EP0276190A1 - Process and apparatus for the electrolytic deposition of a continuous nickel film on wire - Google Patents

Process and apparatus for the electrolytic deposition of a continuous nickel film on wire Download PDF

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Publication number
EP0276190A1
EP0276190A1 EP88420002A EP88420002A EP0276190A1 EP 0276190 A1 EP0276190 A1 EP 0276190A1 EP 88420002 A EP88420002 A EP 88420002A EP 88420002 A EP88420002 A EP 88420002A EP 0276190 A1 EP0276190 A1 EP 0276190A1
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European Patent Office
Prior art keywords
nickel
wire
bath
tank
activation
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Granted
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EP88420002A
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German (de)
French (fr)
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EP0276190B1 (en
Inventor
Jacques Léfèbre
Philippe Giménez
Gabriel Colombier
Armand Golay
Jean-Sylvestre Safrany
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Rio Tinto France SAS
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Aluminium Pechiney SA
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires

Definitions

  • the invention relates to a method and a device for electrolytically depositing, on parade, a continuous film of nickel in the form of globules of adjustable size on metallic wire for electrical use.
  • the French patent No. 2526052 owned by the Applicant, teaches a method and apparatus for coating a large length of metal with a metallic layer. It applies in particular to direct nickel plating, that is to say without the application of intermediate layers, of electrical conductors of aluminum or one of its alloys, with a diameter between 1.5 and 3 mm and used for either industrial or domestic purposes.
  • the process consists in passing the wire, previously freed from lubrication residues, firstly through a liquid current socket which will be called hereinafter activation bath where, by passing a continuous or pulsed electric current, it charges positively and acquires, under the action of acidic and / or saline compounds contained in the bath, a so-called active surface which is perfectly suitable for subsequent coating; then, through a nickel-plating bath where, by passing the same current, it becomes negatively charged and gradually becomes covered with nickel until it forms a continuous film.
  • This process made it possible to obtain, on wires traveling at nearly 300 m / minute, a nickel film with a thickness of a few microns having in particular good adhesion and a weak and non-evolving contact resistance, properties which are essential for producing conductors. reliable electrical.
  • This adhesion was such that the wire could then be drawn to a diameter of 0.78 mm without there being any detachment or tearing of the nickel coating.
  • the aforementioned patent also teaches a compact device in which the activation and nickel-plating tanks each have a length close to 5 meters and are each equipped with a planar electrode extending parallel to the wire over its entire path in the bath.
  • the Applicant now aiming to manufacture electric cables from strands made up of a number of nickel-plated aluminum wires with a diameter of less than 1 mm had considered using the above method by supplementing it with a additional range of drawing operations intended to bring the wires to the desired diameter.
  • it then encountered certain difficulties with regard to the behavior of the nickel coating which, for significant reductions in section, deteriorated and led to an unfavorable change in the contact resistance of the wire obtained. This is why she tried to apply her process to the coating of fine wires in order to be able to strand it directly and thus to avoid any drawing operation.
  • new drawbacks have appeared, such as the formation of powdery deposits or discontinuous films.
  • the Applicant has found that it is necessary to reduce the current density in the upstream part of the nickel-plating bath in order to see a layer of nickel appear in the form of globules which adhere and cover the substrate better and which gives a low contact resistance.
  • This improvement has been accentuated by replacing the profile of the current density inherent in the prior process, namely a decreasing curve from the entry to the exit of the bath, a profile in which a regular growth succeeds a slow decay and, in particular , by locating the maximum density at a point in the bath located between a third of the length from the inlet and the middle while reducing as much as possible the difference between this maximum density and the minimum density.
  • the means of the invention consist, on the other hand, in adjusting the acidity of the nickel-plating bath to a pH value of between 1 and 5 because within this range, the Applicant has found that the size of the nickel globules with the advantages mentioned above and this all the more as the acidity increases. These results are particularly clear for pH values between 2.5 and 3.5.
  • This acidity can be increased, for example, by increasing the amount of sulfamic acid in the nickel plating bath which, as described in the aforementioned patent also contains nickel chloride and orthoboric acid while in the activation bath, we find the same constituents described in said patent.
  • the method of the invention can be applied to any metallic wire such as copper wire for example.
  • any metallic wire such as copper wire for example.
  • nickel plating of aluminum wires or in one of its alloys for electrical use because it allows, because of its relatively low specific mass and the lightening which results therefrom, a substantial saving of energy. when it is substituted for copper for making cables intended to equip, for example, land or air transport vehicles.
  • This process is particularly suitable for nickel plating of small section strands (less than 1 mm) because it gives a very adherent coating which makes it suitable for making strands and cables which can be obtained by simultaneously nickel plating several strands placed in vertical tablecloth in the same bath.
  • the invention also relates to a device for applying the method described above.
  • This device comprises, as in the aforementioned patent, in the direction of travel of the wire, a first tank containing the activation bath, a rinsing compartment, a second tank containing the nickel-plating bath, the two tanks each being equipped with at least two pairs of planar electrodes, each pair being formed of electrodes placed on either side of the wire or wires and at least partially immersed in their respective bath, the pairs of the activation bath being connected to a source of negative current and those of the nickel bath being connected to a positive current source.
  • the electrodes of at least one of said pairs are removable, placed at an adjustable distance from at least one neighboring pair and from the wire and which is interposed between each of said electrodes and the wire at least one removable screen made of electrically insulating material.
  • the device according to the invention consists on the one hand by pairs of electrodes which can be moved either along the length of the tank to bring them closer or away from each other or leave free spaces in particular at one of the ends of the tanks, or according to the Another dimension of the tank to bring them more or less close to the wire or wires to be coated.
  • the current density profile along the wire knowing that the absence of electrodes decreases this density and that the approximation of the electrodes of the wire increases it.
  • the profile defined above can be obtained either by leaving a free space in the upstream part of the nickel-plating tank and / or downstream of the activation tank, or by bringing the electrodes of the wire in the part opposite to the aforementioned part.
  • the specific means for moving the electrodes they can be produced from the knowledge of a person skilled in the art.
  • the device of the invention also consists of the presence of at least one removable screen between each of the electrodes of at least one pair and the wire.
  • These screens are made of an electrically insulating material and preferably have good resistance to the activation or nickel-plating bath. These screens are placed more or less far from the wire and at least partially mask the electrodes so that they interrupt or deflect the lines of current flowing in the baths and therefore make it possible to reduce the current density at precise locations in the bath.
  • these screens are placed in the upstream part of the tank and / or downstream of the activation tank.
  • screens provided with holes of variable diameter.
  • the number of holes is varied as a function of the position of the screen in the tank and, in particular, their number is increased in the direction of travel of the wire.
  • the device thus designed is suitable for the treatment of one or more wires by providing in the walls of the tanks located at the end of suitable openings located next to each other and equipped with seals. Preferably, to encourage exchanges between the wire and the baths, a circulation of these can be ensured by means of pumps.
  • the device is also notably completed by a rinsing compartment intended to eliminate by means of demineralized water the bath which may have been entrained out of the nickel-plating tank, the water which wets the wire then being evaporated in a drying compartment.
  • All the rinsing tanks and compartments are designed as modular elements, of length and section adaptable to the coating problem posed and easily associable with each other.
  • FIG. 1 represents a perspective view of a nickel-plating tank cut lengthwise along a vertical plane placed a little in front of the plant of median symmetry .
  • the tank 1 of parallelepiped shape whose small faces 2 are each pierced with three holes 3 through which pass three metal strands 4 which pass in the direction of the arrow 5 in the nickel plating bath 6.
  • the electrodes and the screens are suspended in the bath by means not shown which allow them to be moved longitudinally and transversely in the tank.
  • the bath is driven in a circulation movement from bottom to top by means of a pump, not shown, supplied by the flow of overflows 10 and which discharges said bath into the distribution ramp 11.
  • a pump not shown
  • a device comprising successively: - a first rinsing compartment with internal dimensions 1000 x 120 x 120 mm containing 9 liters of 70 ° C solution pumped from an 80-liter reserve tank - a rinsing compartment - an activation tank with internal dimensions 1000 x 120 x 120 mm fitted with electrodes with dimensions 100 x 80 x 80 mm connected to a negative current source capable of delivering 2000 A at 40 Volts and screens with dimensions 120 x 40 x 5 mm in polypropylene arranged so as to obtain a distribution of the judiciously chosen current density, said tank containing a solution at 45 ° C.
  • nickel-plating tank with internal dimensions 1000 x 120 x 120 mm fitted with electrodes connected to the positive pole of the same current source which supplies the activation tank and screens of the same dimensions as those of the activation tank , the assembly being arranged according to Figure 1; this nickel-plating tank containing a solution at 65 ° C.
  • the invention finds its application in the nickel plating of metallic wires in particular of aluminum, of any diameter and, in particular, less than 1 mm and allows obtaining by stranding and wiring of light and reliable electrical conductors which are particularly advantageous for equipping spacecraft. air or land transport where energy saving by reducing equipment is much appreciated.

Abstract

The invention relates to a process and an apparatus for electrolytically depositing, in a moving mode, a continuous film of nickel on metal wire for electrical use. The process comprises using an activation bath and a nickel-plating bath in which the current density is reduced in the upstream portion of the nickel plating bath and/or the downstream portion of the activation bath and the acidity of the nickel-plating bath is so regulated as to develop the nickel in the form of strongly adhering globules of small diameter, which completely cover the wire. The reduction in the above mentioned current density and control in respect of the current density profile along the bath may be achieved by acting on the position of the electrodes in the bath and/or by interposing screens between the electrodes and the wire.

Description

L'invention concerne un procédé et un dispositif pour déposer électrolytiquement, au défilé, un film continu de nickel sous forme de globules de taille réglable sur du fil métallique à usage électrique.The invention relates to a method and a device for electrolytically depositing, on parade, a continuous film of nickel in the form of globules of adjustable size on metallic wire for electrical use.

Le brevet français no 2 526 052, appartenant à la demanderesse, enseigne un procédé et un dispositif pour revêtir une grande longueur de métal d'une couche métallique. Il s'applique notamment au nickelage direct, c'est-à-dire sans l'application de couches intermédiaires, de conducteurs électriques en aluminium ou en un de ses alliages, de diamètre compris entre 1,5 et 3 mm et utilisés à des fins soit industrielles, soit domestiques.The French patent No. 2526052, owned by the Applicant, teaches a method and apparatus for coating a large length of metal with a metallic layer. It applies in particular to direct nickel plating, that is to say without the application of intermediate layers, of electrical conductors of aluminum or one of its alloys, with a diameter between 1.5 and 3 mm and used for either industrial or domestic purposes.

Le procédé consiste à faire passer le fil, préalablement débarrassé des résidus de lubrification, d'abord à travers une prise de courant liquide qu'on appellera ci-après bain d'activation où, par passage d'un courant électrique continu ou pulsé, il se charge positivement et acquiert sous l'action de composés acides et/ou salins contenus dans le bain une surface dite active convenant parfaitement à un revêtement ultérieur; puis, à travers un bain de nickelage où, par passage du même courant, il se charge négativement et se recouvre progressivement de nickel jusqu'à former un film continu. Ce procédé a permis d'obtenir sur des fils défilant à près de 300 m/minute un film de nickel d'une épaisseur de quelques microns présentant notamment une bonne adhérence et une résistance de contact faible et non évolutive, propriétés indispensables pour réaliser des conducteurs électriques fiables. Cette adhérence était telle que le fil pouvait ensuite être tréfilé jusqu'au diamètre 0,78 mm sans qu'on constate ni décollement, ni arrachement du revêtement de nickel.The process consists in passing the wire, previously freed from lubrication residues, firstly through a liquid current socket which will be called hereinafter activation bath where, by passing a continuous or pulsed electric current, it charges positively and acquires, under the action of acidic and / or saline compounds contained in the bath, a so-called active surface which is perfectly suitable for subsequent coating; then, through a nickel-plating bath where, by passing the same current, it becomes negatively charged and gradually becomes covered with nickel until it forms a continuous film. This process made it possible to obtain, on wires traveling at nearly 300 m / minute, a nickel film with a thickness of a few microns having in particular good adhesion and a weak and non-evolving contact resistance, properties which are essential for producing conductors. reliable electrical. This adhesion was such that the wire could then be drawn to a diameter of 0.78 mm without there being any detachment or tearing of the nickel coating.

Le brevet précité enseigne également un dispositif compact dans lequel les cuves d'activation et de nickelage ont chacune une longueur voisine de 5 mètres et sont équipées chacune d'une électrode plane s'allongeant parallèlement au fil sur tout son parcours dans le bain.The aforementioned patent also teaches a compact device in which the activation and nickel-plating tanks each have a length close to 5 meters and are each equipped with a planar electrode extending parallel to the wire over its entire path in the bath.

La demanderesse ayant maintenant pour but de fabriquer des câbles électriques à partir de torons constitués d'un certain nombre de fils d'aluminium nickelé d'un diamètre inférieur à 1 mm avait envisagé d'utiliser le procédé ci-dessus en le complétant par une gamme supplémentaire d'opérations de tréfilage destinées à amener les fils au diamètre voulu. Mais, elle a alors recontré certaines difficultés en ce qui concerne la tenue du revêtement de nickel qui, pour des réductions de section importantes, se dégradait et conduisait à une évolution défavorable de la résistance de contact du fil obtenu. C'est pourquoi elle a essayé d'appliquer son procédé au revêtement de fils fins afin de pouvoir le toronner directement et d'éviter ainsi toute opération de tréfilage. Mais, de nouveaux inconvénients sont apparus tels que la formation de dépôts pulvérulents ou de films discontinus.The Applicant now aiming to manufacture electric cables from strands made up of a number of nickel-plated aluminum wires with a diameter of less than 1 mm had considered using the above method by supplementing it with a additional range of drawing operations intended to bring the wires to the desired diameter. However, it then encountered certain difficulties with regard to the behavior of the nickel coating which, for significant reductions in section, deteriorated and led to an unfavorable change in the contact resistance of the wire obtained. This is why she tried to apply her process to the coating of fine wires in order to be able to strand it directly and thus to avoid any drawing operation. However, new drawbacks have appeared, such as the formation of powdery deposits or discontinuous films.

C'est dans le but de proposer une solution à ce problème, solution d'ailleurs transposable aux fils de toutes dimensions, que la demanderesse a mis au point selon l'invention un procédé pour déposer électrolytiquement, au défilé, un film continu de nickel sous forme de globules de taille réglable sur du fil métallique à usage électrique dans lequel, après dégraissage, on soumet le fil à une densité de courant qui le charge positivement en le passant à travers un bain d'activation sous tension puis, après rinçage, à une densité de courant qui le charge négativement en le passant à travers un bain acide de nickelage sous tension et enfin à un rinçage et à un séchage et qui est caractérisé en ce que dans le but de moduler la densité de courant le long du parcours du fil,on réduit la densité de courant dans la partie amont du bain de nickelage et/ou aval du bain d'activation et règle l'acidité du bain de nickelage à une valeur de pH comprise entre 1 et 5.It is with the aim of proposing a solution to this problem, a solution which can also be transposed to wires of all sizes, that the Applicant has developed according to the invention a method for electrolytically depositing a continuous film of nickel during the process. in the form of globules of adjustable size on metallic wire for electrical use in which, after degreasing, the wire is subjected to a current density which charges it positively by passing it through an energizing bath under tension then, after rinsing, to a current density which negatively charges it by passing it through an acid nickel plating bath under tension and finally to a rinsing and a drying and which is characterized in that in order to modulate the current density along the course of the wire, the current density in the upstream part of the nickel-plating bath and / or downstream of the activation bath is reduced and the acidity of the nickel-plating bath is adjusted to a pH value of between 1 and 5.

Ainsi retrouve-t-on dans ce procédé les moyens utilisés dans le brevet précité mais auxquels s'ajoutent des moyens particuliers qui permettent dans le bain de nickelage, d'une part de développer un dépôt de nickel sous une forme particulière de globules adhérant parfaitement au fil et d'éviter ainsi tout dépôt pulvérulent et, d'autre part de maitriser la taille et la répartition de ces globules de façon à assurer un revêtement continu du fil. Quant au bain d'activation, on constate que ces moyens particuliers ont un effet bénéfique sur la préparation de la surface du fil en développant notamment des centres d'accrochage pour le nickel.Thus do we find in this process the means used in the aforementioned patent but to which are added particular means which allow in the nickel-plating bath, on the one hand to develop a deposit of nickel in a particular form of globules adhering perfectly wire and thus avoid any powdery deposit and, on the other hand to control the size and distribution of these globules so as to ensure a continuous coating of the wire. As for the activation bath, it can be seen that these particular means have a beneficial effect on the preparation of the surface of the wire, in particular by developing attachment centers for nickel.

Ces moyens sont constitués, d'une part, par une réduction de la densité de courant dans la partie amont du bain de nickelage ou aval du bain d'activation. En effet, on a constaté que dans l'art antérieur où il y a une seule électrode ou même plusieurs électrodes réparties régulièrement le long du bain et parallèles au fil, la densité de courant était très élevée dans la partie amont du bain de nickelage et ce, d'autant plus que l'intensité de courant admise était grande; ce qui pouvait nuire à la qualité du dépôt.These means consist, on the one hand, of a reduction in the current density in the upstream part of the nickel-plating bath or downstream of the activation bath. Indeed, it has been found that in the prior art where there is a single electrode or even several electrodes distributed regularly along the bath and parallel to the wire, the current density was very high in the upstream part of the nickel-plating bath and this, all the more so as the current intensity admitted was great; which could affect the quality of the deposit.

La demanderesse a trouvé qu'il fallait réduire la densité de courant dans la partie amont du bain de nickelage pour voir apparaître une couche de nickel sous forme de globules adhérant et couvrant mieux le substrat et qui confère une résistance de contact faible.The Applicant has found that it is necessary to reduce the current density in the upstream part of the nickel-plating bath in order to see a layer of nickel appear in the form of globules which adhere and cover the substrate better and which gives a low contact resistance.

Cette amélioration a été accentuée en substituant au profil de la densité de courant inhérent au procédé antérieur, à savoir une courbe décroissante de l'entrée à la sortie du bain, un profil dans lequel à une croissance régulière succède une décroissance lente et, en particulier, en situant la densité maximum en un endroit du bain situé entre le tiers de la longueur à partir de l'entrée et le milieu tout en réduisant au mieux l'écart entre cette densité maximum et la densité minimum.This improvement has been accentuated by replacing the profile of the current density inherent in the prior process, namely a decreasing curve from the entry to the exit of the bath, a profile in which a regular growth succeeds a slow decay and, in particular , by locating the maximum density at a point in the bath located between a third of the length from the inlet and the middle while reducing as much as possible the difference between this maximum density and the minimum density.

Dans ces conditions, on observe une réduction de la taille des globules qui conduit à un plus grand taux de recouvrement du fil et par suite à une résistance de contact nettement meilleure.Under these conditions, a reduction in the size of the globules is observed, which leads to a greater rate of covering of the wire and consequently to a significantly better contact resistance.

Les moyens de l'invention consistent, d'autre part, en un réglage de l'acidité du bain de nickelage à une valeur de pH comprise entre 1 et 5 car dans cette fourchette, la demanderesse a constaté qu'on pouvait également réduire la taille des globules de nickel avec les avantages cités plus haut et ce d'autant plus que l'acidité augmente. Ces résultats sont particulièrement nets pour des valeurs de pH comprises entre 2,5 et 3,5.
Cette acidité peut être accrue, par exemple, en augmentant la quantité d'acide sulfamique du bain de nickelage qui, comme il est décrit dans le brevet précité contient en outre du chlorure de nickel et de l'acide orthoborique tandis que dans le bain d'activation, on retrouve les mêmes constituants décrits dans ledit brevet.The means of the invention consist, on the other hand, in adjusting the acidity of the nickel-plating bath to a pH value of between 1 and 5 because within this range, the Applicant has found that the size of the nickel globules with the advantages mentioned above and this all the more as the acidity increases. These results are particularly clear for pH values between 2.5 and 3.5.
This acidity can be increased, for example, by increasing the amount of sulfamic acid in the nickel plating bath which, as described in the aforementioned patent also contains nickel chloride and orthoboric acid while in the activation bath, we find the same constituents described in said patent.

Le procédé de l'invention peut être appliqué à tout fil métallique tel que le fil de cuivre par exemple. Mais, il trouve un intérêt particulier dans le nickelage de fils en aluminium ou en un de ses alliages à usage électrique car il permet, en raison de sa masse spécifique relativement faible et de l'allègement qui en résulte, une économie substantielle d'énergie lorsqu'on le substitue au cuivre pour la confection de câbles destinés à équiper, par exemple, des engins de transport terrestres ou aériens.
Ce procédé s'adapte particulièrement bien au nickelage de brins de faible section (inférieure à 1 mm) car il donne un revêtement très adhérent qui le rend apte à la confection de torons et de câbles qu'on peut obtenir en nickelant simultanément plusieurs brins placés en nappe verticale dans un même bain.The method of the invention can be applied to any metallic wire such as copper wire for example. However, it finds a particular interest in the nickel plating of aluminum wires or in one of its alloys for electrical use because it allows, because of its relatively low specific mass and the lightening which results therefrom, a substantial saving of energy. when it is substituted for copper for making cables intended to equip, for example, land or air transport vehicles.
This process is particularly suitable for nickel plating of small section strands (less than 1 mm) because it gives a very adherent coating which makes it suitable for making strands and cables which can be obtained by simultaneously nickel plating several strands placed in vertical tablecloth in the same bath.

L'invention concerne également un dispositif d'application du procédé décrit ci-dessus.The invention also relates to a device for applying the method described above.

Ce dispositif comporte, comme dans le brevet précité, dans le sens de défilement du fil, une première cuve contenant le bain d'activation, un compartiment de rinçage, une deuxième cuve contenant le bain de nickelage, les deux cuves étant équipées chacune d'au moins deux paires d'électrodes planes, chaque paire étant formée d'électrodes placées de part et d'autre du ou des fils et immergée au moins partiellement dans leur bain respectif, les paires du bain d'activation étant reliées à une source de courant négative et celles du bain de nickelage étant reliées à une source de courant positive. Mais, il est caractérisé en ce que les électrodes d'au moins une desdites paires sont amovibles, placées à une distance réglable par rapport à au moins une paire voisine et par rapport au fil et qu'on interpose entre chacune desdites électrodes et le fil au moins un écran amovible en matériau isolant de l'électricité.This device comprises, as in the aforementioned patent, in the direction of travel of the wire, a first tank containing the activation bath, a rinsing compartment, a second tank containing the nickel-plating bath, the two tanks each being equipped with at least two pairs of planar electrodes, each pair being formed of electrodes placed on either side of the wire or wires and at least partially immersed in their respective bath, the pairs of the activation bath being connected to a source of negative current and those of the nickel bath being connected to a positive current source. However, it is characterized in that the electrodes of at least one of said pairs are removable, placed at an adjustable distance from at least one neighboring pair and from the wire and which is interposed between each of said electrodes and the wire at least one removable screen made of electrically insulating material.

Ainsi, à la différence de l'art antérieur, au lieu de comporter une ou plusieurs électrodes réparties régulièrement le long des cuves et à égale distance du fil, le dispositif selon l'invention est constitué d'une part par des paires d'électrodes qu'on peut déplacer soit suivant la longueur de la cuve pour les rapprocher ou les éloigner les unes des autres ou laisser des espaces libres notamment à l'une des extrémités des cuves, soit suivant l'autre dimension de la cuve pour les rapprocher plus ou moins du ou des fils à revêtir. De cette façon, on peut moduler le profil de densité de courant le long du fil sachant que l'absence d'électrodes diminue cette densité et que le rapprochement des électrodes du fil l'augmente.Thus, unlike the prior art, instead of having one or more electrodes distributed regularly along the tanks and at equal distance from the wire, the device according to the invention consists on the one hand by pairs of electrodes which can be moved either along the length of the tank to bring them closer or away from each other or leave free spaces in particular at one of the ends of the tanks, or according to the Another dimension of the tank to bring them more or less close to the wire or wires to be coated. In this way, one can modulate the current density profile along the wire knowing that the absence of electrodes decreases this density and that the approximation of the electrodes of the wire increases it.

En particulier, le profil défini plus haut peut être obtenu soit en laissant un espace libre dans la partie amont de la cuve de nickelage et/ou aval de la cuve d'activation, soit en rapprochant les électrodes du fil dans la partie opposée à la partie précitée.
Quant aux moyens spécifiques pour déplacer les électrodes, ils peuvent être réalisés à partir des connaissances de l'homme de l'art.In particular, the profile defined above can be obtained either by leaving a free space in the upstream part of the nickel-plating tank and / or downstream of the activation tank, or by bringing the electrodes of the wire in the part opposite to the aforementioned part.
As for the specific means for moving the electrodes, they can be produced from the knowledge of a person skilled in the art.

Le dispositif de l'invention est constitué également par la présence d'au moins un écran amovible entre chacune des électrodes d'au moins une paire et le fil. Ces écrans sont réalisés en un matériau isolant de l'électricité et ont de préférence une bonne tenue au bain d'activation ou de nickelage. Ces écrans sont placés plus ou moins loin du fil et masquent au moins partiellement les électrodes de sorte qu'ils interrompent ou dévient les lignes de courant circulant dans les bains et permettent donc de réduire la densité de courant en des endroits précis du bain.The device of the invention also consists of the presence of at least one removable screen between each of the electrodes of at least one pair and the wire. These screens are made of an electrically insulating material and preferably have good resistance to the activation or nickel-plating bath. These screens are placed more or less far from the wire and at least partially mask the electrodes so that they interrupt or deflect the lines of current flowing in the baths and therefore make it possible to reduce the current density at precise locations in the bath.

Afin de réaliser le profil décrit plus haut, ces écrans sont placés dans la partie amont de la cuve et/ou aval de la cuve d'activation. Mais, on agit encore mieux sur ce profil en utilisant des écrans munis de trous de diamètre variable. De préférence, on fait varier le nombre de trous en fonction de la position de l'écran dans la cuve et, notamment, on fait croître leur nombre dans le sens de défilement du fil. Ainsi, on peut associer des écrans pleins et des écrans percés.In order to achieve the profile described above, these screens are placed in the upstream part of the tank and / or downstream of the activation tank. However, we act even better on this profile by using screens provided with holes of variable diameter. Preferably, the number of holes is varied as a function of the position of the screen in the tank and, in particular, their number is increased in the direction of travel of the wire. Thus, we can combine full screens and pierced screens.

Le dispositif ainsi conçu est adapté au traitement d'un ou de plusieurs fils en prévoyant dans les parois des cuves situées en bout des ouvertures convenables situées les unes à côté des autres et équipées de joints d'étanchéité. De préférence, pour favoriser les échanges entre le fil et les bains, on peut assurer une circulation de ces derniers au moyen de pompes. Le dispositif est aussi heureusement complété par un compartiment de rinçage destiné à éliminer au moyen d'eau déminéralisée le bain qui a pu être entraîné hors de la cuve de nickelage, l'eau qui mouille le fil étant ensuite évaporée dans un compartiment de séchage.The device thus designed is suitable for the treatment of one or more wires by providing in the walls of the tanks located at the end of suitable openings located next to each other and equipped with seals. Preferably, to encourage exchanges between the wire and the baths, a circulation of these can be ensured by means of pumps. The device is also fortunately completed by a rinsing compartment intended to eliminate by means of demineralized water the bath which may have been entrained out of the nickel-plating tank, the water which wets the wire then being evaporated in a drying compartment.

L'ensemble des cuves et des compartiments de rinçage est conçu sous forme d'éléments modulaires, de longueur et de section adaptables au problème de revêtement posé et facilement associables entre eux.All the rinsing tanks and compartments are designed as modular elements, of length and section adaptable to the coating problem posed and easily associable with each other.

L'invention sera mieux comprise à l'aide de la figure 1 ci-jointe qui représente une vue en perspective d'une cuve de nickelage coupée dans le sens de la longueur suivant un plan vertical placé un peu en avant du plant de symétrie médian.
On distingue la cuve 1 de forme parallélépipédique dont les petites faces 2 sont percées chacune de trois trous 3 au travers desquels passent trois brins métalliques 4 qui défilent dans le sens de la flèche 5 dans le bain 6 de nickelage. Dans cette cuve, on voit quatre des huit électrodes 7 placées verticalement de part et d'autre de la nappe et se rapprochant de cette dernière dans le sens de défilement des brins. Ces électrodes sont reliées à une source de courant positive non représentée tandis que les brins 4 sont chargés négativement.
On voit également entre les électrodes et la nappe quatre des huit écrans 8 placés parallèlement à la nappe et à égale distance entre eux dont les deux premiers, dans le sens de défilement, sont pleins, le troisième est percé de six trous 9 et le dernier de douze trous.The invention will be better understood using the attached FIG. 1 which represents a perspective view of a nickel-plating tank cut lengthwise along a vertical plane placed a little in front of the plant of median symmetry .
We distinguish the tank 1 of parallelepiped shape whose small faces 2 are each pierced with three holes 3 through which pass three metal strands 4 which pass in the direction of the arrow 5 in the nickel plating bath 6. In this tank, we see four of the eight electrodes 7 placed vertically on either side of the sheet and approaching the latter in the direction of travel of the strands. These electrodes are connected to a positive current source, not shown, while the strands 4 are negatively charged.
We also see between the electrodes and the sheet four of the eight screens 8 placed parallel to the sheet and at equal distance between them, the first two, in the direction of travel, are full, the third has six holes 9 and the last of twelve holes.

Les électrodes et les écrans sont suspendus dans le bain à l'aide de moyens non représentés qui permettent de les déplacer longitudinalement et transversalement dans la cuve. Le bain est animé d'un mouvement de circulation de bas en haut au moyen d'une pompe, non représentée, alimentée par l'écoulement des surverses 10 et qui refoule ledit bain dans la rampe de distribution 11.
Une telle représentation est valable également pour la cuve d'activation.The electrodes and the screens are suspended in the bath by means not shown which allow them to be moved longitudinally and transversely in the tank. The bath is driven in a circulation movement from bottom to top by means of a pump, not shown, supplied by the flow of overflows 10 and which discharges said bath into the distribution ramp 11.
Such a representation is also valid for the activation tank.

L'invention peut être illustrée à l'aide des exemples d'application suivants :The invention can be illustrated with the aid of the following application examples:

Exemple 1Example 1

Dans un dispositif comportant successivement :
- un premier compartiment de rinçage de dimensions intérieures 1000 x 120 x 120 mm contenant 9 litres de solution à 70°C pompée à partir d'un bac de réserve de 80 litres
- un compartiment de rinçage
- une cuve d'activation de dimensions intérieures 1000 x 120 x 120 mm garnie d'électrodes de dimensions 100 x 80 x 80 mm reliées à une source de courant négatif pouvant débiter 2000 A sous 40 Volts et d'écrans de dimensions 120 x 40 x 5 mm en polypropylène disposés de manière à obtenir une répartition de la densité de courant judicieusement choisie,ladite cuve renfermant une solution à 45°C contenant 125 g/l de chlorure de nickel à 6 H₂O, 12,5 g/l d'acide orthoborique, et 6 cm³­/l d'acide fluorhydrique et circulant de bas en haut à raison de 6 m³/h
- un deuxième compartiment de rinçage
- une cuve de nickelage de dimensions intérieures 1000 x 120 x 120 mm garnie d'électrodes reliées au pôle positif de la même source de courant qui alimente la cuve d'activation et d'écrans de mêmes dimensions que ceux de la cuve d'activation, l'ensemble étant disposé suivant la figure 1; cette cuve de nickelage renfermant une solution à 65°C contenant 300 g/l de sulfamate de nickel, 30 g/l de chlorure de nickel, 30 g/l d'acide orthoborique ayant un pH de 3,2 et circulant de bas en haut à raison de 6 m³/h.
- un troisième compartiment de rinçage
- un four de séchage.In a device comprising successively:
- a first rinsing compartment with internal dimensions 1000 x 120 x 120 mm containing 9 liters of 70 ° C solution pumped from an 80-liter reserve tank
- a rinsing compartment
- an activation tank with internal dimensions 1000 x 120 x 120 mm fitted with electrodes with dimensions 100 x 80 x 80 mm connected to a negative current source capable of delivering 2000 A at 40 Volts and screens with dimensions 120 x 40 x 5 mm in polypropylene arranged so as to obtain a distribution of the judiciously chosen current density, said tank containing a solution at 45 ° C. containing 125 g / l of nickel chloride at 6 H₂O, 12.5 g / l of orthoboric acid, and 6 cm³ / l of hydrofluoric acid and flowing from bottom to top at the rate of 6 m³ / h
- a second rinsing compartment
- a nickel-plating tank with internal dimensions 1000 x 120 x 120 mm fitted with electrodes connected to the positive pole of the same current source which supplies the activation tank and screens of the same dimensions as those of the activation tank , the assembly being arranged according to Figure 1; this nickel-plating tank containing a solution at 65 ° C. containing 300 g / l of nickel sulfamate, 30 g / l of nickel chloride, 30 g / l of orthoboric acid having a pH of 3.2 and circulating from bottom to high at a rate of 6 m³ / h.
- a third rinsing compartment
- a drying oven.

On a passé simultanément 5 brins en aluminium du type 1310.50 suivant les normes de l'Aluminium Association de diamètre 0,51 mm défilant à une vitesse de 50 m/min.
Les brins obtenus étaient recouverts chacun d'une épaisseur moyenne de nickel de 1,5 µm sous forme de globules de diamètre 1,0 um dont on a une représentation au grossissement 3000 sur la figure 2 et qu'on peut comparer à la figure 3 correspondant à l'art antérieur et qui donnait des globules beaucoup plus gros (3 µm) et ne formant pas une couche continue.
Ces brins ont pu être toronnés et ont donné au cours d'essais de résistance de contact sous 500 g des valeurs comprises entre 1,5 et 2 m Ω alors que dans l'art antérieur pour de tels brins, on obtenait des valeurs supérieures à 2 m Ω.5 aluminum strands of the 1310.50 type were passed simultaneously according to the standards of the Aluminum Association with a diameter of 0.51 mm traveling at a speed of 50 m / min.
The strands obtained were each covered with an average thickness of nickel of 1.5 μm in the form of globules with a diameter of 1.0 μm, a representation of which at 3000 magnification is shown in FIG. 2 and which can be compared in FIG. 3 corresponding to the prior art and which gave much larger globules (3 μm) and not forming a continuous layer.
These strands could have been stranded and gave during contact resistance tests under 500 g values between 1.5 and 2 m Ω whereas in the prior art for such strands, we obtained values greater than 2 m Ω.

Exemple 2Example 2

Sur le même dispositif, on a traité des nappes de 5 fils de diamètre inférieur à celui de l'Exemple 1, c'est-à-dire des fils de diamètre 0,32 - 0,30 - 0,25 - 0,20 et 0,15 mm à des vitesses de défilement comprises entre 25 et 50 m/min et obtenu un dépôt de nickel de 1,0 µm d'épaisseur moyenne, formé de globules de diamètre inférieur au micron, présentant des résistances de contact inférieures au m Ω.
Ces fils nickelés ont été toronnés et câblés, puis isolés avec les matériaux agréés par l'Aéronautique.On the same device, plies of 5 wires of diameter smaller than that of Example 1 were treated, that is to say wires of diameter 0.32 - 0.30 - 0.25 - 0.20 and 0.15 mm at running speeds of between 25 and 50 m / min and obtained a nickel deposit of 1.0 μm in average thickness, formed of globules of diameter less than one micron, having contact resistances less than m Ω.
These nickel-plated wires were stranded and wired, then insulated with materials approved by the aeronautics industry.

L'invention trouve son application dans le nickelage de fils métalliques notamment en aluminium, de tout diamètre et, en particulier, inférieurs à 1 mm et permet l'obtention par toronnage et câblage de conducteurs électriques légers et fiables particulièrement intéressants pour équiper les engins de transport aériens ou terrestres où l'économie d'énergie par allègement des équipements est très appréciée.The invention finds its application in the nickel plating of metallic wires in particular of aluminum, of any diameter and, in particular, less than 1 mm and allows obtaining by stranding and wiring of light and reliable electrical conductors which are particularly advantageous for equipping spacecraft. air or land transport where energy saving by reducing equipment is much appreciated.

Claims (18)

1. Procédé pour déposer électrolytiquement, au défilé, un film continu de nickel sous forme de globules de taille réglable sur du fil métallique à usage électrique dans lequel, après dégraissage, on soumet le fil à une densité de courant qui le charge positivement en le passant à travers un bain d'activation sous tension puis, après rinçage, à une densité de courant qui le charge négativement en le passant à travers un bain acide de nickelage sous tension et enfin à un rinçage et à un séchage caractérisé en ce que dans le but de moduler la densité de courant le long du parcours du fil,on réduit la densité de courant dans la partie amont du bain de nickelage et/ou aval du bain d'activation et règle l'acidité du bain de nickelage à une valeur de pH comprise entre 1 et 5.1. A method for electrolytically depositing, on parade, a continuous film of nickel in the form of globules of adjustable size on metallic wire for electrical use in which, after degreasing, the wire is subjected to a current density which positively charges it by passing through a energized activation bath and then, after rinsing, at a current density which charges it negatively by passing it through an acid nickel-plating bath under tension and finally to rinsing and drying, characterized in that in the purpose of modulating the current density along the path of the wire, the current density in the upstream part of the nickel plating bath and / or downstream of the activation bath is reduced and the acidity of the nickel plating bath is adjusted to a value with a pH between 1 and 5. 2. Procédé selon la revendication 1 caractérisé en ce que l'on fait croître puis décroître lentement la densité de courant dans le sens de défilement du fil.2. Method according to claim 1 characterized in that the current density is slowly increased and then decreased in the direction of travel of the wire. 3. Procédé selon la revendication 2 caractérisé en ce que l'on fait croître la densité de manière à avoir un maximum entre le premier tiers et le milieu du bain.3. Method according to claim 2 characterized in that the density is increased so as to have a maximum between the first third and the middle of the bath. 4. Procédé selon la revendication 3 caractérisé en ce que l'on récuit l'écart entre la densité maximum et la densité minimum pour diminuer la taille des globules.4. Method according to claim 3 characterized in that one anneals the difference between the maximum density and the minimum density to reduce the size of the globules. 5. Procédé selon la revendication 1 caractérisé en ce que l'on augmente l'acidité du bain de nickelage pour diminuer la taille des globules déposés.5. Method according to claim 1 characterized in that the acidity of the nickel-plating bath is increased to reduce the size of the deposited globules. 6. Procédé selon la revendication 1 caractérisé en ce que l'acidité a une valeur comprise entre 2,5 et 3,5 unités de pH.6. Method according to claim 1 characterized in that the acidity has a value between 2.5 and 3.5 pH units. 7. Procédé selon la revnedication 1 caractérisé en ce que l'on nickèle du fil en aluminium ou en un de ses alliages à usage électrique.7. Method according to revnedication 1 characterized in that it nickels aluminum wire or one of its alloys for electrical use. 8. Procédé selon la revendication 7 caractérisé en ce que l'on nickèle du fil de diamètre inférieur à 1 mm.8. Method according to claim 7 characterized in that one nickele wire of diameter less than 1 mm. 9. Procédé selon la revendication 8 caractérisé en ce que l'on nickèle du fil sous forme de nappe verticale d'au moins 2 brins séparés qui sont ensuite toronnés.9. Method according to claim 8 characterized in that the wire is nickelled in the form of a vertical sheet of at least 2 separate strands which are then stranded. 10. Dispositif d'application du procédé selon la revendication 1 comportant dans le sens (5) de défilement du fil (4) une première cuve contenant le bain d'activation, un compartiment de rinçage, une deuxième cuve (1)contenant le bain de nickelage, les deux cuves étant équipées chacune d'au moins deux paires d'électrodes (7) planes, chaque paire étant formée d'électrodes placées de part et d'autre du ou des fils et immergées au moins partiellement dans leur bain respectif, les paires du bain d'activation étant reliées à une source de courant négative et celles du bain de nickelage étant reliées à une source de courant positive caractérisé en ce que les électrodes d'au moins une desdites paires sont amovibles, placées à une distance réglable par rapport à au moins une paire voisine et par rapport au fil et qu'on interpose entre chacune desdites électrodes et le fil au moins un écran (8) amovible en matériau isolant de l'électricité.10. Device for applying the method according to claim 1 comprising in the direction (5) of travel of the wire (4) a first tank containing the activation bath, a rinsing compartment, a second tank (1) containing the bath nickel plating, the two tanks being each equipped with at least two pairs of planar electrodes (7), each pair being formed of electrodes placed on either side of the wire or wires and at least partially immersed in their respective bath , the pairs of the activation bath being connected to a negative current source and those of the nickel-plating bath being connected to a positive current source characterized in that the electrodes of at least one of said pairs are removable, placed at a distance adjustable with respect to at least one neighboring pair and with respect to the wire and which is interposed between each of said electrodes and the wire at least one removable screen (8) made of electrically insulating material. 11. Dispositif selon la revendication 10 caractérisé en ce que la distance par rapport à une paire voisine est réglée de manière à laisser un espace libre dans la partie amont de la cuve de nickelage et/ou aval de la cuve d'activation.11. Device according to claim 10 characterized in that the distance relative to a neighboring pair is adjusted so as to leave a free space in the upstream part of the nickel-plating tank and / or downstream of the activation tank. 12. Dispositif selon la revendication 10 caractérisé en ce que la distance par rapport au fil est réglée de manière quelle soit plus grande dans la partie amont de la cuve de nickelage et/ou aval de la cuve d'activation.12. Device according to claim 10 characterized in that the distance relative to the wire is adjusted so that it is greater in the upstream part of the nickel-plating tank and / or downstream of the activation tank. 13. Dispositif selon la revendication 10 caractérisé en ce que les écrans sont placés dans la partie amont de la cuve de nickelage et/ou aval de la cuve d'activation.13. Device according to claim 10 characterized in that the screens are placed in the upstream part of the nickel-plating tank and / or downstream of the activation tank. 14. Dispositif selon la revendication 10 caractérisé en ce que au moins un des écrans est muni de trous (9).14. Device according to claim 10 characterized in that at least one of the screens is provided with holes (9). 15. Dispositif selon la revendication 14 caractérisé en ce que le nombre de trous est variable suivant la position de l'écran dans la cuve.15. Device according to claim 14 characterized in that the number of holes is variable depending on the position of the screen in the tank. 16. Dispositif selon la revendication 15, caractérisé en ce que le nombre de trous croît dans le sens de défilement du fil dans la cuve de nickelage et dans le sens inverse dans la cuve d'activation.16. Device according to claim 15, characterized in that the number of holes increases in the direction of travel of the wire in the nickel-plating tank and in the opposite direction in the activation tank. 17. Dispositif selon la revendication 10, caractérisé en ce que la cuve de nickelage est suivie d'un compartiment de rinçage et d'un compartiment de séchage.17. Device according to claim 10, characterized in that the nickel-plating tank is followed by a rinsing compartment and a drying compartment. 18. Dispositif selon la revendication 10 caractérisé en ce que les cuves et compartiments sont sous forme d'éléments du type modulaire.18. Device according to claim 10 characterized in that the tanks and compartments are in the form of elements of the modular type.
EP88420002A 1987-01-06 1988-01-04 Process and apparatus for the electrolytic deposition of a continuous nickel film on wire Expired - Lifetime EP0276190B1 (en)

Applications Claiming Priority (2)

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FR8700952A FR2609292B1 (en) 1987-01-06 1987-01-06 METHOD AND DEVICE FOR ELECTROLYTICALLY DEPOSITED NICKEL CONTINUOUS FILM ON METALLIC WIRE FOR ELECTRICAL USE
FR8700952 1987-01-06

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AU589106B2 (en) 1989-09-28
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ATE56758T1 (en) 1990-10-15
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NO880019L (en) 1988-07-07
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CA1309690C (en) 1992-11-03
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JPS63213694A (en) 1988-09-06
FR2609292B1 (en) 1989-03-24
DK388D0 (en) 1988-01-04
AU1005988A (en) 1988-07-07

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