EP1204787B1 - Method for continuous nickel-plating of an aluminium conductor and corresponding device - Google Patents

Method for continuous nickel-plating of an aluminium conductor and corresponding device Download PDF

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Publication number
EP1204787B1
EP1204787B1 EP00953251A EP00953251A EP1204787B1 EP 1204787 B1 EP1204787 B1 EP 1204787B1 EP 00953251 A EP00953251 A EP 00953251A EP 00953251 A EP00953251 A EP 00953251A EP 1204787 B1 EP1204787 B1 EP 1204787B1
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EP
European Patent Office
Prior art keywords
conductor
nickel plating
nickel
bath
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP00953251A
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German (de)
French (fr)
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EP1204787A2 (en
Inventor
Gabriel Colombier
Jean-Sylvestre Safrany
Bernard Loreau
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Rio Tinto France SAS
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Aluminium Pechiney SA
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Publication of EP1204787A2 publication Critical patent/EP1204787A2/en
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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium

Definitions

  • the invention relates to conductors made of aluminum or aluminum alloy nickel. It relates more specifically to the nickel plating processes of aluminum or aluminum alloy conductors, as well as allowing them to be implemented.
  • the invention also relates to wires and cables aluminum or aluminum alloy cores comprising at least one nickel plated conductor.
  • the word “aluminum” is understood in the broad sense of aluminum and its alloys. It will be so throughout the rest of the text.
  • the word “driver” here refers to a body electrically conductive, elongated, the length of which is large by relative to its transverse dimensions, such as a wire, a band, a bar or a tube.
  • Aluminum electrical conductors are widely used in the transportation of electrical energy. These drivers are most often in the form of bars, flats, wires or cables.
  • Aluminum-core electrical wires and cables which may include a coating made of insulating material, are generally obtained from a wire "machine” cast and rolled continuously which is then drawn to the desired diameter. Sons, or strands, unitary can then be assembled to form the conductive core of a cable.
  • aluminum conductors can be used in the raw state, that is to say without special treatment of the driver's surface, in addition to brushing possible parts of the conductor intended for the establishment of an electrical contact.
  • the driver travels in at less an electrolytic nickel plating tank.
  • This tank is equipped with an electrode of nickel which acts as anode and which, for this purpose, is connected to the positive terminal of a power supply.
  • the driver to be treated acts as a virgin cathode and, for this, is electrically connected to the negative terminal of this power supply.
  • the applicant has proposed a method and a nickel-plating device electrolytic parade of an aluminum conductor to achieve scroll speeds of 300 m / minute.
  • the electrolytic current is transmitted to the driver by a so-called liquid current tap, that is to say without mechanical contact, which avoids the inconvenience of mechanical sockets, especially electric arcs.
  • the driver to be coated circulates in a first tank provided with a negatively polarized electrode, then in a second vessel provided with a positively polarized electrode; an electric current then circulates in the driver during his passage in the tanks.
  • the first tank contains an aqueous ionic solution capable of transmitting the electric current of the electrode to said driver.
  • the second tank contains the nickel bath.
  • the nickel plating of the drivers is an additional operation we are looking at both minimizing the cost and maximizing productivity.
  • conductors in the form of wire or cable costs and satisfactory productivity by performing the nickeling of the elementary wires at the parade to great speed.
  • some markets, such as aeronautics want have nickel-plated aluminum wire with a diameter between 0.1 and 0.5 mm, and cables consisting of such wires.
  • the plaintiff therefore sought ways to obtain drivers nickel-plated aluminum with a diameter of less than 1 mm, which avoids the disadvantages of the prior art while maintaining acceptable profitability and productivity, with investment costs as low as possible.
  • the subject of the invention is a method of continuous nickel plating (or "parade") of a aluminum conductor.
  • the nickel plating process of an aluminum conductor or aluminum alloy according to the invention comprises a pre-treatment step P able to promote adhesion of the nickel layer and an electrolytic nickel plating step N, and is characterized by that said pre-treatment P is produced electrolytically and is also capable of conferring on the said driver sufficient contact properties to allow mechanical electrical contact and in that the nickel plating current is transmitted to said driver via a mechanical electrical contact on the driver's part after the pre-treatment step.
  • the electrolytic nickel plating step N makes it possible to form, by electrodeposition, a uniform nickel layer on said conductor.
  • the invention also relates to a continuous nickel plating device (or "parade”) an aluminum conductor.
  • the invention mainly concerns aluminum conductors intended for for electrical applications, it also applies to aluminum conductors intended for non-electrical purposes, such as thermal uses (which exploit the high thermal conductivity of aluminum, such as a heat exchanger) or, possibly, essentially mechanical uses.
  • the invention can also be applied to the nickel plating of aluminum products, such as wires, strips or tubes of aluminum, intended to be brazed.
  • the subject of the invention is the use of the method or device according to the invention for the nickel plating of an aluminum product so as to allow a brazing of it.
  • the nickel layer with a thickness typically of the order than 1 ⁇ m, can allow the formation of a satisfactory soldered joint without recourse to a specific soldering flux.
  • the subject of the invention is also a method of manufacture of an assembled product, characterized in that it comprises the use of a product made of nickel-plated aluminum according to the invention. Said manufacturing process possibly comprises a soldering operation of said aluminum product nickel.
  • Said mechanical contact (7) preferably comprises at least one rolling mechanical contact means (70) which typically comprises at least one grooved wheel or a sheave.
  • the mechanical electrical contact can be made, for example, using rollers, rollers, rubbing contacts or brushes.
  • the composition of the nickel plating bath is advantageously as follows: 300 ⁇ 30 g / l of Ni (NH 2 SO 3 ) 2 (sulphamate), 30 ⁇ 5 g / l of NiCl 2 , 6H 2 O, 30 ⁇ 5 g / l of H 3 BO 3 ⁇
  • the nickel-plating device with the passage of at least one conductor made of aluminum or aluminum alloy (or "treatment line") comprises a nickel-plating tank (30) comprising a tank (2) capable of containing a nickel-plating bath (4) and at least one electrode (3) containing nickel, called anode, at least one power supply (5) for applying an electric voltage (V 1 ) between the or each electrode and said conductor, and means (21, 22) for scrolling the or each conductor (1) in the nickel-plating bath (4), and is characterized in that it also comprises at least one electrolytic pre-treatment tank (40, 41,42) comprising a tray (17,43,46) adapted to contain a pre-treatment bath (16,44,47), and means for scrolling the or each conductor in the pre-treatment bath (16, 44, 47), and in that it comprises mechanical contact means (7, 13, 14) for applying said electrical voltage to the part (6) of the, or e, each said driver (1) from the pre-treatment step P.
  • the driver in the raw state (10)
  • the pre-treatment step is chosen to give the driver properties of sufficient contact to allow mechanical electrical contact therewith.
  • the pre-treatment step P is performed electrolytically, which makes it easier to control the pre-treatment according to the operating conditions of the treatment line.
  • the pre-treatment tank (40) is provided with at least one electrode (15) and the device comprises a power supply (8) for the pre-treatment.
  • the voltage V 2 delivered by this power supply can be alternating, continuous or pulsed, or a combination thereof.
  • the socket on the conductor is made by a mechanical contact placed downstream of the pre-treatment tank (40). This mechanical power outlet is advantageously common to that of the nickel-plating step, as illustrated in FIG. 1, which makes it possible to simplify the device without leading to an overloading of the mechanical contact means (7, 13, 14).
  • the intensity of the pre-treatment current (I 2 ) is generally much lower than the intensity of the nickel-plating current (I 1 ).
  • the pre-treatment step P comprises an activation A in a strongly acidic or alkaline bath which allows, in particular, a rapid dissolution of the surface oxides.
  • the activation is performed in an activation tank (40, 42) comprising a tank (17, 46) capable of containing the activation bath (16, 47), in which the conductor (1) scrolls.
  • the activation vessel (40, 42) also comprises at least one electrode (15, 48) and the device comprises a power supply (8) for this activation.
  • the voltage V 2 delivered by this power supply can be alternating, continuous or pulsed, or a combination thereof.
  • the pretreatment step P comprises, in addition to an activation step A to dissolve in particular the oxides present on the surface of the conductor (1), a pre-nickeling step PN making it possible to coat the aluminum conductor (1) of a "primary" nickel deposit.
  • the nickel plating current (I 1 ) is then transmitted to said conductor via mechanical contact means (7, 13, 14) on the portion (6) of the conductor (1) coated with said primary nickel deposit.
  • primary nickel deposition means a layer of nickel, which is in the form of nodules, whose equivalent thickness is significantly less than the targeted thickness of the final layer. It was found preferable to aim for a thickness equivalent which is, on average, less than about 0.1 of the final thickness. Typically, the thickness of the final layer being about 1 ⁇ m, we will aim at equivalent thickness of the pre-nickel plating layer less than about 0.1 ⁇ m.
  • the pre-nickel plating is carried out in a tank (40, 4 1) comprising a tank (17, 43) adapted to contain the pre-nickel bath (16, 44), in which the conductor (1) scrolls.
  • the pre-nickel bath (16, 44) contains a nickel salt so as to coat the aluminum conductor of a primary nickel deposit when the driver scrolls in this bath.
  • the pre-nickel plating step is preferably carried out electrolytically, which makes it easier to control the thickness of the layer depending on the operating conditions of the treatment line.
  • the pre-nickel plating tank (40, 41) is provided with at least one electrode (15, 45) containing nickel and the device comprises a power supply (8) for the pre-nickel plating.
  • the voltage V 2 delivered by this power supply can be alternating, continuous or pulsed, or a combination thereof.
  • the PN pre-nickeling stage is wholly or partly combined with the activation step A, which greatly simplifies the device.
  • the steps of pre-nickel plating and activation are carried out jointly with a liquid outlet.
  • FIG. 2 illustrates a device that makes it possible to implement this variant of the invention.
  • This device comprises an electrolytic activation tank (42) and a electrolytic pre-nickel plating tank (41), preferably close to each other and possibly adjacent, a first power supply (8) common to these two tanks, an electrolytic nickel plating tank (30), a second feed (5) and mechanical contact means (7, 13, 14) on the part (6) of the conductor (1) between the pre-nickel plating tank (41) and the nickel-plating tank (30).
  • the first power supply (8) is preferably DC, optionally modulated or pulsed; the positive terminal is connected to at least one electrode (45) immersed, in whole or in part, in the pre-nickel bath (44) and the negative terminal is connected to at least one submerged electrode (48) in all or part, in the activation bath (47).
  • the current flows through the conductor (1) through a liquid outlet effect.
  • the same power supply (8) is used for activation and pre-nickel plating.
  • the second power supply (5) is in direct current, possibly modulated or pulsed; the positive terminal is connected to at least one electrode (3) containing all or part of the nickel in the nickel-plating bath (4) and the negative terminal is connected to the part (6) of the conductor (1) between the tank pre-nickel plating (41) and the nickel-plating tank (30) via means of mechanical contact (7, 13, 14).
  • the pre-nickel plating and activation A stages can be carried out simultaneously, in the same bath (40) and with common electrodes (15) (and having the same polarization), as illustrated in FIG.
  • the pre-treatment step operates a dual function of activation and pre-nickel plating.
  • the activation bath / pre-nickel plating (16) is then able to operate both treatments, for example by having a mixed composition that allows both a satisfactory activation and a sufficient pre-nickel plating.
  • the Applicant has found that it is possible to effectively perform these two functions using a single bath.
  • the first power supply (8) is in direct current, optionally modulated or pulsed, the positive terminal being connected to the conductor (1) via the mechanical contact (7) and the negative terminal being connected to at least one electrode (15) immersed, in whole or in part, in said bath activation / pre-nickel plating (16).
  • the second power supply (5) is in direct current, optionally modulated or pulsed; the positive terminal is connected to an electrode (3) containing nickel immersed, in whole or in part, in the bath of nickel plating (4) and the negative terminal is connected to the part (6) of the conductor (1) located between the activation / pre-nickel plating tank (40) and the nickel-plating tank (30) by intermediate mechanical contact means (7, 13, 14), preferably common to those of the first diet (8).
  • the mechanical contact is immersed in a liquid (14) such as water or a neutral solution, so as to avoid the melting of the conductor to the right of mechanical contact.
  • a liquid (14) such as water or a neutral solution
  • the device can include an intermediate tray (13), generally small, containing the liquid (14) and the mechanical contact (7).
  • the liquid (14) can optionally be cooled.
  • the mechanical contact may comprise several parallel wheels rotating around a common axis (as shown in Figure 3).
  • the rolling mechanical contact means (70) illustrated in FIG. corresponds to a preferred embodiment of the invention, comprises one or a plurality of wheels (71) rotating about an axle (73) whose central axis (75) is substantially perpendicular to said wheels (71).
  • the (or each) wheel (71) is preferably provided with a groove (74) in which the conductor (6) rests, which allows in particular to avoid variations in position thereof.
  • the flow electrical transits from the axle (73) to the driver (6) via the wheel (71).
  • the axle-wheel assembly (70) can be immersed in a liquid (14).
  • the contact means (70) may comprise a ring (72), typically made of graphite, to facilitate the rolling of the wheels (71) around the axle (73) and to improve the electric contact. This last variant also makes it possible to avoid resorting to a ball bearing.
  • the wheels (71) were in copper (possibly nickel plated) and the axle (73) was made of stainless steel.
  • the mechanical contact means illustrated in FIG. 4, which also corresponds to a preferred embodiment of the invention, comprises a set of at least three wheels (701, 702, 703) which cooperate to provide satisfactory electrical contact on the (or each) driver (6).
  • each driver comprises such means when several conductors are processed simultaneously.
  • At least one said mechanical contact means (7, 13, 14) comprises such a means of contact.
  • Each wheel rotates around a proper axis (731, 732, 733) and exerts a effort (F1, F2, F3) on the driver. In practice, it is sufficient to adjust the effort exerted on the driver by moving only the central wheel (702).
  • the three wheels can be immersed in a liquid (14).
  • the temperature of the different baths is generally chosen so that the ionic conductivity and the reactivity of the baths are sufficient. Typically, the bath temperature is between 45 and 60 ° C.
  • the method according to the invention may comprise complementary steps, such as any shaving and / or degreasing of the driver in the raw state (10) before the activation and / or pre-nickeling step.
  • the conductor is typically an AA 1370 alloy, AA 1110 or AA 6101 according to the nomenclature of the Aluminum Association.
  • the process of manufacturing a cable electric aluminum can include a nickel plating operation the invention of at least one of the elementary threads.
  • the device comprises means to simultaneously scroll two or more drivers in at least one said treatment tanks.
  • layers of conductors of a series of separate unwinders circulate in parallel in said baths and, after treatment, wind up on a series of separate reels.
  • the contact means (7, 13, 14) on the part of the conductors (6) resulting from the pre-treatment step can to be wholly or partly common to them; for example, said means can include a strip of carbon material that can be brought into contact with all the drivers of a tablecloth.
  • the driver (s) can scroll horizontally, vertically or with a certain angle to the horizontal.
  • Tests have been carried out on the 0.20 mm diameter wires according to the prior art and according to the invention.
  • the activation and nickel-plating currents were of the same intensity and came from a common power supply configured as a liquid outlet (as described in application FR 2 646 174); screens had been interposed between the nickel electrodes and the wire (as described in the application FR 2 609 292).
  • the activation and nickel plating baths had the same composition, namely: 125 ⁇ 15 g / l of nickel chloride (NiCl 2 , 6 H 2 O), 12.5 ⁇ 2 g / l of orthoboric acid and 6 ⁇ 2 ml / l of hydrofluoric acid.
  • the tests according to the invention were carried out using a device similar to that of FIG. 2.
  • the electrodes (48) of the activation tank (42) were made of graphite and the electrodes (45) of the pre-nickel plating tank (41) were made of nickel.
  • Activation baths and pre-nickel plating baths had the following composition: 125 ⁇ 15 g / l of nickel chloride (NiCl 2 , 6 H 2 O), 12.5 ⁇ 2 g / l of orthoboric acid and 6 ⁇ 2 ml / l of hydrofluoric acid.
  • the nickel plating bath had the following composition: 300 ⁇ 30 g / l of Ni (NH 2 SO 3 ) 2 (sulfamate), 30 ⁇ 5 g / l of NiCl 2 , 6H 2 O, 30 ⁇ 5 g / l of H 3 BO 3 .
  • Table I below groups together the main treatment parameters used in these tests and certain characteristics of the treated son.
  • the contact resistance was measured using a so-called "cross-wire” method, at an intensity of 0.1 mA and with a bearing force of 0.2 N.
  • the adhesion of the layer nickel on the wire was measured by winding the wire on its own diameter; it is considered excellent if the nickel layer uniformly follows the deformation of the wire without detaching from the surface.
  • Prior art Invention Scroll Speed (m / min) 50 80 Intensity of activation current-nickel plating (A) 12.5 not applicable Intensity of the pre-treatment current (A) not applicable 3-10 Intensity of the nickel-plating current (A) not applicable 15-30 Average thickness of the deposit ( ⁇ m) 0.8 0.8 Average contact resistance (m ⁇ ) 15 15 Deposit adhesion excellent excellent
  • the pre-nickel plating obtained electrolytically was in the form of nodules that did not cover the entire surface of the driver.
  • the term "deposit of primary nickel means a layer of nickel, the thickness of which is typically average of about 0.1 ⁇ m.
  • the nickel layer obtained according to the invention therefore has high adhesion and a low electrical contact resistance.
  • the invention makes it possible to nickel efficiently, and with high productivity, wires of different diameters. It allows in particular an easy adjustment of the parameters of treatment under the conditions of production, thanks to the decoupling between the pre-treatment stages and nickel plating. In particular it is possible to adjust independently the intensity of the pre-treatment and nickel-plating currents, and in particular to impose a low current intensity in the pre-treatment stage and high in the step of nickel plating.
  • the invention makes it possible to benefit from the advantages of mechanical sockets, in particular the possibility of passing on high intensities, and to avoid disadvantages, in particular the propensity to form electric arcs which can damage the driver's surface.
  • the low intensity of the pre-treatment current required according to the invention leads to a considerably slower aluminum enrichment of the pre-treatment bath, which significantly reduces the replacement frequency of this bath.
  • the low intensity of the pre-treatment current also limits the dissolution of the metal and, in Consequently, the formation of roughnesses on the surface of the wire.
  • the pre-treatment step according to the invention also makes it possible to confer on the surface of the conductor defined roughness to obtain optimal mechanical properties.

Abstract

A process for continuous nickel plating of an aluminum conductor, by electrolytically pre-treating the aluminum conductor to improve adherence of a nickel coat thereon by passing the aluminum conductor through a pre-treating bath in which is disposed an electrode connected to a first current source at a first voltage, for supplying to the aluminum conductor a pre-treating current, then electrolytically plating the pre-treated aluminum conductor with nickel in a plating bath in which is disposed an anode connected to a second current source at a second voltage, in which a nickel coat is deposited on the conductor by action of a nickel plating current In. At least the nickel plating current In is transmitted to the conductor through a mechanical electrical contact which contacts the conductor between the pre-treating bath and the plating bath, the pre-treating improving the contact properties of the conductor sufficient to permit the transmitting through the mechanical electrical conductor.

Description

Domaine de l'inventionField of the invention

L'invention concerne les conducteurs en aluminium ou en alliage d'aluminium nickelés. Elle concerne plus spécifiquement les procédés de nickelage des conducteurs en aluminium ou en alliage d'aluminium, ainsi que les dispositifs permettant de les mettre en oeuvre. L'invention concerne également les fils et câbles électriques à âme en aluminium ou en alliage d'aluminium comprenant au moins un conducteur nickelé.The invention relates to conductors made of aluminum or aluminum alloy nickel. It relates more specifically to the nickel plating processes of aluminum or aluminum alloy conductors, as well as allowing them to be implemented. The invention also relates to wires and cables aluminum or aluminum alloy cores comprising at least one nickel plated conductor.

Le mot "aluminium" s'entend au sens large de l'aluminium et ses alliages. Il en sera ainsi dans toute la suite du texte. Le mot "conducteur" désigne ici un corps électriquement conducteur, de forme allongée, dont la longueur est grande par rapport à ses dimensions transversales, tel qu'un fil, une bande, une barre ou un tube.The word "aluminum" is understood in the broad sense of aluminum and its alloys. It will be so throughout the rest of the text. The word "driver" here refers to a body electrically conductive, elongated, the length of which is large by relative to its transverse dimensions, such as a wire, a band, a bar or a tube.

Etat de la techniqueState of the art

Les conducteurs électriques en aluminium sont largement utilisés dans le transport de l'énergie électrique. Ces conducteurs se présentent le plus souvent sous forme de barres, méplats, fils ou câbles.Aluminum electrical conductors are widely used in the transportation of electrical energy. These drivers are most often in the form of bars, flats, wires or cables.

Les fils et câbles électriques à âme en aluminium, qui peuvent comprendre un revêtement en matériau isolant, sont généralement obtenus à partir d'un fil "machine" coulé et laminé en continu qui est ensuite tréfilé jusqu'au diamètre souhaité. Des fils, ou brins, unitaires peuvent ensuite être assemblés pour former l'âme conductrice d'un câble.Aluminum-core electrical wires and cables, which may include a coating made of insulating material, are generally obtained from a wire "machine" cast and rolled continuously which is then drawn to the desired diameter. Sons, or strands, unitary can then be assembled to form the conductive core of a cable.

Dans une grande partie des applications, telles que le transport et la distribution d'énergie électrique, les conducteurs en aluminium peuvent être utilisés à l'état brut, c'est-à-dire sans traitement particulier de la surface du conducteur, outre un brossage éventuel des parties du conducteur destinées à l'établissement d'un contact électrique. Pour certaines applications, cependant, il est préférable de revêtir le conducteur en aluminium d'une couche de nickel, de manière à améliorer les propriétés de contact électrique.In a large part of the applications, such as transport and distribution electrical energy, aluminum conductors can be used in the raw state, that is to say without special treatment of the driver's surface, in addition to brushing possible parts of the conductor intended for the establishment of an electrical contact. For some applications, however, it is best to wear the driver aluminum with a nickel layer, so as to improve the contact properties electric.

Selon les procédés connus de nickelage au défilé, le conducteur circule dans au moins une cuve de nickelage électrolytique. Cette cuve est munie d'une électrode de nickel qui fait fonction d'anode et qui, dans ce but, est raccordée à la borne positive d'une l'alimentation électrique. Le conducteur à traiter fait fonction de cathode vierge et, pour cela, est relié électriquement à la borne négative de cette alimentation.According to known methods of nickel plating, the driver travels in at less an electrolytic nickel plating tank. This tank is equipped with an electrode of nickel which acts as anode and which, for this purpose, is connected to the positive terminal of a power supply. The driver to be treated acts as a virgin cathode and, for this, is electrically connected to the negative terminal of this power supply.

Dans la demande française FR 2 526 052 (correspondant au brevet américain US 4 492 615), la demanderesse a proposé un procédé et un dispositif de nickelage électrolytique au défilé d'un conducteur en aluminium permettant d'atteindre des vitesses de défilement de 300 m/minute. Selon ce procédé, le courant électrolytique est transmis au conducteur par une prise dite de courant liquide, c'est-à-dire sans contact mécanique, ce qui évite les inconvénients des prises de courant mécaniques, notamment les arcs électriques. Plus précisément, le conducteur à revêtir circule dans une première cuve munie d'une électrode polarisée négativement, puis dans une seconde cuve munie d'une électrode polarisée positivement ; un courant électrique circule alors dans le conducteur lors de son passage dans les cuves. La première cuve contient une solution ionique aqueuse apte à transmettre le courant électrique de l'électrode au dit conducteur. La seconde cuve contient le bain de nickelage.In the French application FR 2 526 052 (corresponding to the US patent US 4 492 615), the applicant has proposed a method and a nickel-plating device electrolytic parade of an aluminum conductor to achieve scroll speeds of 300 m / minute. According to this method, the electrolytic current is transmitted to the driver by a so-called liquid current tap, that is to say without mechanical contact, which avoids the inconvenience of mechanical sockets, especially electric arcs. More specifically, the driver to be coated circulates in a first tank provided with a negatively polarized electrode, then in a second vessel provided with a positively polarized electrode; an electric current then circulates in the driver during his passage in the tanks. The first tank contains an aqueous ionic solution capable of transmitting the electric current of the electrode to said driver. The second tank contains the nickel bath.

Problème poséProblem

Le nickelage des conducteurs constitue toutefois une opération supplémentaire dont on cherche, à la fois, à minimiser le coût et à maximiser la productivité. Dans le cas des conducteurs sous forme de fil ou de câble, on obtient des coûts et une productivité satisfaisants en réalisant le nickelage des fils élémentaires au défilé à grande vitesse. Or, certains marchés, tels que celui de l'aéronautique, souhaitent disposer de fils d'aluminium nickelé de diamètre compris entre 0,1 et 0,5 mm, et de câbles constitués de tels fils.However, the nickel plating of the drivers is an additional operation we are looking at both minimizing the cost and maximizing productivity. In the case conductors in the form of wire or cable, costs and satisfactory productivity by performing the nickeling of the elementary wires at the parade to great speed. However, some markets, such as aeronautics, want have nickel-plated aluminum wire with a diameter between 0.1 and 0.5 mm, and cables consisting of such wires.

La méthode selon la demande française FR 2 526 052 permet difficilement de nickeler de manière satisfaisante, et avec une grande productivité, des fils de diamètre inférieur à 1 mm. En effet, la demanderesse a constaté que la qualité du revêtement de nickel devenait insuffisante lorsque la vitesse de défilement dépassait les 20 m/minute. D'autre part, puisque toute l'intensité du courant de nickelage transite dans le conducteur à traiter, les risques de rupture du conducteur en cours de traitement augmentent de manière rédhibitoire en dessous de 1 mm de diamètre lorsque, pour une épaisseur de la couche de nickel donnée, l'on cherche à maintenir la vitesse de déroulement (et par conséquent le courant de nickelage) à une valeur élevée. Par ailleurs, cette solution impose un courant dans la première cuve égal au courant de nickelage dans la seconde cuve. Les très fortes densités surfaciques de courant atteintes entraínent une attaque importante du conducteur dans la première cuve et, par conséquent, des irrégularités de la surface du conducteur qui le rendent plus fragile. Enfin, il s'est avéré, à l'usage, que la durée de vie des bains était relativement limitée, notamment en raison de l'important courant transitant dans le premier bain et entraínant un dépôt important de précipités.The method according to the French application FR 2 526 052 makes it difficult to nickeler satisfactorily, and with high productivity, son of diameter less than 1 mm. Indeed, the plaintiff found that the quality of the nickel coating was becoming insufficient when the scroll speed exceeded the 20 m / minute. On the other hand, since all the intensity of the current of nickel plating transits in the driver to be treated, the risk of breakage of the driver during the treatment increase unacceptably below 1 mm in diameter when, for a thickness of the given nickel layer, one seeks to maintain the unwinding speed (and consequently the nickel-plating current) to a value high. Moreover, this solution imposes a current in the first tank equal to nickel plating current in the second tank. The very high surface densities of currents reached lead to a major driver attack in the first tank and, consequently, unevenness of the driver's surface which makes it more fragile. Finally, it turned out, in use, that the life of the baths was relatively limited, in particular because of the large flow through the first bath and resulting in a large deposit of precipitates.

Dans la demande française FR 2 646 174 (correspondant au brevet américain US 5 015 340), la demanderesse a proposé de résoudre certains de ces inconvénients en utilisant des bains de composition identique, l'un pour une première étape dite d'activation et l'autre pour l'étape suivante de nickelage, ce qui permet de maintenir immergé le conducteur lors du passage d'une cuve à l'autre. Cette solution permet certes d'atteindre des vitesses de défilement de l'ordre de 130 m/minute, mais elle ne permet pas de limiter l'intensité du courant d'activation aux valeurs strictement nécessaires puisqu'elle est imposée par l'intensité du courant de nickelage. Cette solution ne résout pas les problèmes liés à la prise de courant liquide.In the French application FR 2,646,174 (corresponding to the US patent US 5 015 340), the applicant has proposed to solve some of these drawbacks by using baths of identical composition, one for a so-called first step activation and the other for the next step of nickel plating, which helps to maintain immersed the driver when passing from one tank to another. This solution allows although it is possible to reach scroll speeds of the order of 130 m / minute, but it does not does not limit the intensity of the activation current to the values strictly necessary since it is imposed by the intensity of the nickel-plating current. This solution does not solve the problems related to the liquid outlet.

Dans la demande française FR 2 609 292 (correspondant au brevet américain US 4 741 811), la demanderesse a également proposé de moduler la densité de courant le long du parcours du conducteur en réduisant la densité de courant dans la partie amont du bain de nickelage et/ou aval du bain dit d'activation et en réglant l'acidité du bain de nickelage à une valeur de pH comprise entre 1 et 5. Cette modulation est obtenue en pratique par l'utilisation de séries d'électrodes et d'écrans interposés entre les électrodes et le conducteur. Cette solution permet de nickeler des fils de diamètres compris entre 0,51 et 0,15 mm, à des vitesses de défilement comprises entre 25 et 50 m/minute. Toutefois, cette solution nécessite un dispositif complexe qui nécessite réglage précis des dimensions et de la position des composants, qui de surcroít peut évoluer dans le temps.In the French application FR 2 609 292 (corresponding to the US patent US 4 741 811), the Applicant has also proposed to modulate the current density on along the path of the driver by reducing the current density in the upstream of the bath of nickel plating and / or downstream of the so-called activation bath and by regulating the acidity of the nickel plating bath at a pH value of between 1 and 5. This modulation is obtained in practice by the use of series of electrodes and screens interposed between the electrodes and the conductor. This solution allows to nickle wires from diameters between 0.51 and 0.15 mm, with scrolling speeds included between 25 and 50 m / minute. However, this solution requires a complex device which requires precise adjustment of the dimensions and position of the components, which overhead can evolve over time.

Dans la demande française FR 2 650 696, il a été proposé un procédé de revêtement en continu d'un conducteur à base d'aluminium comprenant un pré-traitement chimique de la surface du conducteur pour y créer des points d'accrochage sous forme de germes métalliques microscopiques et le dépôt d'une couche métallique sur le conducteur par électrodéposition. Le procédé et le dispositif décrits dans ce document présentent l'inconvénient de fonctionner à vitesse de défilement réduite (les temps d'immersion sont de l'ordre de 20 à 24 secondes).In the French application FR 2,650,696, it was proposed a coating process continuously of an aluminum-based conductor comprising a pretreatment the surface of the conductor to create snap points under it form of microscopic metallic germs and the deposition of a metallic layer on the conductor by electroplating. The method and device described in this document have the disadvantage of operating at reduced scrolling speed (The immersion times are of the order of 20 to 24 seconds).

La demanderesse a donc recherché des moyens pour obtenir des conducteurs d'aluminium nickelé de diamètre inférieur à 1 mm qui évitent les inconvénients de l'art antérieur tout en maintenant une rentabilité et une productivité acceptables, avec des coûts d'investissement le plus bas possible.The plaintiff therefore sought ways to obtain drivers nickel-plated aluminum with a diameter of less than 1 mm, which avoids the disadvantages of the prior art while maintaining acceptable profitability and productivity, with investment costs as low as possible.

Description de l'inventionDescription of the invention

L'invention a pour objet un procédé de nickelage en continu (ou "au défilé") d'un conducteur en aluminium.The subject of the invention is a method of continuous nickel plating (or "parade") of a aluminum conductor.

Plus précisément, le procédé de nickelage au défilé d'un conducteur en aluminium ou en alliage d'aluminium selon l'invention comprend une étape de pré-traitement P apte à favoriser l'adhérence de la couche de nickel et une étape de nickelage électrolytique N, et est caractérisé en ce que ledit pré-traitement P est réalisé par voie électrolytique et est également apte à conférer au dit conducteur des propriétés de contact suffisantes pour permettre un contact électrique mécanique et en ce que le courant de nickelage est transmis au dit conducteur par l'intermédiaire d'un contact électrique mécanique sur la partie du conducteur issue de l'étape de pré-traitement.Specifically, the nickel plating process of an aluminum conductor or aluminum alloy according to the invention comprises a pre-treatment step P able to promote adhesion of the nickel layer and an electrolytic nickel plating step N, and is characterized by that said pre-treatment P is produced electrolytically and is also capable of conferring on the said driver sufficient contact properties to allow mechanical electrical contact and in that the nickel plating current is transmitted to said driver via a mechanical electrical contact on the driver's part after the pre-treatment step.

L'étape de nickelage électrolytique N permet de former, par électrodéposition, une couche de nickel uniforme sur ledit conducteur.The electrolytic nickel plating step N makes it possible to form, by electrodeposition, a uniform nickel layer on said conductor.

La demanderesse a constaté, de manière inattendue, que, grâce à l'opération de pré-traitement, il était possible d'utiliser des contacts mécaniques sur des conducteurs de très faible diamètre et de faire transiter toute l'intensité de nickelage dans le conducteur par ces contacts (appelés aussi "prises de courant"). Elle a de surplus observé que, de manière surprenante, cette solution permettait d'atteindre des vitesses de défilement nettement supérieures à 20 m/minute, comme le met en évidence l'exemple présenté plus loin.The Applicant has found, unexpectedly, that, thanks to the pre-treatment operation, it was possible to use mechanical contacts on conductors of very small diameter and to pass through all the nickel-plating intensity in the driver by these contacts (also known as "sockets"). She has surplus observed that, surprisingly, this solution made it possible to reach much higher than 20 m / minute, as highlighted by the example presented below.

L'invention a aussi pour objet un dispositif de nickelage en continu (ou "au défilé") d'un conducteur en aluminium.The invention also relates to a continuous nickel plating device (or "parade") an aluminum conductor.

Même si l'invention concerne principalement les conducteurs en aluminium destinés aux applications électriques, elle s'applique également aux conducteurs en aluminium destinés à des usages non électriques, tels que des usages thermiques (qui exploitent la conductivité thermique élevée de l'aluminium, comme un échangeur thermique) ou, éventuellement, des usages essentiellement mécaniques.Although the invention mainly concerns aluminum conductors intended for for electrical applications, it also applies to aluminum conductors intended for non-electrical purposes, such as thermal uses (which exploit the high thermal conductivity of aluminum, such as a heat exchanger) or, possibly, essentially mechanical uses.

L'invention peut également être appliquée au nickelage de produits en aluminium, tels que des fils, des bandes ou des tubes en aluminium, destinés à être brasés. En particulier, l'invention a pour objet l'utilisation du procédé ou du dispositif selon l'invention pour le nickelage d'un produit en aluminium de manière à permettre un brasage de celui-ci. La couche de nickel, avec une épaisseur typiquement de l'ordre de 1 µm, peut permettre la formation d'un joint brasé satisfaisant sans avoir recours à un flux de brasage spécifique. L'invention a également pour objet un procédé de fabrication d'un produit assemblé, caractérisé en ce qu'il comprend l'utilisation d'un produit en aluminium nickelé selon l'invention. Ledit procédé de fabrication comprend éventuellement une opération de brasage dudit produit en aluminium nickelé.The invention can also be applied to the nickel plating of aluminum products, such as wires, strips or tubes of aluminum, intended to be brazed. In In particular, the subject of the invention is the use of the method or device according to the invention for the nickel plating of an aluminum product so as to allow a brazing of it. The nickel layer, with a thickness typically of the order than 1 μm, can allow the formation of a satisfactory soldered joint without recourse to a specific soldering flux. The subject of the invention is also a method of manufacture of an assembled product, characterized in that it comprises the use of a product made of nickel-plated aluminum according to the invention. Said manufacturing process possibly comprises a soldering operation of said aluminum product nickel.

Description des figuresDescription of figures

  • La figure 1 illustre schématiquement un premier mode de réalisation préféré du procédé nickelage au défilé selon l'invention. Dans ce mode de réalisation, l'étape de pré-traitement P est effectuée par voie électrolytique et est réalisée avec des moyens de contact mécanique communs à ceux de l'étape de nickelage N.Figure 1 schematically illustrates a first preferred embodiment of the nickel plating process according to the invention. In this embodiment, the step of pretreatment P is carried out electrolytically and is carried out with of mechanical contact common to those of the nickel plating step N.
  • La figure 2 illustre schématiquement un deuxième mode de réalisation préféré de l'invention selon lequel l'étape de pré-traitement P est configurée en prise de courant liquide.Figure 2 schematically illustrates a second preferred embodiment of the invention according to which the pre-treatment step P is configured as a power socket liquid.
  • La figure 3 illustre un moyen de contact mécanique selon l'invention comprenant une ou plusieurs roues.FIG. 3 illustrates a mechanical contact means according to the invention comprising a or more wheels.
  • La figure 4 illustre un autre moyen de contact selon l'invention comprenant trois roues.FIG. 4 illustrates another contact means according to the invention comprising three wheels.

    • Description détaillée de l'inventionDetailed description of the invention

    Le procédé de nickelage au défilé d'au moins un conducteur (1) en aluminium ou en alliage d'aluminium selon l'invention comprend une étape de pré-traitement P apte à favoriser l'adhérence d'une couche de nickel et une étape de nickelage électrolytique N dans laquelle ladite couche de nickel est déposée sur ledit conducteur par l'action d'un courant dit de nickelage (In = I1), et est caractérisé en ce que ledit pré-traitement P est réalisé par voie électrolytique et est également apte à conférer au dit conducteur (1) des propriétés de contact suffisantes pour permettre un contact électrique mécanique et en ce que le courant de nickelage (In = I1) est transmis au dit conducteur par l'intermédiaire d'un contact électrique mécanique (7), de préférence immergé dans un liquide (14), sur la partie (6) du conducteur (1) issue de l'étape de pré-traitement P.
    Ledit contact mécanique (7) comprend de préférence au moins un moyen de contact mécanique par roulement (70) qui comporte typiquement au moins une roue à gorge ou une réa.    The method of nickel-plating with at least one conductor (1) made of aluminum or aluminum alloy according to the invention comprises a pre-treatment step P capable of promoting the adhesion of a nickel layer and a step electrolytic nickel plating apparatus in which said nickel layer is deposited on said conductor by the action of a so-called nickel-plating current (I n = I 1 ), and is characterized in that said pre-treatment P is electrolytically performed. and is also capable of conferring on the said conductor (1) sufficient contact properties to allow mechanical electrical contact and in that the nickel-plating current (I n = I 1 ) is transmitted to said conductor via a mechanical electrical contact (7), preferably immersed in a liquid (14), on the part (6) of the conductor (1) resulting from the pre-treatment step P.
    Said mechanical contact (7) preferably comprises at least one rolling mechanical contact means (70) which typically comprises at least one grooved wheel or a sheave.

    Les propriétés de contact sont suffisantes lorsqu'il est possible de faire transiter toute l'intensité du courant de nickelage par le contact mécanique sans endommager le conducteur. Typiquement, le contact mécanique doit permettre de faire transiter un courant de nickelage de l'ordre de 5 A pour un fil de 0,15 mm de diamètre lorsque la vitesse de défilement est de 50 m/minute.Contact properties are sufficient when it is possible to transit any the intensity of the nickel-plating current by the mechanical contact without damaging the driver. Typically, the mechanical contact must make it possible to transit a nickel plating current of the order of 5 A for a wire of 0.15 mm diameter when the scroll speed is 50 m / minute.

    Le contact électrique mécanique peut être réalisé, par exemple, à l'aide de roulettes, galets, contacts frottants ou de brosses.The mechanical electrical contact can be made, for example, using rollers, rollers, rubbing contacts or brushes.

    La composition du bain de nickelage est avantageusement la suivante : 300 ± 30 g/l de Ni(NH2SO3)2 (sulfamate), 30 ± 5 g/l de NiCl2,6H2O, 30 ± 5 g/l de H3BO3·The composition of the nickel plating bath is advantageously as follows: 300 ± 30 g / l of Ni (NH 2 SO 3 ) 2 (sulphamate), 30 ± 5 g / l of NiCl 2 , 6H 2 O, 30 ± 5 g / l of H 3 BO 3 ·

    Le dispositif de nickelage au défilé d'au moins un conducteur en aluminium ou en alliage d'aluminium (ou "ligne de traitement") selon l'invention comprend une cuve de nickelage (30) comprenant un bac (2) apte à contenir un bain de nickelage (4) et au moins une électrode (3) contenant du nickel, dite anode, au moins une alimentation électrique (5) pour appliquer une tension électrique (V1) entre la, ou chaque, électrode et ledit conducteur, et des moyens (21, 22) pour faire défiler le, ou chaque, conducteur (1) dans le bain de nickelage (4), et est caractérisé en ce qu'il comprend aussi au moins une cuve de pré-traitement électrolytique (40,41,42) comprenant un bac (17,43,46) apte à contenir un bain de pré-traitement (16, 44, 47), et des moyens pour faire défiler le, ou chaque, conducteur dans le bain de pré-traitement (16, 44, 47), et en ce qu'il comprend des moyens de contact mécaniques (7, 13, 14) pour appliquer ladite tension électrique sur la partie (6) du, ou de chaque, dit conducteur (1) issue de l'étape de pré-traitement P. Typiquement, le conducteur à l'état brut (10), provenant d'au moins un premier dérouleur (22), transite successivement dans les bains de traitement (40, 41, 42, 30) et s'enroule, à l'état nickelé (11), sur au moins un deuxième dérouleur (21).The nickel-plating device with the passage of at least one conductor made of aluminum or aluminum alloy (or "treatment line") according to the invention comprises a nickel-plating tank (30) comprising a tank (2) capable of containing a nickel-plating bath (4) and at least one electrode (3) containing nickel, called anode, at least one power supply (5) for applying an electric voltage (V 1 ) between the or each electrode and said conductor, and means (21, 22) for scrolling the or each conductor (1) in the nickel-plating bath (4), and is characterized in that it also comprises at least one electrolytic pre-treatment tank (40, 41,42) comprising a tray (17,43,46) adapted to contain a pre-treatment bath (16,44,47), and means for scrolling the or each conductor in the pre-treatment bath (16, 44, 47), and in that it comprises mechanical contact means (7, 13, 14) for applying said electrical voltage to the part (6) of the, or e, each said driver (1) from the pre-treatment step P. Typically, the driver in the raw state (10), from at least a first unwinder (22), passes successively in the baths of treatment (40, 41, 42, 30) and rolls, in the nickeled state (11), on at least one second unwinder (21).

    L'étape de pré-traitement est choisie pour conférer au conducteur des propriétés de contact suffisantes pour permettre un contact électrique mécanique sur celui-ci.The pre-treatment step is chosen to give the driver properties of sufficient contact to allow mechanical electrical contact therewith.

    L'étape de pré-traitement P est réalisée par voie électrolytique, ce qui permet de maítriser plus facilement le pré-traitement en fonction des conditions de fonctionnement de la ligne de traitement. La cuve de pré-traitement (40) est munie d'au moins une électrode (15) et le dispositif comprend une alimentation électrique (8) destinée au pré-traitement. La tension électrique V2 délivrée par cette alimentation peut être alternative, continue ou pulsée, ou une combinaison de celles-ci. La prise de courant sur le conducteur est réalisée par un contact mécanique placé en aval de la cuve de pré-traitement (40). Cette prise de courant mécanique est avantageusement commune à celle de l'étape de nickelage, tel qu'illustré à la figure 1, ce qui permet de simplifier le dispositif sans entraíner une surcharge des moyens de contact mécanique (7, 13, 14) car l'intensité du courant de pré-traitement (I2) est généralement nettement inférieur à l'intensité du courant de nickelage (I1).The pre-treatment step P is performed electrolytically, which makes it easier to control the pre-treatment according to the operating conditions of the treatment line. The pre-treatment tank (40) is provided with at least one electrode (15) and the device comprises a power supply (8) for the pre-treatment. The voltage V 2 delivered by this power supply can be alternating, continuous or pulsed, or a combination thereof. The socket on the conductor is made by a mechanical contact placed downstream of the pre-treatment tank (40). This mechanical power outlet is advantageously common to that of the nickel-plating step, as illustrated in FIG. 1, which makes it possible to simplify the device without leading to an overloading of the mechanical contact means (7, 13, 14). the intensity of the pre-treatment current (I 2 ) is generally much lower than the intensity of the nickel-plating current (I 1 ).

    Selon une première variante de l'invention, l'étape de pré-traitement P comprend une activation A dans un bain fortement acide ou alcalin qui permette, notamment, une dissolution rapide des oxydes de surface. L'activation est réalisée dans une cuve d'activation (40, 42) comprenant un bac (17, 46) apte à contenir le bain d'activation (16, 47), dans lequel défile le conducteur (1). Lorsque l'étape d'activation est réalisée par voie électrolytique, la cuve d'activation (40, 42) comprend également au moins une électrode (15, 48) et le dispositif comprend une alimentation électrique (8) destinée à cette activation. La tension électrique V2 délivrée par cette alimentation peut être alternative, continue ou pulsée, ou une combinaison de celles-ci.According to a first variant of the invention, the pre-treatment step P comprises an activation A in a strongly acidic or alkaline bath which allows, in particular, a rapid dissolution of the surface oxides. The activation is performed in an activation tank (40, 42) comprising a tank (17, 46) capable of containing the activation bath (16, 47), in which the conductor (1) scrolls. When the activation step is performed electrolytically, the activation vessel (40, 42) also comprises at least one electrode (15, 48) and the device comprises a power supply (8) for this activation. The voltage V 2 delivered by this power supply can be alternating, continuous or pulsed, or a combination thereof.

    Selon une deuxième variante de l'invention, l'étape de pré-traitement P comprend, outre une étape d'activation A pour dissoudre notamment les oxydes présents en surface du conducteur (1), une étape de pré-nickelage PN permettant de revêtir le conducteur d'aluminium (1) d'un dépôt de nickel "primaire". Le courant de nickelage (I1) est alors transmis au dit conducteur par l'intermédiaire de moyens de contact mécanique (7, 13, 14) sur la partie (6) du conducteur (1) revêtue dudit dépôt de nickel primaire.According to a second variant of the invention, the pretreatment step P comprises, in addition to an activation step A to dissolve in particular the oxides present on the surface of the conductor (1), a pre-nickeling step PN making it possible to coat the aluminum conductor (1) of a "primary" nickel deposit. The nickel plating current (I 1 ) is then transmitted to said conductor via mechanical contact means (7, 13, 14) on the portion (6) of the conductor (1) coated with said primary nickel deposit.

    Le terme "dépôt de nickel primaire" s'entend d'une couche de nickel, qui se présente sous forme de nodules, dont l'épaisseur équivalente est nettement inférieure à l'épaisseur visée de la couche finale. Il a été trouvé préférable de viser une épaisseur équivalente qui est, en moyenne, inférieure à environ 0,1 de l'épaisseur finale. Typiquement, l'épaisseur de la couche finale étant de 1 µm environ, on visera une épaisseur équivalente de la couche de pré-nickelage inférieure à 0,1 µm environ.The term "primary nickel deposition" means a layer of nickel, which is in the form of nodules, whose equivalent thickness is significantly less than the targeted thickness of the final layer. It was found preferable to aim for a thickness equivalent which is, on average, less than about 0.1 of the final thickness. Typically, the thickness of the final layer being about 1 μm, we will aim at equivalent thickness of the pre-nickel plating layer less than about 0.1 μm.

    Le pré-nickelage est réalisé dans une cuve (40, 4 1 ) comprenant un bac (17, 43) apte à contenir le bain de pré-nickelage (16, 44), dans lequel défile le conducteur (1). Le bain de pré-nickelage (16, 44) contient un sel de nickel de manière à revêtir le conducteur d'aluminium d'un dépôt de nickel primaire lorsque le conducteur défile dans ce bain.The pre-nickel plating is carried out in a tank (40, 4 1) comprising a tank (17, 43) adapted to contain the pre-nickel bath (16, 44), in which the conductor (1) scrolls. The pre-nickel bath (16, 44) contains a nickel salt so as to coat the aluminum conductor of a primary nickel deposit when the driver scrolls in this bath.

    L'étape de pré-nickelage est de préférence réalisée par voie électrolytique, ce qui permet de maítriser plus facilement l'épaisseur de la couche en fonction des conditions de fonctionnement de la ligne de traitement. Dans ce cas la cuve de pré-nickelage (40, 41) est munie d'au moins une électrode (15, 45) contenant du nickel et le dispositif comprend une alimentation électrique (8) destinée au pré-nickelage. La tension électrique V2 délivrée par cette alimentation peut être alternative, continue ou pulsée, ou une combinaison de celles-ci.The pre-nickel plating step is preferably carried out electrolytically, which makes it easier to control the thickness of the layer depending on the operating conditions of the treatment line. In this case the pre-nickel plating tank (40, 41) is provided with at least one electrode (15, 45) containing nickel and the device comprises a power supply (8) for the pre-nickel plating. The voltage V 2 delivered by this power supply can be alternating, continuous or pulsed, or a combination thereof.

    Avantageusement, l'étape de pré-nickelage PN est, en tout ou partie, combinée à l'étape d'activation A, ce qui permet de simplifier considérablement le dispositif. Dans une variante préférée de ce mode de réalisation, les étapes de pré-nickelage et d'activation sont réalisées de manière conjointe avec une prise de courant liquide. Advantageously, the PN pre-nickeling stage is wholly or partly combined with the activation step A, which greatly simplifies the device. In a preferred variant of this embodiment, the steps of pre-nickel plating and activation are carried out jointly with a liquid outlet.

    La figure 2 illustre un dispositif qui permet de mettre en oeuvre cette variante de l'invention. Ce dispositif comprend une cuve d'activation électrolytique (42) et une cuve de pré-nickelage électrolytique (41), de préférence proches l'une de l'autre et éventuellement adjacentes, une première alimentation électrique (8) commune à ces deux cuves, une cuve de nickelage électrolytique (30), une seconde alimentation électrique (5) et des moyens de contact mécanique (7, 13, 14) sur la partie (6) du conducteur (1) située entre la cuve de pré-nickelage (41) et la cuve de nickelage (30).FIG. 2 illustrates a device that makes it possible to implement this variant of the invention. This device comprises an electrolytic activation tank (42) and a electrolytic pre-nickel plating tank (41), preferably close to each other and possibly adjacent, a first power supply (8) common to these two tanks, an electrolytic nickel plating tank (30), a second feed (5) and mechanical contact means (7, 13, 14) on the part (6) of the conductor (1) between the pre-nickel plating tank (41) and the nickel-plating tank (30).

    La première alimentation électrique (8) est, de préférence, en courant continu, éventuellement modulé ou pulsé ; la borne positive est raccordée à au moins une électrode (45) immergée, en tout ou partie, dans le bain de pré-nickelage (44) et la borne négative est raccordée à au moins une électrode (48) immergée, en tout ou partie, dans le bain d'activation (47). Le courant transite dans le conducteur (1) par un effet de prise de courant liquide. Ainsi, la même alimentation électrique (8) est utilisée pour l'activation et le pré-nickelage.The first power supply (8) is preferably DC, optionally modulated or pulsed; the positive terminal is connected to at least one electrode (45) immersed, in whole or in part, in the pre-nickel bath (44) and the negative terminal is connected to at least one submerged electrode (48) in all or part, in the activation bath (47). The current flows through the conductor (1) through a liquid outlet effect. Thus, the same power supply (8) is used for activation and pre-nickel plating.

    La deuxième alimentation électrique (5) est en courant continu, éventuellement modulé ou pulsé ; la borne positive est raccordée à au moins une électrode (3) contenant du nickel immergée, en tout ou partie, dans le bain de nickelage (4) et la borne négative est raccordée sur la partie (6) du conducteur (1) située entre la cuve de pré-nickelage (41) et la cuve de nickelage (30) par l'intermédiaire de moyens de contact mécanique (7, 13, 14).The second power supply (5) is in direct current, possibly modulated or pulsed; the positive terminal is connected to at least one electrode (3) containing all or part of the nickel in the nickel-plating bath (4) and the negative terminal is connected to the part (6) of the conductor (1) between the tank pre-nickel plating (41) and the nickel-plating tank (30) via means of mechanical contact (7, 13, 14).

    Pour la variante illustrée à la figure 2, il a été trouvé avantageux d'utiliser la composition suivante pour les bains d'activation et de pré-nickelage : 125 ± 15 g/l de chlorure de nickel (NiCl2, 6 H2O), 12,5 ± 2 g/l d'acide orthoborique et 6 ± 2 ml/l d'acide fluorhydrique.For the variant illustrated in FIG. 2, it has been found advantageous to use the following composition for the activation and pre-nickel plating baths: 125 ± 15 g / l of nickel chloride (NiCl 2 , 6 H 2 O ), 12.5 ± 2 g / l of orthoboric acid and 6 ± 2 ml / l of hydrofluoric acid.

    Les étapes de pré-nickelage PN et d'activation A peuvent être réalisées de manière simultanée, dans un même bain (40) et avec des électrodes (15) communes (et ayant la même polarisation), tel qu'illustré à la figure 1. Dans ce cas, l'étape de pré-traitement opère une double fonction d'activation et de pré-nickelage. Le bain d'activation/pré-nickelage (16) est alors apte à opérer les deux traitements, par exemple en ayant une composition mixte qui permet à la fois une activation satisfaisante et un pré-nickelage suffisant. La demanderesse a constaté qu'il était possible de réaliser efficacement ces deux fonction à l'aide d'un bain unique. La composition suivante a donné d'excellents résultats : 125 ± 15 g/l de chlorure de nickel (NiCl2, 6 H2O), 12,5 ± 2 g/l d'acide orthoborique et 6 ± 2 ml/l d'acide fluorhydrique.The pre-nickel plating and activation A stages can be carried out simultaneously, in the same bath (40) and with common electrodes (15) (and having the same polarization), as illustrated in FIG. In this case, the pre-treatment step operates a dual function of activation and pre-nickel plating. The activation bath / pre-nickel plating (16) is then able to operate both treatments, for example by having a mixed composition that allows both a satisfactory activation and a sufficient pre-nickel plating. The Applicant has found that it is possible to effectively perform these two functions using a single bath. The following composition gave excellent results: 125 ± 15 g / l of nickel chloride (NiCl 2 , 6 H 2 O), 12.5 ± 2 g / l of orthoboric acid and 6 ± 2 ml / l of hydrofluoric acid.

    Dans cette variante, la première alimentation électrique (8) est en courant continu, éventuellement modulé ou pulsé, la borne positive étant raccordée au conducteur (1) par l'intermédiaire du contact mécanique (7) et la borne négative étant raccordée à au moins une électrode (15) immergée, en tout ou partie, dans ledit bain d'activation/pré-nickelage (16). La deuxième alimentation électrique (5) est en courant continu, éventuellement modulé ou pulsé ; la borne positive est raccordée à une électrode (3) contenant du nickel immergée, en tout ou partie, dans le bain de nickelage (4) et la borne négative est raccordée sur la partie (6) du conducteur (1) située entre la cuve d'activation/pré-nickelage (40) et la cuve de nickelage (30) par l'intermédiaire des moyens de contact mécanique (7, 13, 14), de préférence communs à ceux de la première alimentation (8).In this variant, the first power supply (8) is in direct current, optionally modulated or pulsed, the positive terminal being connected to the conductor (1) via the mechanical contact (7) and the negative terminal being connected to at least one electrode (15) immersed, in whole or in part, in said bath activation / pre-nickel plating (16). The second power supply (5) is in direct current, optionally modulated or pulsed; the positive terminal is connected to an electrode (3) containing nickel immersed, in whole or in part, in the bath of nickel plating (4) and the negative terminal is connected to the part (6) of the conductor (1) located between the activation / pre-nickel plating tank (40) and the nickel-plating tank (30) by intermediate mechanical contact means (7, 13, 14), preferably common to those of the first diet (8).

    Pour les conducteurs de très faible section, notamment pour les fils de diamètre inférieur à 0,2 mm, il est préférable que le contact mécanique soit immergé dans un liquide (14) tel que de l'eau ou une solution neutre, de manière à éviter la fusion du conducteur au droit du contact mécanique. Dans ce but, le dispositif peut comprendre un bac intermédiaire (13), généralement de petites dimensions, contenant le liquide (14) et le contact mécanique (7). Le liquide (14) peut éventuellement être refroidi.For very small section conductors, especially for diameter wires less than 0.2 mm, it is preferable that the mechanical contact is immersed in a liquid (14) such as water or a neutral solution, so as to avoid the melting of the conductor to the right of mechanical contact. For this purpose, the device can include an intermediate tray (13), generally small, containing the liquid (14) and the mechanical contact (7). The liquid (14) can optionally be cooled.

    La demanderesse a également noté que, afin d'atteindre des vitesses de défilement élevées, il était préférable d'utiliser des moyens de contact mécanique qui limitent le plus possible le frottement entre ceux-ci et le conducteur car un coefficient de frottement élevé peut conduire à la fusion du conducteur même lorsque le contact électrique est immergé dans un liquide. Il a été trouvé particulièrement avantageux d'utiliser des contacts mécaniques comprenant au moins une roue, de préférence à gorge, en particulier tel qu'illustré aux figures 3 et 4. L'utilisation de roues de contact permet notamment d'éviter les problèmes d'étincelage et de dégradation de la surface du conducteur après tré-traitement.The Applicant also noted that in order to achieve scroll speeds high, it was preferable to use mechanical contact means which limited the friction between them and the driver as a coefficient of high friction can lead to the fusion of the driver even when the contact electric is immersed in a liquid. It has been found particularly advantageous to use mechanical contacts comprising at least one wheel, preferably in particular as shown in FIGS. 3 and 4. The use of contact wheels in particular to avoid the problems of spark and degradation of the surface of the driver after treatreatment.

    Pour le traitement de deux ou plusieurs conducteurs en parallèle (traitement "en nappe"), le contact mécanique peut comprendre plusieurs roues parallèles tournant autour d'un axe commun (tel qu'illustré à la figure 3).For the treatment of two or more conductors in parallel (treatment "in sheet "), the mechanical contact may comprise several parallel wheels rotating around a common axis (as shown in Figure 3).

    Le moyen de contact mécanique par roulement (70) illustré à la figure 3, qui correspond à un mode de réalisation préféré de l'invention, comprend une ou plusieurs roues (71) tournant autour d'un essieu (73) dont l'axe central (75) est sensiblement perpendiculaire aux dites roues (71). La (ou chaque) roue (71) est de préférence pourvue d'une gorge (74) dans laquelle s'appuie le conducteur (6), ce qui permet notamment d'éviter les variations de position de celui-ci. Le courant électrique transite de l'essieu (73) au conducteur (6) par l'intermédiaire de la roue (71). L'ensemble essieu-roue(s) (70) peut être immergé dans un liquide (14). Le moyen de contact (70) peut comprendre une bague (72), typiquement en graphite, pour faciliter le roulement des roues (71) autour de l'essieu (73) et améliorer le contact électrique. Cette dernière variante permet également d'éviter le recours à un roulement à billes. Dans les essais de la demanderesse, les roues (71) étaient en cuivre (éventuellement nickelé) et l'essieu (73) était en acier inoxydable.The rolling mechanical contact means (70) illustrated in FIG. corresponds to a preferred embodiment of the invention, comprises one or a plurality of wheels (71) rotating about an axle (73) whose central axis (75) is substantially perpendicular to said wheels (71). The (or each) wheel (71) is preferably provided with a groove (74) in which the conductor (6) rests, which allows in particular to avoid variations in position thereof. The flow electrical transits from the axle (73) to the driver (6) via the wheel (71). The axle-wheel assembly (70) can be immersed in a liquid (14). The contact means (70) may comprise a ring (72), typically made of graphite, to facilitate the rolling of the wheels (71) around the axle (73) and to improve the electric contact. This last variant also makes it possible to avoid resorting to a ball bearing. In the tests of the plaintiff, the wheels (71) were in copper (possibly nickel plated) and the axle (73) was made of stainless steel.

    Le moyen de contact mécanique illustré à la figure 4, qui correspond également à un mode de réalisation préféré de l'invention, comprend un ensemble d'au moins trois roues (701, 702, 703) qui coopèrent pour assurer un contact électrique satisfaisant sur le (ou chaque) conducteur (6). De préférence, chaque conducteur comprend de tels moyens lorsque plusieurs conducteurs sont traités simultanément. Au moins un desdits moyens de contacts mécaniques (7, 13, 14) comprend un tel moyen de contact. Chaque roue tourne autour d'un axe propre (731, 732, 733) et exerce un effort (F1, F2, F3) sur le conducteur. En pratique, il est suffisant d'ajuster l'effort exercé sur le conducteur en ne déplaçant que la roue centrale (702). Les trois roues peuvent être immergées dans un liquide (14).The mechanical contact means illustrated in FIG. 4, which also corresponds to a preferred embodiment of the invention, comprises a set of at least three wheels (701, 702, 703) which cooperate to provide satisfactory electrical contact on the (or each) driver (6). Preferably, each driver comprises such means when several conductors are processed simultaneously. At least one said mechanical contact means (7, 13, 14) comprises such a means of contact. Each wheel rotates around a proper axis (731, 732, 733) and exerts a effort (F1, F2, F3) on the driver. In practice, it is sufficient to adjust the effort exerted on the driver by moving only the central wheel (702). The three wheels can be immersed in a liquid (14).

    La température des différents bains est généralement choisie de manière à ce que la conductivité ionique et la réactivité des bains soient suffisantes. Typiquement, la température des bains est comprise entre 45 et 60°C.The temperature of the different baths is generally chosen so that the ionic conductivity and the reactivity of the baths are sufficient. Typically, the bath temperature is between 45 and 60 ° C.

    Le procédé selon l'invention peut comprendre des étapes complémentaires, telles qu'un rasage et/ou un dégraissage éventuels du conducteur à l'état brut (10) avant l'étape d'activation et/ou de pré-nickelage.The method according to the invention may comprise complementary steps, such as any shaving and / or degreasing of the driver in the raw state (10) before the activation and / or pre-nickeling step.

    Le conducteur est typiquement en un alliage AA 1370, le AA 1110 ou le AA 6101 selon la nomenclature de l'Aluminium Association.The conductor is typically an AA 1370 alloy, AA 1110 or AA 6101 according to the nomenclature of the Aluminum Association.

    Le procédé de fabrication d'un câble électrique en aluminium peut comprendre une opération de nickelage selon l'invention d'au moins un des fils élémentaires.The process of manufacturing a cable electric aluminum can include a nickel plating operation the invention of at least one of the elementary threads.

    Selon une autre variante de l'invention, plusieurs conducteurs sont traités simultanément, notamment dans les bains de pré-traitement et de nickelage. Dans ce but, on peut, par exemple, disposer deux ou plusieurs conducteurs en parallèle, lesquels conducteurs peuvent passer simultanément d'une cuve à la suivante à l'aide de moyens de défilement individuels pour chaque conducteur ou communs à l'ensemble des conducteurs. En d'autres termes, le dispositif comprend des moyens pour faire défiler simultanément deux ou plusieurs conducteurs dans au moins une desdites cuves de traitement. Par exemple, des nappes de conducteurs provenant d'une série de dérouleurs distincts circulent en parallèle dans lesdits bains et, après traitement, s'enroulent sur une série d'enrouleurs distincts. Les moyens de contact (7, 13, 14) sur la partie des conducteurs (6) issue de l'étape de pré-traitement peuvent être, en tout ou partie, communs à ceux-ci ; par exemple, lesdits moyens peuvent comprendre une bande en matériau carboné qui peut être mise en contact avec l'ensemble des conducteurs d'une nappe.According to another variant of the invention, several drivers are treated simultaneously, especially in pre-treatment and nickel plating baths. In this purpose, it is possible, for example, to have two or more conductors in parallel, which drivers can pass from one tank to the next using individual scrolling means for each driver or common to all drivers. In other words, the device comprises means to simultaneously scroll two or more drivers in at least one said treatment tanks. For example, layers of conductors of a series of separate unwinders circulate in parallel in said baths and, after treatment, wind up on a series of separate reels. The contact means (7, 13, 14) on the part of the conductors (6) resulting from the pre-treatment step can to be wholly or partly common to them; for example, said means can include a strip of carbon material that can be brought into contact with all the drivers of a tablecloth.

    Le ou les conducteurs peuvent défiler horizontalement, verticalement ou avec un certain angle par rapport à l'horizontale.The driver (s) can scroll horizontally, vertically or with a certain angle to the horizontal.

    ExempleExample

    Des essais ont été réalisés, sur les fils d'un diamètre de 0,20 mm, selon l'art antérieur et selon l'invention.Tests have been carried out on the 0.20 mm diameter wires according to the prior art and according to the invention.

    Dans les essais correspondant à l'art antérieur, les courants d'activation et de nickelage étaient de même intensité et provenaient d'une alimentation commune configurée en prise de courant liquide (tel que décrit dans la demande FR 2 646 174) ; des écrans avaient été interposés entre les électrodes de nickel et le fil (tel que décrit dans la demande FR 2 609 292). Les bains d'activation et de nickelage avaient la même composition, à savoir : 125 ± 15 g/l de chlorure de nickel (NiCl2, 6 H2O), 12,5 ± 2 g/l d'acide orthoborique et 6 ± 2 ml/l d'acide fluorhydrique.In the tests corresponding to the prior art, the activation and nickel-plating currents were of the same intensity and came from a common power supply configured as a liquid outlet (as described in application FR 2 646 174); screens had been interposed between the nickel electrodes and the wire (as described in the application FR 2 609 292). The activation and nickel plating baths had the same composition, namely: 125 ± 15 g / l of nickel chloride (NiCl 2 , 6 H 2 O), 12.5 ± 2 g / l of orthoboric acid and 6 ± 2 ml / l of hydrofluoric acid.

    Les essais selon l'invention ont été réalisés à l'aide d'un dispositif similaire à celui de la figure 2. Les électrodes (48) de la cuve d'activation (42) étaient en graphite et les électrodes (45) de la cuve de pré-nickelage (41) étaient en nickel. Les bains d'activation et de pré-nickelage avaient la composition suivante : 125 ± 15 g/l de chlorure de nickel (NiCl2, 6 H2O), 12,5 ± 2 g/l d'acide orthoborique et 6 ± 2 ml/l d'acide fluorhydrique. Le bain de nickelage avait la composition suivante : 300 ± 30 g/l de Ni(NH2SO3)2 (sulfamate), 30 ± 5 g/l de NiCl2,6H2O, 30 ± 5 g/l de H3BO3.The tests according to the invention were carried out using a device similar to that of FIG. 2. The electrodes (48) of the activation tank (42) were made of graphite and the electrodes (45) of the pre-nickel plating tank (41) were made of nickel. Activation baths and pre-nickel plating baths had the following composition: 125 ± 15 g / l of nickel chloride (NiCl 2 , 6 H 2 O), 12.5 ± 2 g / l of orthoboric acid and 6 ± 2 ml / l of hydrofluoric acid. The nickel plating bath had the following composition: 300 ± 30 g / l of Ni (NH 2 SO 3 ) 2 (sulfamate), 30 ± 5 g / l of NiCl 2 , 6H 2 O, 30 ± 5 g / l of H 3 BO 3 .

    Le tableau I ci-dessous regroupe les principaux paramètres de traitement utilisés dans ces essais et certaines caractéristiques des fils traités. La résistance de contact a été mesurée à l'aide d'une méthode dite de "fil en croix", sous une intensité de 0,1 mA et avec un force d'appui de 0,2 N. L'adhérence de la couche de nickel sur le fil a été mesurée par un enroulement du fil sur son propre diamètre ; elle est considérée comme étant excellente si la couche de nickel suit uniformément la déformation du fil sans se détacher de la surface. Art antérieur Invention Vitesse de défilement (m/min) 50 80 Intensité du courant d'activation-nickelage (A) 12,5 sans objet Intensité du courant de pré-traitement (A) sans objet 3-10 Intensité du courant de nickelage (A) sans objet 15-30 Epaisseur moyenne du dépôt (µm) 0,8 0,8 Résistance de contact moyenne (mΩ) 15 15 Adhérence du dépôt excellente excellente Table I below groups together the main treatment parameters used in these tests and certain characteristics of the treated son. The contact resistance was measured using a so-called "cross-wire" method, at an intensity of 0.1 mA and with a bearing force of 0.2 N. The adhesion of the layer nickel on the wire was measured by winding the wire on its own diameter; it is considered excellent if the nickel layer uniformly follows the deformation of the wire without detaching from the surface. Prior art Invention Scroll Speed (m / min) 50 80 Intensity of activation current-nickel plating (A) 12.5 not applicable Intensity of the pre-treatment current (A) not applicable 3-10 Intensity of the nickel-plating current (A) not applicable 15-30 Average thickness of the deposit (μm) 0.8 0.8 Average contact resistance (mΩ) 15 15 Deposit adhesion excellent excellent

    Dans les essais selon l'art antérieur, il n'a pas été possible d'effectuer le traitement à une vitesse de défilement aussi élevée que 80 m/min. En effet, à une vitesse aussi élevée, on observait une "brûlure" du dépôt, c'est-à-dire un dépôt noir non-adhérent provoqué par une densité de courant trop importante dans l'étape d'activation.In the tests according to the prior art, it was not possible to perform the treatment at a scrolling speed as high as 80 m / min. Indeed, at a speed too high, we observed a "burn" of the deposit, that is to say a non-adherent black deposit caused by too much current density in the activation step.

    La couche de pré-nickelage obtenue par voie électrolytique se présentait sous forme de nodules qui ne recouvraient pas toute la surface du conducteur. La demanderesse a observé qu'il n'était pas nécessaire que ledit dépôt de nickel primaire (ou "couche de pré-nickelage") soit uniforme ou qu'elle revête entièrement la surface du conducteur ; il s'est avéré suffisant d'atteindre un taux de recouvrement équivalent correspondant à environ 0,1 de l'épaisseur finale de la couche de nickel. La demanderesse a émis l'hypothèse qu'un tel taux de recouvrement confère une qualité de contact électrique suffisante pour permettre la transmission par contact mécanique de fortes intensités de courant de nickelage sans dégrader la surface du conducteur et assure une adhérence élevée de la couche de nickel finale. Ainsi, le terme "dépôt de nickel primaire", s'entend d'une couche de nickel dont l'épaisseur est typiquement, en moyenne, de 0,1 µm environ. The pre-nickel plating obtained electrolytically was in the form of nodules that did not cover the entire surface of the driver. The plaintiff observed that it was not necessary for the said primary nickel deposit (or pre-nickel plating ") is uniform or completely covering the surface of the driver; it has proved sufficient to achieve an equivalent recovery rate corresponding to about 0.1 of the final thickness of the nickel layer. The plaintiff has speculated that such a recovery rate confers a quality sufficient electrical contact to allow transmission by mechanical contact high current levels of nickel plating without degrading the driver's surface and ensures high adhesion of the final nickel layer. Thus, the term "deposit of primary nickel "means a layer of nickel, the thickness of which is typically average of about 0.1 μm.

    La couche de nickel obtenue selon l'invention présente donc une grande adhérence et une faible résistance de contact électrique.The nickel layer obtained according to the invention therefore has high adhesion and a low electrical contact resistance.

    AvantagesAdvantages

    L'invention permet de nickeler efficacement, et avec une grande productivité, des fils de différents diamètres. Elle permet notamment un ajustement aisé des paramètres de traitement aux conditions de production, grâce au découplage entre les étapes de pré-traitement et de nickelage. Il est en particulier possible d'ajuster indépendamment l'intensité des courants de pré-traitement et de nickelage, et notamment d'imposer une intensité de courant faible dans l'étape de pré-traitement et élevée dans l'étape de nickelage.The invention makes it possible to nickel efficiently, and with high productivity, wires of different diameters. It allows in particular an easy adjustment of the parameters of treatment under the conditions of production, thanks to the decoupling between the pre-treatment stages and nickel plating. In particular it is possible to adjust independently the intensity of the pre-treatment and nickel-plating currents, and in particular to impose a low current intensity in the pre-treatment stage and high in the step of nickel plating.

    L'invention permet de bénéficier des avantages des prises de courant mécaniques, notamment la possibilité de faire transiter de fortes intensités, et d'en éviter les inconvénients, notamment la propension à former des arcs électriques qui peuvent endommager la surface du conducteur.The invention makes it possible to benefit from the advantages of mechanical sockets, in particular the possibility of passing on high intensities, and to avoid disadvantages, in particular the propensity to form electric arcs which can damage the driver's surface.

    La faible intensité du courant de pré-traitement requise selon l'invention conduit à un enrichissement en aluminium nettement plus lent du bain de pré-traitement, ce qui permet de réduire considérablement la fréquence de remplacement de ce bain. La faible intensité du courant de pré-traitement limite aussi la dissolution du métal et, en conséquence, la formation de rugosités sur la surface du fil. En d'autres termes, l'étape de pré-traitement selon l'invention permet également de conférer à la surface du conducteur une rugosité définie pour obtenir des propriétés mécaniques optimales.The low intensity of the pre-treatment current required according to the invention leads to a considerably slower aluminum enrichment of the pre-treatment bath, which significantly reduces the replacement frequency of this bath. The low intensity of the pre-treatment current also limits the dissolution of the metal and, in Consequently, the formation of roughnesses on the surface of the wire. In other words, the pre-treatment step according to the invention also makes it possible to confer on the surface of the conductor defined roughness to obtain optimal mechanical properties.

    Claims (26)

    1. Continuous nickel plating process of at least one aluminium or aluminium alloy conductor (1) comprising a pre-treatment step (P) that improves the adherence of a nickel coat, and an electrolytic nickel plating step (N) in which the said nickel coat is deposited on the said conductor by the action of a nickel plating current (In = I1), and characterized in that the said pre-treatment step (P) is done electrolytically and also makes the contact properties of the said conductor (1) sufficient to enable a mechanical electrical contact and in that the nickel plating current In is transmitted to the said conductor through a mechanical electrical contact (7) on the part (6) of the conductor (1) output from the pre-treatment step (P).
    2. Process according to claim 1, characterized in that the pre-treatment step (P) comprises an activation (A) in a strongly acid or alkaline bath, that in particular enables fast dissolution of surface oxides.
    3. Process according to any one of claims 1 or 2, characterized in that the pre-treatment step (P) comprises a pre-nickel plating step (PN) to coat the aluminium or aluminium alloy conductor (1) with a primary nickel deposit.
    4. Process according to claim 1, characterized in that the pre-treatment step (P) comprises an activation (A) in a strongly acid or alkaline bath (47), which in particular enables fast dissolution of surface oxides, and a pre-nickel plating step (PN) in a pre-nickel plating bath (44) that coats the aluminium or aluminium alloy conductor (1) with a primary nickel deposit, and in that the pre-nickel plating step (PN) and the activation step (A) are done jointly and electrolytically, with a liquid current connection.
    5. Process according to claim 4, characterized in that the compositions of the activation bath (47) and the pre-nickel plating bath (44) are approximately the same.
    6. Process according to claim 1, characterized in that the pre-treatment step (P) comprises an activation (A) in a strongly acid or alkaline bath that in particular enables fast dissolution of surface oxides, and a pre-nickel plating step (PN) in which the aluminium or aluminium alloy conductor (1) is coated with a primary nickel deposit, and in that the pre-nickel plating step (PN) and the activation step (A) are done simultaneously in the same bath (16).
    7. Process according to any one of claims 3 to 6, characterized in that the equivalent average thickness of the said primary nickel deposit is less than about 0.1 µm.
    8. Process according to any one of claims 1 to 7, characterized in that the mechanical contact (7) is immersed in a liquid (14), possibly cooled, such as water or a neutral solution.
    9. Process according to any one of claims 1 to 8, characterized in that the said mechanical contact (7) comprises at least one mechanical rolling contact means (70).
    10. Process according to any one of claims 1 to 9, characterized in that several conductors are treated simultaneously.
    11. Process according to any one of claims 1 to 10, characterized in that the conductor (1) is made of an aluminium alloy chosen from among AA 1370, AA 1110 and AA 6101 according to the nomenclature of the Aluminum Association.
    12. Manufacturing process for an aluminium or aluminium alloy electrical cable comprising a nickel plating operation on at least one of the elementary wires using the nickel plating process according to any one of claims 1 to 11.
    13. Continuous nickel plating device for at least one aluminium or aluminium alloy conductor (1) to implement the nickel plating process according to any one of claims 1 to 12, the said device comprising a nickel plating tank (30) comprising a receptacle (2) that can contain the nickel plating bath (4) and at least one electrode (3) called the anode, containing nickel, at least one electrical power supply (5) to apply an electrical voltage (V1) between the electrode (3), or each electrode, and the said conductor (1), and means (21, 22) of moving the conductor (1) in the nickel plating bath (4), the said device being characterized in that it also comprises at least one electrolytic pre-treatment tank (40, 41, 42) comprising a receptacle (17, 43, 46) that may contain a pre-treatment bath (16, 44, 47) and means of moving the conductor (1), or each conductor, in the pre-treatment bath (16, 44, 47) and in that it comprises mechanical contact means (7, 13, 14) of applying the said voltage on the part (6) of the conductor (1), or each conductor, output from the pre-treatment step (P).
    14. Device according to claim 13, characterized in that the pre-treatment tank (40, 41, 42), or each pre-treatment tank, is provided with at least one electrode (15, 45, 48) and in that the device comprises at least one electrical power supply (8) for the pre-treatment (P).
    15. Device according to claim 14, characterized in that the voltage of the electrical power supplies for the nickel plating (5) and the pre-treatment (8) is applied to the conductor (1) through the same mechanical contact means (7, 13, 14).
    16. Device according to any one of claims 13 to 15, characterized in that the mechanical contact means (7, 13, 14) comprise a tank (13) that may contain a liquid (14) in which the mechanical contact (7) is immersed.
    17. Device according to any one of claims 13 to 16, characterized in that it comprises an activation tank (42) comprising a receptacle (46) that may contain an activation bath (47) and at least one electrode (48), in that it comprises a pre-nickel plating tank (41) comprising a receptacle (43) that may contain a pre-nickel plating bath (44) and at least one electrode (45), and in that it comprises at least one common electrical power supply (8) for activation (A) and pre-nickel plating (PN).
    18. Device according to claim 17, characterized in that the electrical power supply of the activation tank (42) and the pre-nickel plating tank (41) is configured as a liquid current connection through the conductor (1).
    19. Device according to any one of claims 13 to 18, characterized in that it can be used for nickel plating of several conductors simultaneously.
    20. Device according to any one of claims 13 to 18, characterized in that it comprises means of advancing two or more conductors simultaneously in at least one of the said treatment tanks.
    21. Device according to any one of claims 13 to 20, characterized in that the said mechanical contact means (7, 13, 14) comprise at least one mechanical rolling contact means (70).
    22. Device according to claim 21, characterized in that the mechanical rolling contact means, or each of these means, comprises one or several wheels (71) rotating about an axle (73) whose central axis (75) is approximately perpendicular to the said wheels (71).
    23. Device according to claim 22, characterized in that the wheel (71), or each wheel, comprises a ring (72) typically made of graphite, to make it easier for the wheels (71) to rotate around the axle (73) and to improve the electrical contact.
    24. Device according to any one of claims 21 to 23, characterized in that at least one of the said mechanical contact means (7, 13, 14) comprises a set of at least three wheels (701, 702, 703) that work together to make an electrical contact on the conductor (6).
    25. Device according to any one of claims 22 to 24, characterized in that the wheel, or each wheel, is grooved.
    26. Use of the process according to any one of claims 1 to 12, or the device according to any one of claims 13 to 25, for nickel plating of an aluminium or aluminium alloy product such as an aluminium or aluminium alloy strip or tube, to enable brazing of the said product.
    EP00953251A 1999-07-22 2000-07-18 Method for continuous nickel-plating of an aluminium conductor and corresponding device Expired - Lifetime EP1204787B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    FR9909690A FR2796656B1 (en) 1999-07-22 1999-07-22 CONTINUOUS NICKELING PROCESS OF AN ALUMINUM CONDUCTOR AND CORRESPONDING DEVICE
    FR9909690 1999-07-22
    PCT/FR2000/002061 WO2001007685A2 (en) 1999-07-22 2000-07-18 Method for continuous nickel-plating of an aluminium conductor and corresponding device

    Publications (2)

    Publication Number Publication Date
    EP1204787A2 EP1204787A2 (en) 2002-05-15
    EP1204787B1 true EP1204787B1 (en) 2005-03-16

    Family

    ID=9548528

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP00953251A Expired - Lifetime EP1204787B1 (en) 1999-07-22 2000-07-18 Method for continuous nickel-plating of an aluminium conductor and corresponding device

    Country Status (7)

    Country Link
    US (1) US6780303B2 (en)
    EP (1) EP1204787B1 (en)
    AT (1) ATE291111T1 (en)
    DE (1) DE60018764T2 (en)
    ES (1) ES2238300T3 (en)
    FR (1) FR2796656B1 (en)
    WO (1) WO2001007685A2 (en)

    Families Citing this family (25)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US6942765B2 (en) * 2001-05-31 2005-09-13 Surfect Technologies, Inc. Submicron and nano size particle encapsulation by electrochemical process and apparatus
    US20060011487A1 (en) * 2001-05-31 2006-01-19 Surfect Technologies, Inc. Submicron and nano size particle encapsulation by electrochemical process and apparatus
    US20040038070A1 (en) * 2001-11-21 2004-02-26 Dockus Kostas F. Fluxless brazing
    US6815086B2 (en) * 2001-11-21 2004-11-09 Dana Canada Corporation Methods for fluxless brazing
    US20060102696A1 (en) * 2001-11-21 2006-05-18 Graham Michael E Layered products for fluxless brazing of substrates
    US20040035910A1 (en) * 2001-11-21 2004-02-26 Dockus Kostas F. Low temperature fluxless brazing
    US7451906B2 (en) * 2001-11-21 2008-11-18 Dana Canada Corporation Products for use in low temperature fluxless brazing
    US20040035911A1 (en) * 2001-11-21 2004-02-26 Dockus Kostas F. Fluxless brazing
    WO2004052547A2 (en) * 2002-12-05 2004-06-24 Surfect Technologies, Inc. Coated and magnetic particles and applications thereof
    WO2005076977A2 (en) * 2004-02-04 2005-08-25 Surfect Technologies, Inc. Plating apparatus and method
    FR2876493B1 (en) * 2004-10-12 2007-01-12 F S P One Soc Par Actions Simp COPPER ALUMINUM TORONIC CABLE AND METHOD FOR MANUFACTURING THE SAME
    US20060157352A1 (en) * 2005-01-19 2006-07-20 Corus Aluminium Walzprodukte Gmbh Method of electroplating and pre-treating aluminium workpieces
    RU2397154C2 (en) * 2005-02-08 2010-08-20 Дайно Нобель Инк. Delay devices and method of making said devices
    US8084158B2 (en) * 2005-09-02 2011-12-27 A123 Systems, Inc. Battery tab location design and method of construction
    WO2007028152A2 (en) * 2005-09-02 2007-03-08 A123 Systems, Inc. Battery cell design and method of its construction
    DE102007022632A1 (en) * 2007-05-11 2008-11-13 Visteon Global Technologies Inc., Van Buren Method of joining components of high strength aluminum material and heat exchangers mounted by this method
    US8236441B2 (en) 2007-07-24 2012-08-07 A123 Systems, Inc. Battery cell design and methods of its construction
    PL3242347T3 (en) * 2007-11-30 2019-11-29 Lithium Werks Tech Bv Battery cell design with asymmetrical terminals
    WO2010006313A1 (en) * 2008-07-10 2010-01-14 Robert Norman Calliham Method for producing copper-clad aluminum wire
    US8794152B2 (en) 2010-03-09 2014-08-05 Dyno Nobel Inc. Sealer elements, detonators containing the same, and methods of making
    CN102560579B (en) * 2011-12-10 2015-02-25 中国振华集团永光电子有限公司 Nickel plating method for silicon-aluminum alloy
    DE102012018159A1 (en) * 2012-09-14 2014-03-20 Feindrahtwerk Adolf Edelhoff Gmbh & Co. Kg Continuous coating of electrical conductors of aluminum or aluminum alloy present in wire- and band form, comprises subjecting aluminum conductor to degreasing, activation of surface in an alkaline bath or coating with desired coating layer
    USD779440S1 (en) 2014-08-07 2017-02-21 Henkel Ag & Co. Kgaa Overhead transmission conductor cable
    FR3057180B1 (en) 2016-12-12 2018-10-12 Constellium Issoire METHOD FOR IMPROVING THE WETTING OF A SURFACE OF A SOLID SUBSTRATE BY A LIQUID METAL
    EP3604624A4 (en) * 2017-03-31 2021-01-13 Furukawa Electric Co., Ltd. Plated wire rod material, method for producing same, and cable, electric wire, coil and spring member, each of which is formed using same

    Family Cites Families (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3867265A (en) * 1971-03-29 1975-02-18 Ericsson Telefon Ab L M Process for electroplating an aluminum wire
    US4126522A (en) * 1976-08-09 1978-11-21 Telefonaktiebolaget L M Ericsson Method of preparing aluminum wire for electrical conductors
    FR2526052B1 (en) * 1982-04-29 1985-10-11 Pechiney Aluminium METHOD AND DEVICE FOR COATING A LONG LENGTH OF METAL WITH A METAL LAYER
    DE3822503A1 (en) * 1988-07-03 1990-01-04 Lpw Galvanotechnik Gmbh System for electroplating treatment of continuous-treatment material
    FR2646174B1 (en) * 1989-04-25 1992-04-30 Pechiney Aluminium METHOD AND DEVICE FOR CONTINUOUS COATING OF ELECTRICALLY CONDUCTIVE SUBSTRATES BY HIGH SPEED ELECTROLYSIS
    FR2650696B1 (en) * 1989-08-04 1994-09-02 Axon Cable Sa CONTINUOUS COATING METHOD OF AN AT LEAST PARTIALLY ALUMINUM CONDUCTOR
    JPH10237674A (en) * 1997-02-20 1998-09-08 Totoku Electric Co Ltd Plated aluminum electric wire, insulating plated aluminum electric wire and their production

    Also Published As

    Publication number Publication date
    DE60018764D1 (en) 2005-04-21
    ES2238300T3 (en) 2005-09-01
    WO2001007685A2 (en) 2001-02-01
    ATE291111T1 (en) 2005-04-15
    WO2001007685A3 (en) 2001-10-25
    US6780303B2 (en) 2004-08-24
    DE60018764T2 (en) 2006-04-13
    FR2796656A1 (en) 2001-01-26
    FR2796656B1 (en) 2001-08-17
    EP1204787A2 (en) 2002-05-15
    US20020139685A1 (en) 2002-10-03

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