EP0298887A1 - Conductor roll for continuously electroplating a metal or other conductive strip - Google Patents

Conductor roll for continuously electroplating a metal or other conductive strip Download PDF

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Publication number
EP0298887A1
EP0298887A1 EP88440055A EP88440055A EP0298887A1 EP 0298887 A1 EP0298887 A1 EP 0298887A1 EP 88440055 A EP88440055 A EP 88440055A EP 88440055 A EP88440055 A EP 88440055A EP 0298887 A1 EP0298887 A1 EP 0298887A1
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EP
European Patent Office
Prior art keywords
conductive
coated
roller according
area
electrolyte
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Granted
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EP88440055A
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German (de)
French (fr)
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EP0298887B1 (en
Inventor
Gilbert Bertrand
Gérard Collin
Pierre Gasperment
Gérard Cottet
Guy Dupoyet
Georges Michel
Jean-Marc Truchot
André Klein
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Sollac Te Puteaux En Stowe Woodward France Sa Te
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STOWE WOODWARD FRANCE SA
Sollac SA
Lorraine de Laminage Continu SA SOLLAC
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Application filed by STOWE WOODWARD FRANCE SA, Sollac SA, Lorraine de Laminage Continu SA SOLLAC filed Critical STOWE WOODWARD FRANCE SA
Priority to AT88440055T priority Critical patent/ATE71413T1/en
Publication of EP0298887A1 publication Critical patent/EP0298887A1/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils
    • C25D7/0657Conducting rolls

Definitions

  • the present invention is in the field of surface coating of metallurgical products or semi-finished products in strips and is aimed in particular at coatings applied to electrically conductive strips by electrolytic deposition, such as steel sheets for example.
  • the invention is in particular intended for the metallurgical industry and more precisely for circular apparatuses, included in electrodeposition lines of the type for example "continuous electrogalvanizing", called conductive rollers, and known for example from documents US-P- 3,483,113 (in particular Figures 7,8,9) US-P-3,634,223 or EP-A 0089790.
  • These conductive rollers which play a cathode role, most often consist of at least one cylindrical conductive ferrule, generally made of stainless steel, mounted on a carbon steel body wider than the active area or areas of the at least one ferrules and through which the electric current passes.
  • This steel body is covered with a flexible polymeric substance, both elastic and insulating, on each side of the active zone or zones, this substance playing a role of eventual entrainment, sealing, electrical insulation and protection of the body against corrosion.
  • These rollers are partially immersed in an electrolyte, the temperature of which is generally substantially higher than ambient temperature.
  • the strip is partially wrapped around a conductive roller, the internal face which will not be coated being in contact on the one hand with the active area of the conductive shell in order to establish the electrical contact, and on the other hand with the elastic insulating substance in order to ensure the tightness of the contact device.
  • the sealing rings are sometimes mounted on a hard insulating bandage (see fig. 7 of document US-p-3,483,113).
  • the elastic elastomer bandage due to its immersion in an electrolyte, also sees its thickness increase due to the phenomena of absorption and chemical combination with the electrolyte (phenomenon well known in the profession of elastomers ), which again contributes to the deterioration of the quality and uniformity of the physical and electrical contact between the strip and the ferrule.
  • the purpose of the present invention is to significantly reduce these drawbacks while ensuring the vital functions of sealing, electrical insulation, protection of the roller body against corrosion and possible entrainment.
  • the invention also aims to improve the coatings applied to the strips, as well as the energy efficiency of the installation, and to reduce the maintenance costs and the frequency of plant shutdowns.
  • At least one intermediate ring is interposed between the active conductive area constituted by the ferrule and the area coated with the elastic and insulating substance, this ring being made of a polymer whose coefficient of dilation, flexibility or changes by swelling following absorption or chemical combination with the electrolyte, have values intermediate between those of the material constituting the conductive active area and those of the material of said coated area.
  • the flexible or sealing elastomer or polymer coating as well as its optional adhesive are not in direct contact with the lateral edges of the active zone (s) of the conductive shell (s), but it is provided to insert between the elastomer or the flexible or sealing polymer and the lateral edges of the active area (s) of the conductive shell (s) one or more polymers, which will be called in the remainder of this text: "intermediate polymers" , put in the form of juxtaposed rings with or without partial superposition, whose expansion coefficients, flexibility or the risks of swelling by absorption or by chemical combination with the electrolyte, or two or three of these parameters at the same time, are intermediate between those, very weak, of stainless steel (generally used for the shell) and those of the elastomer or of the flexible or sealing polymer.
  • this intermediate polymers of the sulfur rubber type (natural or nitrile) hardened commonly called ebonite in the profession or epoxy resins, or any other polymer with relatively closed crosslinking system, resistant to acids and low coefficient of expansion, high hardness of this or these intermediate polymers not being a handicap taking into account the particular geometry of the coating provided for in the invention.
  • a fiber reinforcement (which may for example be: metallic, glass, textile, or synthetic) which radially blocks the intermediate polymer or polymers and limits the variations radial dimension of this part of the intermediate polymer coating, and which can play, in the case of conductive fibers, a possible advantageous role of degressive conduction of electricity from the edge of the active conductive area of the ferrule concerned.
  • Figure 1 shows the rotary roller 1 of electrodeposi tion, partially immersed in an electrolyte 5.
  • Figure 2 highlights the active area 3 of the conductive shell, surrounded by the area 4 coated with an elastic and insulating substance.
  • the strip 2 is partially wrapped around the conductive roller 1, the face that one does not want to cover during this passage being brought into contact with the active area 3 of the shell conductive in order to establish electrical contact, and also being brought into contact with the elastic and insulating substance 4 in order to ensure the tightness of the contact device.
  • the elastic and insulating coating according to the invention consists of two different polymers, although in intimate or sealed lateral contact with each other.
  • the polymer 41 fulfills the functions of sealing, elasticity, entrainment, and electrical insulation whereas the polymer 42, called here intermediate polymer, must only fulfill the functions of sealing and electrical insulation. This therefore allows the choice of harder polymers, with a more closed reticular structure and whose expansion or swelling characteristics are much more acceptable with regard to steel than are those of the types of polymers which one can choose as polymer 41.
  • This intermediate polymer 42 must be adhered perfectly with the lateral end face 3a of the active area 3 of the conductive ferrule and must of course be adhered correctly with the body 1 and with the polymer 41.
  • intermediate polymer 42 we have already defined what we can choose as intermediate polymer 42; as regards polymer 41, one can choose either a polyurethane, or a Hypalon (from Du Pont de Nemours), or even more advantageously, the compound VARIOLASTIC (from the company SW INDUSTRIES, located at Southborough Technology Park, 333 Turnpike Road , SOUTHBOROUGH, MA 01772, USA).
  • FIG. 5 represents another arrangement of the invention according to which the polymer 42 is also used as a sub-layer 42a of the polymer 41 which makes it possible to increase the seal of the assembly.
  • FIG. 6 shows a particular geometry of the polymer coatings 43 and 41 in that their connecting face is inclined in order to make the passage from one zone to the other even more gradual in terms of expansion or swelling.
  • the intermediate polymer 43 here in inclined connection with the polymer 41, also serves as an underlayer 43a.
  • two intermediate polymers 42 and 44 are seen, chosen so that their physicochemical characteristics ensure good progressiveness between the characteristics of the stainless steel used for the conductive shell and those of the elastic and insulating polymer. 41.
  • these polymers 42 and 44 are doped with conductive elements, such as conductive particles of the powder or metallic or carbon fibers in order to ensure the progressiveness of the diffusion of the electric current in the strip from the edge 3a of the conductive ferrule, which avoids resorting to very delicate machining of the edges of conductive ferrules and which makes it possible to 'be perfectly master of the diffusion of electric current.
  • conductive elements such as conductive particles of the powder or metallic or carbon fibers in order to ensure the progressiveness of the diffusion of the electric current in the strip from the edge 3a of the conductive ferrule, which avoids resorting to very delicate machining of the edges of conductive ferrules and which makes it possible to 'be perfectly master of the diffusion of electric current.
  • the flexible or sealing polymer may itself be partially doped with electrically conductive elements.
  • the second intermediate polymer 45 serves as a partial sublayer 45a to the polymer 41.
  • FIG. 10 represents an intermediate polymer 42 of the type of that shown in FIG. 2 but comprising a frame 7 of natural or synthetic fibers.
  • This armature then plays the very interesting role of a mechanical clamping on the one hand, which limits the dimensional radial variations and the no less interesting role, if it is conductive, of vector of progressive electric diffusion on the other hand.
  • the reinforced intermediate polymer can also serve as a sub-layer and be the subject of variants of FIGS. 5 to 7.
  • all or part of an intermediate ring is housed under an edge flange of the conductive active area.
  • the conductive ferrule 3 has an edge 3b with a progressive profile as described in document US-P-3,634,223, and the intermediate polymer 42 comes to fill the entire "hollowed out” part of this ferrule end.
  • the advantage of this harder, more inert intermediate polymer 42 than polymer 41 is even more evident here because in conventional solutions, the slightest swelling of the elastomer causes this wing to lift. edge immediately deteriorating the quality of the strip electrical contact on the conductive ferrule.
  • the invention described here makes it possible to guarantee the straightness of the entire external generator of the active surface of the conductive ferrule 3 by producing, thanks to the intermediate polymer 42, a real blocking of the end wing of the conductive ferrule.
  • FIGS. 12 to 15 Variants of the invention appear in FIGS. 12 to 15 with an undercoat for the polymer 41 and / or therefore progressive inclined contact between the polymers 42 and 41.
  • any width can be given to the areas filled with the intermediate polymers as long as the contact of the strip on the polymer 41 remains sufficient to ensure the functions of sealing, insulation, d elasticity and possible entrainment by adhesion.
  • the number of intermediate polymers is not limiting.
  • this invention applies particularly well to the continuous electrogalvanizing industry, but it is obvious that it can be applied wherever it is desired to carry out a continuous coating by electrodeposition.

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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)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Windings For Motors And Generators (AREA)
  • Prevention Of Electric Corrosion (AREA)

Abstract

A rotary conductor roll intended to be partially immersed in an electrolyte in a manufacturing line for continuously electroplating a strip (2), the roll includes, on its periphery, at least one electrically conductive active zone (3) and at least one coated zone (41) coated with a flexible material which may optionally be associated with an adhesive and which serves to seal the contact between the strip (2) and the conductive active zone (3) from the electrolyte. At least one intermediate ring (42) is interposed between said conductive active zone (3) and said coated zone (41), said intermediate ring being made of a polymer for which at least one of the following coefficients is intermediate in value between the corresponding coefficients of the material constituting the conductive active zone (3) and of the material constituting said coated zone (41), said coefficients being: coefficient of expansion, flexibility, and swelling due to contact with the electrolyte, e.g. by absorption or by chemical combination.

Description

La présente invention se situe dans le domaine du revêtement de surface de produits ou demi-produits métallurgiques en bande et vise notamment les revêtements appliqués sur des feuillards conducteurs de l'électricité par dépôt électrolytique, tels que tôles d'acier par exemple.The present invention is in the field of surface coating of metallurgical products or semi-finished products in strips and is aimed in particular at coatings applied to electrically conductive strips by electrolytic deposition, such as steel sheets for example.

L'invention est notamment destinée à l'industrie métal­lurgique et plus précisément aux appareils circulaires, inclus dans des lignes d'électrodéposition du type par exemple "électro­zingage en continu", appelés rouleaux conducteurs, et connus par exemple par les documents US-P-3 483 113 (notamment les figures 7,8,9) US-P-3 634 223 ou EP-A 0089790.The invention is in particular intended for the metallurgical industry and more precisely for circular apparatuses, included in electrodeposition lines of the type for example "continuous electrogalvanizing", called conductive rollers, and known for example from documents US-P- 3,483,113 (in particular Figures 7,8,9) US-P-3,634,223 or EP-A 0089790.

Ces rouleaux conducteurs, qui jouent un rôle de cathode, sont constitués le plus souvent d'au moins une virole cylindrique conductrice, généralement en acier inoxydable, montée sur un corps en acier au carbone plus large que la ou les zones actives de la ou des viroles et par lequel passe le courant électrique. Ce corps en acier est recouvert d'une substance polymérique souple, à la fois élastique et isolante, de chaque côté de la ou des zones actives, cette substance jouant un rôle d'entraînement éventuel, d'étan­chéïté, d'isolation électrique et de protection du corps contre la corrosion. Ces rouleaux sont immergés partiellement dans un électrolyte dont la température est en général sensiblement supérieure à la température ambiante.These conductive rollers, which play a cathode role, most often consist of at least one cylindrical conductive ferrule, generally made of stainless steel, mounted on a carbon steel body wider than the active area or areas of the at least one ferrules and through which the electric current passes. This steel body is covered with a flexible polymeric substance, both elastic and insulating, on each side of the active zone or zones, this substance playing a role of eventual entrainment, sealing, electrical insulation and protection of the body against corrosion. These rollers are partially immersed in an electrolyte, the temperature of which is generally substantially higher than ambient temperature.

Le feuillard s'enroule partiellement autour d'un rouleau conducteur, la face interne qui ne sera pas revêtue étant au contact d'une part de la zone active de la virole conductrice afin d'établir le contact électrique, et d'autre part de la substance isolante élastique afin d'assurer l'étanchéïté du dispositif de contact.The strip is partially wrapped around a conductive roller, the internal face which will not be coated being in contact on the one hand with the active area of the conductive shell in order to establish the electrical contact, and on the other hand with the elastic insulating substance in order to ensure the tightness of the contact device.

On comprend aisément que si l'on veut une uniformité de dépôt sur le feuillard au cours de son passage dans l'électrolyte, la qualité et l'uniformité du contact entre la virole et le feuillard ainsi que la qualité et l'uniformité de l'étanchéïté latérale de même que l'uniformité des densités de courant sont essentielles.It is easily understood that if one wants uniformity of deposit on the strip during its passage through the electrolyte, the quality and uniformity of the contact between the ferrule and the strip as well as the quality and uniformity of the lateral sealing as well as the uniformity of the current densities are essential.

Les perfectionnement faisant l'objet des brevets américains précités relatifs à ces rouleaux conducteurs pour électrodéposition sont le plus souvent orientés vers la qualité et l'uniformité de ce contact électrique ainsi que vers la répartition des densités de courant qui sont des facteurs très importants. Pour l'étanchéïté, il est prévu généralement une couverture du corps des rouleaux conducteurs en caoutchouc, en néoprène ou en matière analogue, ou en polyuréthane et l'on insiste également sur la nécessité d'utiliser des adhésifs convenables pour ces bandes d'étanchéïté élastiques compte tenu du rôle essentiel qu'elles jouent également dans ce procédé.The improvements which are the subject of the aforementioned American patents relating to these conductive rollers for electrodeposition are most often oriented towards the quality and uniformity of this electrical contact as well as towards the distribution of the current densities which are very important factors. For sealing, provision is generally made for covering the body of the conductive rollers in rubber, neoprene or similar material, or in polyurethane, and the need is also stressed for the use of suitable adhesives for these sealing strips. elastic given the essential role they also play in this process.

Des dispositions géométriques particulières aux extrémités de la ou des viroles conductrices en "creux", en "protubérance", en "dent de scie" ou en biseau sont parfois prévues pour tenter d'augmenter la fiabilité de cette étanchéité (voir fig.4 de l'US-P-3634223 ou fig.2 de l'EP-A-0089790 déjà cités).Special geometrical arrangements at the ends of the conductive shell (s) in "hollow", "protuberance", "sawtooth" or bevel shape are sometimes provided in an attempt to increase the reliability of this seal (see fig. 4 of US-P-3634223 or fig. 2 of EP-A-0089790 already cited).

Par ailleurs, pour être sûr de cumuler les fonctions de l'étanchéïté et de l'isolation électrique, les anneaux d'étanchéïté sont parfois montés sur un bandage isolant dur (voir fig.7 du document US-p-3 483 113).Furthermore, to be sure of combining the functions of sealing and electrical insulation, the sealing rings are sometimes mounted on a hard insulating bandage (see fig. 7 of document US-p-3,483,113).

Cependant, toutes ces dispositions ne permettent pas de garantir totalement la régularité du contact et de la diffusion du courant électrique entre le feuillard et la virole conductrice, ni l'étanchéïté. En effet, dans toutes les dispositions précédentes, le bandage élastique d'étanchéïté arrive directement (à l'exception d'un interface mince constitué par l'adhésif) au contact des faces latérales de la zone active de la virole conductrice. Ceci présente certains inconvénients.
. Sous l'effet de la température et compte tenu du fait que les élastomères se dilatent beaucoup plus que l'acier, le bandage élastique voit son épaisseur (radiale) augmenter beaucoup plus vite que celle de l'acier, ce qui tend à détériorer la qualité et l'uniformité du contact physique et électrique du feuillard sur la zone active de la virole conductrice malgré l'effort de traction exercé sur le feuillard.
. Sous l'effet du temps le bandage élastique en élastomère, du fait de son immersion dans un électrolyte, voit également son épaisseur augmenter de par les phénomènes d'absorbtion et de combinaison chimique avec l'électrolyte (phénomène bien connu dans la profession des élastomères), ce qui là encore contribue à la déterioration de la qualité et de l'uniformité du contact physique et électrique entre le feuillard et la virole.
However, all of these provisions do not fully guarantee the regularity of the contact and the diffusion of the electric current between the strip and the conductive ferrule, nor the seal. In fact, in all of the above arrangements, the elastic sealing bandage comes directly (with the exception of a thin interface formed by the adhesive) into contact with the lateral faces of the active area of the conductive ferrule. This has certain drawbacks.
. Under the effect of temperature and taking into account the fact that elastomers expand much more than steel, the elastic bandage sees its (radial) thickness increase much faster than that of steel, which tends to deteriorate the quality and the uniformity of the physical and electrical contact of the strip on the active area of the conductive shell despite the tensile force exerted on the strip.
. Under the effect of time, the elastic elastomer bandage, due to its immersion in an electrolyte, also sees its thickness increase due to the phenomena of absorption and chemical combination with the electrolyte (phenomenon well known in the profession of elastomers ), which again contributes to the deterioration of the quality and uniformity of the physical and electrical contact between the strip and the ferrule.

On comprend aisément que les détériorations de qualité et d'uniformité de contact sont surtout sensibles aux bords latéraux de la virole conductrice puisque l'élastomère (qui se dilate et qui gonfle) arrive au ras de ces bords, et que le métal, comparative­ment, évolue très peu : or c'est précisément dans ces zones que la diffusion du courant électrique est la plus délicate, puisque la largeur du feuillard à révêtir est supérieure à celle de la virole conductrice et qu'on recherche dans le feuillard une densité de courant d'électrodéposition la plus uniforme possible.It is easy to understand that the deteriorations in quality and uniformity of contact are especially sensitive to the lateral edges of the conductive shell since the elastomer (which expands and swells) arrives close to these edges, and that the metal, comparatively, changes very little: however it is precisely in these areas that the diffusion of electric current is most delicate, since the width of the strip to be coated is greater than that of the conductive ferrule and that a current density is sought in the strip as uniform as possible.

Ces tendances au décollement, même infimes, sont tout de suite très importantes du point de vue de la variation de résistance électrique, donc du point de vue de l'uniformité du dépôt et du rendement de l'installation. On pratique donc couramment des retouches de profil sur ces bandages élastiques, ce qui impose des opérations d'arrêt et de démontage de l'instal­lation.These detachment tendencies, even minute, are immediately very important from the point of view of the variation of electrical resistance, therefore from the point of view of the uniformity of the deposit and the efficiency of the installation. Profile retouching is therefore commonly practiced on these elastic bandages, which requires stopping and dismantling the installation.

Par ailleurs, ces mouvements relatifs entre l'élastomère et le métal finissent par dégrader l'adhésion élastomère-métal et par laisser passer ainsi l'électrolyte qui s'infiltre alors entre les deux constituants, détériorant encore un peu plus l'uniformité de la diffusion du courant électrique, mais aussi et surtout corrodant le corps du rouleau conducteur.Furthermore, these relative movements between the elastomer and the metal end up degrading the elastomer-metal adhesion and thus allowing the electrolyte to pass, which then infiltrates between the two constituents, further deteriorating the uniformity of the diffusion of the electric current, but also and especially corroding the body of the conducting roller.

Le but de la présente invention est de réduire notablement ces inconvénients tout en assurant les fonctions vitales d'étanchéïté, d'isolation électrique, de protection du corps de rouleau contre la corrosion et d'entraînement éventuel. L'invention a aussi pour but d'améliorer les revêtements appliqués sur les feuillards, ainsi que le rendement énergétique de l'installation, et de réduire les coûts d'entretien et la fréquence des arrêts de l'installation.The purpose of the present invention is to significantly reduce these drawbacks while ensuring the vital functions of sealing, electrical insulation, protection of the roller body against corrosion and possible entrainment. The invention also aims to improve the coatings applied to the strips, as well as the energy efficiency of the installation, and to reduce the maintenance costs and the frequency of plant shutdowns.

Ce but est atteint en ce que, selon l'invention, au moins un anneau intermédiaire est intercalé entre la zone active conductrice constituée par la virole et la zone revêtue de la substance élastique et isolante, cet anneau étant en un polymère dont le coefficient de dilatation, la souplesse ou les évolutions par gonflement à la suite d'absorbtion ou combinaison chimique avec l'électrolyte, ont des valeurs intermédiaire entre celles du matériau constituant la zone active conductrice et celles du matériau de ladite zone revêtue.This object is achieved in that, according to the invention, at least one intermediate ring is interposed between the active conductive area constituted by the ferrule and the area coated with the elastic and insulating substance, this ring being made of a polymer whose coefficient of dilation, flexibility or changes by swelling following absorption or chemical combination with the electrolyte, have values intermediate between those of the material constituting the conductive active area and those of the material of said coated area.

Ainsi, selon l'invention, le revêtement élastomère ou polymère souple ou d'étanchéité ainsi que son adhésif éventuel, ne sont pas en contact direct avec les bords latéraux de la ou des zones actives de la ou des viroles conductrices, mais il est prévu d'intercaler entre l'élastomère ou le polymère souple ou d'étanchéité et les bords latéraux de la ou des zones actives de la ou des viroles conductrices un ou plusieurs polymères, qui seront appelés dans la suite de ce texte : "polymères intermé­diaires", mis sous la forme d'anneaux juxtaposés avec ou sans superposition partielle, dont les coefficients de dilatation, la souplesse ou les risques de gonflement par absorption ou par combinaison chimique avec l'électrolyte, ou deux ou trois de ces paramètres à la fois, sont intermédiaires entre ceux, très faibles, de l'acier inoxydable (utilisé en général pour la virole) et ceux de l'élastomère ou du polymère souple ou d'étan­chéité.Thus, according to the invention, the flexible or sealing elastomer or polymer coating as well as its optional adhesive, are not in direct contact with the lateral edges of the active zone (s) of the conductive shell (s), but it is provided to insert between the elastomer or the flexible or sealing polymer and the lateral edges of the active area (s) of the conductive shell (s) one or more polymers, which will be called in the remainder of this text: "intermediate polymers" , put in the form of juxtaposed rings with or without partial superposition, whose expansion coefficients, flexibility or the risks of swelling by absorption or by chemical combination with the electrolyte, or two or three of these parameters at the same time, are intermediate between those, very weak, of stainless steel (generally used for the shell) and those of the elastomer or of the flexible or sealing polymer.

On pourra par exemple choisir pour ce faire des polymères intermédiaires du type caoutchouc au soufre (naturel ou nitrile) durci appelé couramment ebonite dans la profession, ou des résines epoxy, ou tout autre polymère à système de réticulation relativement fermé, résistant aux acides et à faible coefficient de dilatation, la dureté élevée de ce ou ces polymères intermédiaires n'étant pas un handicap compte tenu de la géométrie particulière du revêtement prévue dans l'invention.We can for example choose to do this intermediate polymers of the sulfur rubber type (natural or nitrile) hardened commonly called ebonite in the profession, or epoxy resins, or any other polymer with relatively closed crosslinking system, resistant to acids and low coefficient of expansion, high hardness of this or these intermediate polymers not being a handicap taking into account the particular geometry of the coating provided for in the invention.

Dans une réalisation particulière de l'invention, on prévoit dans le ou les polymères intermédiaires une armature en fibres (qui peuvent être par exemple : métalliques, de verre, textiles, ou synthétiques) qui bloque radialement le ou les poly­mères intermédiaires et limite les variations radiales de dimen­sion de cette partie du revêtement en polymère intermédiaire, et qui peut jouer, dans le cas de fibres conductrices, un rôle éven­tuel avantageux de conduction dégressive de l'électricité à partir du bord de la zone active conductrice de la virole concernée.In a particular embodiment of the invention, there is provided in the intermediate polymer or polymers a fiber reinforcement (which may for example be: metallic, glass, textile, or synthetic) which radially blocks the intermediate polymer or polymers and limits the variations radial dimension of this part of the intermediate polymer coating, and which can play, in the case of conductive fibers, a possible advantageous role of degressive conduction of electricity from the edge of the active conductive area of the ferrule concerned.

L'invention sera mieux comprise et d'autres caractéristi­ques seront mises en évidence à l'aide de la description qui suit, en référence aux dessins schématiques annexés illustrant à titre d'exemples non limitatifs plusieurs formes de réalisation du revêtement isolant selon l'invention.

  • Les figures 1 et 2 sont des vues de côté et de dessus d'un rouleau de l'art antérieur, la figure 3 étant une vue en coupe transversale partielle III-III du rouleau de la figure 1.
  • La figure 4 est une vue en coupe transversale partielle du rouleau conducteur, d'une virole conductrice et du revêtement isolant selon une première forme de réalisation.
  • Les figures 5 à 7 sont des vues similaires à figure 2 illustrant trois autres formes de réalisation du revêtement isolant.
  • Les figures 8 et 9 sont des vues en coupe similaires aux précédentes mais illustrant des modes de réalisation de revêtement isolant comportant plusieurs polymères intermédiaires.
  • La figure 10 est une vue en coupe similaire à la figure 4, avec un polymère intermédiaire à armature de fibres.
  • Les figures 11 à 14 sont des vues en coupe similaires aux précédentes dans lesquelles la virole conductrice comporte des bords à profil dégressif, comme décrit dans le document US-A-3 634 223.
The invention will be better understood and other characteristics will be highlighted with the aid of the description which follows, with reference to the appended schematic drawings illustrating by way of nonlimiting examples several embodiments of the insulating coating according to the invention .
  • FIGS. 1 and 2 are side and top views of a roller of the prior art, FIG. 3 being a view in partial cross-section III-III of the roller of FIG. 1.
  • Figure 4 is a partial cross-sectional view of the conductive roller, a conductive ferrule and the insulating coating according to a first embodiment.
  • Figures 5 to 7 are views similar to Figure 2 illustrating three other embodiments of the insulating coating.
  • Figures 8 and 9 are sectional views similar to the preceding but illustrating embodiments of insulating coating comprising several intermediate polymers.
  • Figure 10 is a sectional view similar to Figure 4, with an intermediate fiber-reinforced polymer.
  • FIGS. 11 to 14 are sectional views similar to the previous ones in which the conductive ferrule has edges with a decreasing profile, as described in document US-A-3,634,223.

La figure 1 montre le rouleau rotatif 1 d'électrodéposi­ tion, immergé partiellement dans une électrolyte 5. La figure 2 met en évidence la zone active 3 de la virole conductrice, entourée de la zone 4 revêtue d'une substance élastique et isolante.Figure 1 shows the rotary roller 1 of electrodeposi tion, partially immersed in an electrolyte 5. Figure 2 highlights the active area 3 of the conductive shell, surrounded by the area 4 coated with an elastic and insulating substance.

Ainsi que le montrent les figures 1 à 3, le feuillard 2 s'enroule partiellement autour du rouleau conducteur 1, la face que l'on ne veut pas revêtir au cours de ce passage étant mise en contact avec la zone active 3 de la virole conductrice afin d'établir le contact électrique, et étant mise en contact également avec la substance élastique et isolante 4 afin d'assurer l'étanchéïté du dispositif de contact.As shown in Figures 1 to 3, the strip 2 is partially wrapped around the conductive roller 1, the face that one does not want to cover during this passage being brought into contact with the active area 3 of the shell conductive in order to establish electrical contact, and also being brought into contact with the elastic and insulating substance 4 in order to ensure the tightness of the contact device.

Ainsi que le montre la figure 4, le revêtement élastique et isolant selon l'invention se compose de deux polymères différents, quoique en contact latéral intime ou étanche l'un avec l'autre. Le polymère 41 remplit les fonctions d'étanchéïté, d'élasticité, d'entraînement, et d'isolation électrique alors que le polymère 42, appelé ici polymère intermédiaire, doit seulement remplir les fonctions d'étanchéïté et d'isolation électrique. Ceci autorise donc le choix de polymères plus durs, à structure réticulaire plus fermée et dont les caractéristiques de dilatation ou de gonflement sont beaucoup plus acceptables en regard de l'acier que ne le sont celles des types de polymères que l'on peut choisir comme polymère 41.As shown in Figure 4, the elastic and insulating coating according to the invention consists of two different polymers, although in intimate or sealed lateral contact with each other. The polymer 41 fulfills the functions of sealing, elasticity, entrainment, and electrical insulation whereas the polymer 42, called here intermediate polymer, must only fulfill the functions of sealing and electrical insulation. This therefore allows the choice of harder polymers, with a more closed reticular structure and whose expansion or swelling characteristics are much more acceptable with regard to steel than are those of the types of polymers which one can choose as polymer 41.

Ce polymère intermédiaire 42 doit être adhérisé parfaitement avec la face latérale d'etrémité 3a de la zone active 3 de la virole conductrice et doit bien sûr être adhérisé correctement avec le corps 1 et avec le polymère 41.This intermediate polymer 42 must be adhered perfectly with the lateral end face 3a of the active area 3 of the conductive ferrule and must of course be adhered correctly with the body 1 and with the polymer 41.

On a déjà défini ce qu'on peut choisir comme polymère intermédiaire 42 ; en ce qui concerne le polymère 41, on peut choisir soit un polyuréthane, soit un Hypalon (de Du Pont de Nemours), soit encore plus avantageusement, le compound VARIOLASTIC (de la compagnie SW INDUSTRIES, sise à Southborough Technology Park, 333 Turnpike Road, SOUTHBOROUGH, MA 01772, USA).We have already defined what we can choose as intermediate polymer 42; as regards polymer 41, one can choose either a polyurethane, or a Hypalon (from Du Pont de Nemours), or even more advantageously, the compound VARIOLASTIC (from the company SW INDUSTRIES, located at Southborough Technology Park, 333 Turnpike Road , SOUTHBOROUGH, MA 01772, USA).

On comprend aisément que grâce à ce polymère intermédiaire les mouvements ou variations de dimensions du polymère 41 affecteront beaucoup moins la qualité et l'uniformité du contact électrique du feuillard 2 sur la face active de la virole conductrice 3 et que l'étanchéïté, donc là encore l'uniformité de la diffusion électrique en extrémité de virole conductrice 3 ainsi que la protection du corps 1 contre la corrosion se trouveront largement augmentées. Les essais réalisés en vraie grandeur ont prouvé l'efficacité de l'invention par rapport aux solutions classiques, en améliorant très sensiblement le rendement général de l'installation ainsi que la qualité et l'uniformité du dépôt et en multipliant par un facteur supérieur à trois le temps de travail du rouleau conducteur entre deux retouches du profil par rectification, donc en réduisant dans les mêmes proportions la fréquence des arrêts nécessaires.It is easy to understand that, thanks to this intermediate polymer, the movements or variations in dimensions of the polymer 41 will affect the quality and uniformity much less. of the electrical contact of the strip 2 on the active face of the conductive ferrule 3 and that the seal, therefore again the uniformity of the electrical diffusion at the end of the conductive ferrule 3 as well as the protection of the body 1 against corrosion will be largely increased. Full-scale tests have proven the effectiveness of the invention compared to conventional solutions, by very significantly improving the overall yield of the installation as well as the quality and uniformity of the deposit and multiplying by a factor greater than three the working time of the conductive roller between two retouching of the profile by rectification, thus reducing in the same proportions the frequency of necessary stops.

On obtient déjà de bons résultats avec une largeur de polymère intermédiaire 42 supérieure à 10 mm, l'optimum se situant, selon bien sûr les largeurs de feuillard à travailler, entre 10 et 40mm.Good results are already obtained with an intermediate polymer width 42 greater than 10 mm, the optimum being, of course, depending on the strip widths to be worked, between 10 and 40 mm.

La figure 5 représente une autre disposition de l'invention selon laquelle le polymère 42 est également utilisé en sous-couche 42a du polymère 41 ce qui permet d'augmenter l'étanchéïté de l'ensemble.FIG. 5 represents another arrangement of the invention according to which the polymer 42 is also used as a sub-layer 42a of the polymer 41 which makes it possible to increase the seal of the assembly.

La figure 6 représente une géométrie particulière des revêtements polymères 43 et 41 en ce que leur face de liaison est inclinée afin de rendre encore plus progressif le passage d'une zone à l'autre en matière de dilatation ou de gonflement.FIG. 6 shows a particular geometry of the polymer coatings 43 and 41 in that their connecting face is inclined in order to make the passage from one zone to the other even more gradual in terms of expansion or swelling.

Dans la figure 7, comme dans la figure 5, le polymère intermédiaire 43, ici à liaison inclinée avec le polymère 41, sert également de sous-couche 43a.In FIG. 7, as in FIG. 5, the intermediate polymer 43, here in inclined connection with the polymer 41, also serves as an underlayer 43a.

Dans la figure 8, l'on voit deux polymères intermédiaires 42 et 44, choisis de telle façon que leurs caractéristiques physico-chimiques assurent une bonne progressivité entre les carac­téristiques de l'acier inoxydable utilisé pour la virole conductrice et celles du polymère élastique et isolant 41.In FIG. 8, two intermediate polymers 42 and 44 are seen, chosen so that their physicochemical characteristics ensure good progressiveness between the characteristics of the stainless steel used for the conductive shell and those of the elastic and insulating polymer. 41.

Dans une variante de l'invention, ces polymères 42 et 44, par nature relativement isolants, sont dopés en éléments conducteurs, tels que des particules conductrices du type poudre ou fibres métalliques ou de carbone afin d'assurer la progressivité de la diffusion du courant électrique dans le feuillard à partir du bord 3a de la virole conductrice, ce qui évite de recourir à des usinages très délicats des bords de viroles conductrices et ce qui permet d'être parfaitement maître de la diffusion du courant électrique. Dans certains cas le polymère souple ou d'étanchéïté pourra lui-même être dopé partiellement en éléments conducteurs de l'électricité.In a variant of the invention, these polymers 42 and 44, by their nature relatively insulating, are doped with conductive elements, such as conductive particles of the powder or metallic or carbon fibers in order to ensure the progressiveness of the diffusion of the electric current in the strip from the edge 3a of the conductive ferrule, which avoids resorting to very delicate machining of the edges of conductive ferrules and which makes it possible to 'be perfectly master of the diffusion of electric current. In some cases the flexible or sealing polymer may itself be partially doped with electrically conductive elements.

Dans la figure 9, le deuxième polymère intermédiaire 45 sert de sous-couche partielle 45a au polymère 41.In FIG. 9, the second intermediate polymer 45 serves as a partial sublayer 45a to the polymer 41.

La figure 10 représente un polymère intermédiaire 42 du type de celui représenté en figure 2 mais comportant une armature 7 de fibres naturelles ou synthétiques.FIG. 10 represents an intermediate polymer 42 of the type of that shown in FIG. 2 but comprising a frame 7 of natural or synthetic fibers.

Dans une réalisation de l'invention, on a choisi des fibres isolantes, mais dans une autre réalisation de l'invention, on a choisi des fibres conductrices de l'électricité afin de créer une certaine conductivité électrique dans cette zone pour mieux maîtriser la diffusion électrique dans le feuillard.In one embodiment of the invention, we have chosen insulating fibers, but in another embodiment of the invention, we have chosen electrically conductive fibers in order to create a certain electrical conductivity in this area to better control the diffusion. electric in the strip.

Cette armature joue alors le rôle très intéressant d'un bridage mécanique d'une part, ce qui limite les variations radiales dimensionnelles et le rôle non moins intéressant, si elle est conductrice, de vecteur de diffusion électrique progressive d'autre part.This armature then plays the very interesting role of a mechanical clamping on the one hand, which limits the dimensional radial variations and the no less interesting role, if it is conductive, of vector of progressive electric diffusion on the other hand.

Le polymère intermédiaire armé peut également servir de sous-couche et faire l'objet des variantes des figures 5 à 7.The reinforced intermediate polymer can also serve as a sub-layer and be the subject of variants of FIGS. 5 to 7.

Selon une variante de l'invention, tout ou partie d'un anneau intermédiaire vient se loger sous une aile de bord de la zone active conductrice.According to a variant of the invention, all or part of an intermediate ring is housed under an edge flange of the conductive active area.

Dans la figure 11, la virole conductrice 3 comporte un bord 3b à profil progressif comme décrit dans le document US-P-3 634 223, et le polymère intermédiaire 42 vient garnir toute la partie "évidée" de cette extrémité de virole. L'intérêt de ce polymère intermédiaire 42 plus dur, plus inerte que le polymère 41 est encore plus évident ici car dans les solutions classiques, le moindre gonflement de l'élastomère fait soulever cette aile de bord détériorant immédiatement la qualité du contact électrique feuillard sur la virole conductrice.In FIG. 11, the conductive ferrule 3 has an edge 3b with a progressive profile as described in document US-P-3,634,223, and the intermediate polymer 42 comes to fill the entire "hollowed out" part of this ferrule end. The advantage of this harder, more inert intermediate polymer 42 than polymer 41 is even more evident here because in conventional solutions, the slightest swelling of the elastomer causes this wing to lift. edge immediately deteriorating the quality of the strip electrical contact on the conductive ferrule.

L'invention ici décrite permet de garantir la rectitude de la totalité de la génératrice extérieure de la surface active de la virole conductrice 3 en réalisant grâce au polymère intermédiaire 42 un véritable blocage de l'aile d'extrémité de la virole conductrice.The invention described here makes it possible to guarantee the straightness of the entire external generator of the active surface of the conductive ferrule 3 by producing, thanks to the intermediate polymer 42, a real blocking of the end wing of the conductive ferrule.

Des variantes de l'invention apparaissent dans les figures 12 à 15 avec sous-couche pour le polymère 41 et/ou contact incliné donc progressif entre les polymères 42 et 41.Variants of the invention appear in FIGS. 12 to 15 with an undercoat for the polymer 41 and / or therefore progressive inclined contact between the polymers 42 and 41.

Comme il va de soi, la présente invention ne se limite pas aux seuls exemples de réalisation montrés ci-avant à titre d'exemples non limitatifs, mais en embrasse, au contraire, toutes les formes de réalisation mettant en oeuvre des moyens similaires ou équivalents.It goes without saying that the present invention is not limited to the sole exemplary embodiments shown above by way of nonlimiting examples, but on the contrary embraces all of the embodiments employing similar or equivalent means. .

C'est ainsi que, par exemple, n'importe quelles largeurs peuvent être conférées aux zones remplies par les polymères intermédiaires du moment que le contact du feuillard sur le polymère 41 reste suffisant pour assurer les fonctions d'étanchéïté, d'isolation, d'élasticité et d'entraînement éventuel par adhérence. De même le nombre de polymères intermédiaires n'est pas limitatif.Thus, for example, any width can be given to the areas filled with the intermediate polymers as long as the contact of the strip on the polymer 41 remains sufficient to ensure the functions of sealing, insulation, d elasticity and possible entrainment by adhesion. Similarly, the number of intermediate polymers is not limiting.

Par ailleurs, les différentes formes de réalisation montrées ci-avant peuvent être combinées ensemble sans que l'on sorte pour autant du cadre de la présente invention.Furthermore, the various embodiments shown above can be combined together without departing from the scope of the present invention.

Enfin, cette invention s'applique particulièrement bien à l'industrie d'électrozingage en continu, mais il est évident qu'elle peut être appliquée partout où l'on souhaite effectuer un revêtement en continu par électrodéposition.Finally, this invention applies particularly well to the continuous electrogalvanizing industry, but it is obvious that it can be applied wherever it is desired to carry out a continuous coating by electrodeposition.

Claims (10)

1. Rouleau conducteur rotatif, destiné à être immergé partiel­lement dans un électrolyte (5) dans une ligne d'électrodéposition sur feuillard (2) en continu, du type comportant à sa périphérie au moins une zone active médiane (3) conductrice du courant électri­que et au moins une zone d'extrémité (41) à chaque extrémité revêtue d'un matériau souple et destinée à assurer l'étanchéité vis-à-vis de l'électrolyte de la surface de contact entre le feuillard (2) et la zone active conductrice (3), rouleau caractérisé en ce qu'au moins un anneau intermédiaire (42,43, 44,45) est intercalé entre ladite zone active conductrice (3) et ladite zone revêtue (41), cet anneau étant en un polymère dont le coefficient de dilatation, la souplesse ou les évolutions par gonflement à la suite d'absorp­tion ou combinaison chimique avec l'électrolyte, ont des valeurs intermédiaires entre celles du matériau constituant la zone active conductrice (3) et celles du matériau de ladite zone revêtue (41).1. Rotating conductive roller, intended to be partially immersed in an electrolyte (5) in a continuous plating line on strip (2), of the type comprising at its periphery at least one median active area (3) conducting the electric current and at least one end zone (41) at each end coated with a flexible material and intended to seal against the electrolyte the contact surface between the strip (2) and the zone active conductive (3), roller characterized in that at least one intermediate ring (42,43, 44,45) is interposed between said active conductive zone (3) and said coated zone (41), this ring being made of a polymer whose coefficient of expansion, flexibility or changes by swelling following absorption or chemical combination with the electrolyte, have intermediate values between those of the material constituting the active conductive area (3) and those of the material of said area coated (41). 2. Rouleau selon la revendication 1 caractérisé en ce que le polymère utilise pour constituer l'anneau intermédiaire (42) est armé avec des fibres naturelles ou synthétiques à caractère isolant.2. Roller according to claim 1 characterized in that the polymer used to form the intermediate ring (42) is reinforced with natural or synthetic fibers of insulating nature. 3. Rouleau selon la revendication 1 caractérisé en ce que le polymère utilise pour constituer l'anneau intermédiaire (42) est armé avec des fibres naturelles ou synthétiques à caractère conducteur de l'électricité.3. Roller according to claim 1 characterized in that the polymer used to form the intermediate ring (42) is reinforced with natural or synthetic fibers of an electrically conductive nature. 4. Rouleau selon la revendication 1, 2 ou 3, caractérisé en ce que le polymère utilisé pour constituer l'anneau intermédiaire sont dopés en éléments conducteurs.4. Roller according to claim 1, 2 or 3, characterized in that the polymer used to form the intermediate ring are doped with conductive elements. 5. Rouleau selon la revendication 1, caractérisé en ce que le matériau souple de la zone revêtue (41) est dopé partiellement en éléments conducteurs.5. Roller according to claim 1, characterized in that the flexible material of the coated area (41) is partially doped with conductive elements. 6. Rouleau selon la revendicatin 1 ou 5, caractérisé en ce que l'anneau intermédiaire (42,43,45) forme une sous-couche (42a,43a, 45a) pour le matériau de la zone revêtue (41).6. Roller according to claim 1 or 5, characterized in that the intermediate ring (42,43,45) forms a sub-layer (42a, 43a, 45a) for the material of the coated area (41). 7. Rouleau selon la revendication 1, caractérisé en ce que l'anneau intermédiaire (42,43) vient se loger au moins partiellement sous une aile de bord (3b) de la zone active conductrice (3).7. Roller according to claim 1, characterized in that the intermediate ring (42,43) is housed at least partially under an edge flange (3b) of the active conductive area (3). 8. Rouleau selon la revendication 1, caractérisé en ce que l'anneau intermédiaire (42-43) comporte une surface de liaison inclinée par rapport à un plan perpendiculaire à l'axe de rotation du rouleau conducteur (1).8. Roller according to claim 1, characterized in that the intermediate ring (42-43) has a connecting surface inclined relative to a plane perpendicular to the axis of rotation of the conductive roller (1). 9. Rouleau selon la revendication 1, caractérisé en ce qu'il comporte deux anneaux intermédiaires juxtaposés (42,44) en poly­mères de propriétés physico-chimiques différentes, les caractéri­stiques de dilatation ou de souplesse ou de gonflement par absorp­tion ou combinaison chimique avec l'électrolyte de ces différents polymères ayant des valeurs progressives anneau par anneau pour passer de celles de la zone active conductrice (3) à celle de la zone revêtue (41).9. Roller according to claim 1, characterized in that it comprises two juxtaposed intermediate rings (42,44) made of polymers of different physicochemical properties, the characteristics of expansion or flexibility or swelling by absorption or chemical combination with l electrolyte of these different polymers having progressive values ring by ring to pass from those of the active conductive area (3) to that of the coated area (41). 10. Rouleau selon la revendication 1 caractérisé en ce que le matériau souple de la zone d'éxtrémité (41) est revêtu par un adhésif.10. Roller according to claim 1 characterized in that the flexible material of the end zone (41) is coated with an adhesive.
EP88440055A 1987-07-07 1988-07-04 Conductor roll for continuously electroplating a metal or other conductive strip Expired - Lifetime EP0298887B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88440055T ATE71413T1 (en) 1987-07-07 1988-07-04 CURRENT FEED ROLLER FOR CONTINUOUS ELECTROLYTIC PLATING OF METALLIC OR OTHER CONDUCTING TAPES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8709651A FR2617869B1 (en) 1987-07-07 1987-07-07 ROTARY CONDUCTIVE ROLLER FOR CONTINUOUS ELECTROLYTIC DEPOSITION ON METAL STRIPS OR OTHER ELECTRICALLY CONDUCTIVE STRIPS
FR8709651 1987-07-07

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EP0298887A1 true EP0298887A1 (en) 1989-01-11
EP0298887B1 EP0298887B1 (en) 1992-01-08

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EP (1) EP0298887B1 (en)
JP (1) JPH0768636B2 (en)
KR (1) KR950013596B1 (en)
AT (1) ATE71413T1 (en)
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CA (1) CA1321165C (en)
DE (1) DE3867550D1 (en)
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KR100373677B1 (en) * 1998-09-16 2003-05-09 주식회사 포스코 Electroplating Conduction Roll
DE10019720A1 (en) * 2000-04-20 2001-10-31 Atotech Deutschland Gmbh Method and device for electrical contacting of plate-like items to be treated in electrolytic processes
KR20020001079A (en) * 2000-06-24 2002-01-09 이구택 Device for preventing conductor roll band mark
US7045043B1 (en) * 2000-07-24 2006-05-16 Pohang Iron And Steel Co., Ltd. Method of reducing a band mark of an electroplating steel sheet
KR100460667B1 (en) * 2000-11-22 2004-12-09 주식회사 포스코 A conductor roll
US20060243593A1 (en) * 2005-04-29 2006-11-02 Bowman Kenneth A Apparatus and method for improving contact between a web and a roll
FR2919511B1 (en) * 2007-07-30 2010-01-29 Snecma Propulsion Solide COMPOSITE THERMOSTRUCTURAL ROLL
CN109652793A (en) * 2019-03-04 2019-04-19 厦门佰事兴新材料科技有限公司 A kind of processing method of the conductive bar of squirrel-cage silver conductive rollers

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CN113757382A (en) * 2021-09-09 2021-12-07 广东嘉元科技股份有限公司 Special online anti-oxidation device for cathode roller

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BR8803359A (en) 1989-01-31
FR2617869B1 (en) 1989-12-15
EP0298887B1 (en) 1992-01-08
JPH01127694A (en) 1989-05-19
US4849083A (en) 1989-07-18
FR2617869A1 (en) 1989-01-13
ES2029726T3 (en) 1992-09-01
KR890002446A (en) 1989-04-10
DE3867550D1 (en) 1992-02-20
KR950013596B1 (en) 1995-11-13
ATE71413T1 (en) 1992-01-15
JPH0768636B2 (en) 1995-07-26
SU1722236A3 (en) 1992-03-23
GR3004293T3 (en) 1993-03-31
CA1321165C (en) 1993-08-10

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