * 2004-03-25 2005-09-28 De Nora Deutschland GmbH Moyens hydrodynamiques pour cellules électrochimiques
EP1580303A3 (fr) * 2004-03-25 2008-06-25 De Nora Deutschland GmbH Moyens hydrodynamiques pour cellules électrochimiques
WO2009145994A1 (fr) * 2008-03-31 2009-12-03 Michael Steven Georgia Anode de protection cathodique polymère non corrosive
US8329004B2 (en) 2008-03-31 2012-12-11 Aep & T, Llc Polymeric, non-corrosive cathodic protection anode
AU2009251723B2 (en) * 2008-03-31 2013-04-18 Aep & T, Inc. Polymeric, non-corrosive cathodic protection anode

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Publication number Publication date
ITMI20022382A1 (it) 2004-05-12
AU2003301914A1 (en) 2004-06-03

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