Classifications

• • 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 nickel-plated aluminum or aluminum alloy. It relates more specifically to the nickel plating processes of aluminum or aluminum alloy conductors, as well as the devices making it possible to implement them.
• the invention also relates to electric wires and cables with an aluminum or aluminum alloy core comprising at least one nickel-plated conductor.
• the word “aluminum” is used in the broad sense of aluminum and its alloys. This will be the case throughout the text.
• the word “conductor” here designates an electrically conductive body, of elongated shape, the length of which is large compared to its transverse dimensions, such as a wire, a strip, a bar or a tube.
• Aluminum electrical conductors are widely used in the transport of electrical energy. These conductors are most often in the form of bars, flats, wires or cables.
• Aluminum core electric wires and cables which may include a coating of insulating material, are generally obtained from a continuously rolled "machine" wire, which is then drawn to the desired diameter. Unit wires or strands 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 surface of the conductor, in addition to a brushing any parts of the conductor intended for establishing an electrical contact.
• the conductor circulates in at least one electrolytic nickel plating tank.
• This tank is provided with a nickel electrode which acts as an anode and which, for this purpose, is connected to the positive terminal of an electrical supply.
• the conductor to be treated acts as a blank cathode and, for this, is electrically connected to the negative terminal of this supply.
• the applicant has proposed a process and a device for electrolytic nickel-plating on the passing of an aluminum conductor making it possible to reach running speeds of 300 m /minute.
• the electrolytic current is transmitted to the conductor by a so-called liquid current socket, that is to say without mechanical contact, which avoids the drawbacks of mechanical current sockets, in particular electric arcs.
• the conductor to be coated circulates in a first tank provided with a negatively polarized electrode, then in a second tank provided with a positively polarized electrode; an electric current then flows through the conductor as it passes through the tanks.
• the first tank contains an aqueous ionic solution capable of transmitting the electric current from the electrode to said conductor.
• the second tank contains the nickel plating bath.
• the nickel plating of the conductors however constitutes an additional operation, the aim of which is both to minimize the cost and to maximize the productivity.
• satisfactory costs and productivity are obtained by carrying out nickel plating of the elementary wires at high speed.
• certain markets, such as that of aeronautics wish have nickel-plated aluminum wires with a diameter between 0.1 and 0.5 mm, and cables made up of such wires.
• the Applicant has therefore sought means to obtain nickel-plated aluminum conductors with a diameter of less than 1 mm which avoid the drawbacks of the prior art while maintaining acceptable profitability and productivity, with the lowest possible investment costs. .
• the subject of the invention is a process for continuous nickel plating (or "passing") of an aluminum conductor.
• the process for nickel-plating an aluminum conductor comprises a pre-treatment step P capable of promoting the adhesion of the nickel layer and a step of electrolytic nickel-plating N, and is characterized in what said preprocessing P is also able to confer on said driver sufficient contact properties to allow mechanical electrical contact and in that the nickel-plating current is transmitted to said conductor via a mechanical electrical contact on the part of the conductor resulting from the pretreatment step.
• the electrolytic nickel-plating step N makes it possible to form, by electrodeposition, a uniform nickel layer on said conductor.
• the subject of the invention is also a device for continuous nickel plating (or "in the process") of an aluminum conductor.
• the invention relates mainly to aluminum conductors intended for electrical applications, it also applies to aluminum conductors intended for non-electrical uses, 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 aluminum wires, strips or tubes, intended to be brazed.
• the invention relates to the use of the method or the device according to the invention for nickel plating an aluminum product so as to allow it to be brazed.
• the nickel layer with a thickness typically of the order of 1 ⁇ m, can allow the formation of a satisfactory brazed joint without having recourse to a specific brazing flux.
• the invention also relates to a method of manufacture of an assembled product, characterized in that it comprises the use of a nickel-plated aluminum product according to the invention. Said manufacturing process optionally includes a brazing operation of said nickel-plated aluminum product.
• Figure 1 schematically illustrates a first preferred embodiment of the nickel plating process according to the invention.
• the pre-treatment step P is carried out electrolytically and is carried out with mechanical contact means common to those of the nickel-plating step N.
• FIG. 2 schematically illustrates a second preferred embodiment of the invention according to which the pretreatment step P is configured in a liquid current socket.
• FIG. 3 illustrates a mechanical contact means according to the invention comprising one or more wheels.
• FIG. 4 illustrates another contact means according to the invention comprising three wheels.
• Said mechanical contact (7) preferably comprises at least one mechanical contact means by bearing (70) which typically comprises at least one grooved wheel or a sheave.
• the contact properties are sufficient when it is possible to pass the full intensity of the nickel-plating current through mechanical contact without damaging the conductor.
• the mechanical contact must make it possible to pass a nickel-plating current of the order of 5 A for a wire of 0.15 mm in diameter when the running speed is 50 m / minute.
• Mechanical electrical contact can be achieved, for example, using rollers, rollers, rubbing contacts or brushes.
• the composition of the nickel-plating bath is advantageously as follows: 300 ⁇ 30 g / 1 of Ni (NH 2 SO 3 ) 2 (sulfamate), 30 ⁇ 5 g / 1 of NiCl 2 , 6H 2 O, 30 ⁇ 5 g / 1 of H 3 BO 3 .
• the device for nickel-plating at least one aluminum conductor (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 (Vi) between the anode 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 pretreatment tank (40, 41, 42) comprising a tank (17, 43, 46 ) capable of containing 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 each, said conductor (1) resulting from the pre-stroke step ement P.
• a nickel-plating tank comprising a tank (2) capable of
• the pre-treatment stage is chosen to give the conductor sufficient contact properties to allow mechanical electrical contact on the latter.
• the pre-treatment stage P is preferably carried out electrolytically, which makes it easier to control the pre-treatment as a function of the operating conditions of the treatment line.
• the pre-treatment tank (40) is provided with at least one electrode (15) and the device comprises an electrical supply (8) intended for the pre-treatment.
• the electric voltage V 2 delivered by this supply can be alternating, continuous or pulsed, or a combination of these.
• the socket on the conductor is produced by a mechanical contact placed downstream of the pre-treatment tank (40). This mechanical 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 causing an overload of the mechanical contact means (1, 13, 14) because the intensity of the pre-treatment current (I) is generally much lower than the intensity of the nickel-plating current ( ⁇ ⁇ ).
• the pretreatment step P comprises activation A in a strongly acidic or alkaline bath which allows, in particular, rapid dissolution of the surface oxides.
• Activation is carried out in an activation tank (40, 42) comprising a tank (17, 46) capable of containing the activation bath (16, 47), in which the conductor (1) runs.
• the activation tank (40, 42) also comprises at least one electrode (15, 48) and the device comprises an electrical supply (8) intended for this activation.
• the electric voltage V 2 delivered by this supply can be alternating, continuous or pulsed, or a combination of these.
• the pre-treatment 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-nickel-plating step PN for coating the aluminum conductor (1) of a "primary" nickel deposit.
• the nickel-plating current (I I ) is then transmitted to said conductor by means of mechanical contact means (7, 13, 14) on the part (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, the equivalent thickness of which is significantly less than the target thickness of the final layer. It has been found preferable to aim for an equivalent thickness which is, on average, less than about 0.1 of the final thickness. Typically, the thickness of the final layer being approximately 1 ⁇ m, we will aim for an equivalent thickness of the pre-nickel plating layer of less than approximately 0.1 ⁇ m.
• the pre-nickel plating is carried out in a tank (40, 41) comprising a tank (17, 43) capable of containing the pre-nickel plating bath (16, 44), in which the conductor (1) runs.
• the pre-nickel plating bath (16, 44) contains a nickel salt so as to coat the aluminum conductor with a primary nickel deposit when the conductor passes through this bath.
• the pre-nickel plating step is preferably carried out electrolytically, which makes it easier to control the thickness of the layer as a function of 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 an electrical supply (8) intended for pre-nickel plating.
• the electric voltage V 2 delivered by this supply can be alternating, continuous or pulsed, or a combination of these.
• the pre-nickel plating step PN is, in whole or in part, combined with the activation step A, which makes it possible to considerably simplify the device.
• the pre-nickel plating and activation steps are carried out in conjunction with a liquid outlet.
• FIG. 2 illustrates a device which makes it possible to implement this variant of the invention.
• This device comprises an electrolytic activation tank (42) and an electrolytic pre-nickel plating tank (41), preferably close to each other and possibly adjacent, a first electrical supply (8) common to these two tanks , an electrolytic nickel-plating tank (30), a second electrical supply (5) and mechanical contact means (7, 13, 14) on the part (6) of the conductor (1) situated between the pre-nickel-plating tank ( 41) and the nickel-plating tank (30).
• the first electrical supply (8) is preferably direct current, optionally modulated or pulsed; the positive terminal is connected to at least one electrode (45) submerged, in whole or in part, in the pre-nickel plating bath (44) and the negative terminal is connected to at least one submerged electrode (48), in whole or in part , in the activation bath (47).
• the current flows through the conductor (1) by a liquid current pickup effect.
• the same power supply (8) is used for activation and pre-nickel plating.
• the second power supply (5) is direct current, possibly modulated or pulsed; the positive terminal is connected to at least one electrode (3) containing nickel immersed, in whole or in part, in the nickel-plating bath (4) and the negative terminal is connected to the part (6) of the conductor (1) located between the pre-nickel plating tank (41) and the nickel plating tank (30) by means of mechanical contact means (7, 13, 14).
• the PN 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. 1
• the pretreatment step operates a dual function of activation and pre-nickel plating.
• the bath activation / pre-nickel plating (16) is then able to operate the two treatments, for example by having a mixed composition which allows both satisfactory activation and sufficient pre-nickel plating.
• the Applicant has found that it is possible to effectively perform these two functions using a single bath.
• the first electrical supply (8) is 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 an electrode (15) submerged, in whole or in part, in said activation / pre-nickel plating bath (16).
• the second power supply (5) is direct current, possibly modulated or pulsed; the positive terminal is connected to an electrode (3) containing nickel immersed, in whole or in part, in the nickel-plating bath (4) and the negative terminal is connected to the part (6) of the conductor (1) located between the tank activation / pre-nickel plating (40) and the nickel plating tank (30) by means of mechanical contact means (7, 13, 14), preferably common to those of the first supply (8).
• the mechanical contact is immersed in a liquid (14) such as water or a neutral solution, so as to avoid fusion of the conductor at the mechanical contact.
• a liquid (14) such as water or a neutral solution
• the device may include an intermediate tank (13), generally of small dimensions, containing the liquid (14) and the mechanical contact (7).
• the liquid (14) can optionally be cooled.
• the mechanical contact can comprise several parallel wheels rotating around a common axis (as illustrated in FIG. 3).
• the mechanical rolling contact means (70) illustrated in FIG. 3, which corresponds to a preferred embodiment of the invention, comprises one or more wheels (71) rotating around an axle (73) whose axis central (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 in particular makes it possible to avoid variations in the position thereof.
• the electric current flows from the axle (73) to the conductor (6) via the wheel (71).
• the axle-wheel assembly (s) (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 improve the electrical contact. This latter variant also avoids the need for a ball bearing.
• the wheels (71) were made of 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 ensure satisfactory electrical contact on the (or each) driver (6).
• each conductor comprises such means when several conductors are treated simultaneously.
• At least one of said mechanical contact means (7, 13, 14) comprises such contact means.
• Each wheel rotates around its own axis (731, 732, 733) and exerts a force (FI, 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 various baths is generally chosen so that the ionic conductivity and the reactivity of the baths are sufficient. Typically, the temperature of the baths is between 45 and 60 ° C.
• the method according to the invention may comprise additional steps, such as shaving and / or possible degreasing of the conductor in the raw state (10) before the activation and / or pre-nickel-plating step.
• the conductor is typically made of an AA 1370 alloy, AA 1110 or AA 6101 according to the nomenclature of the Aluminum Association.
• the invention also relates to cables comprising at least one elementary nickel-plated wire according to the invention.
• the process for manufacturing an aluminum electric cable can comprise a nickel-plating operation according to the invention of at least one of the elementary wires.
• the device comprises means for simultaneously scrolling two or more conductors in at least one of said treatment tanks.
• plies of conductors from a series of separate unwinders circulate in parallel in said baths and, after treatment, are wound on a series of separate winders.
• the contact means (7, 13, 14) on the part of the conductors (6) resulting from the pre-treatment step may be, in whole or in part, common to these; for example, said means can comprise a strip of carbon material which can be brought into contact with all the conductors of a sheet.
• the conductor (s) can pass horizontally, vertically or at a certain angle with respect to the horizontal.
• Tests were carried out on the wires with a diameter of 0.20 mm, 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 supply configured as a liquid current socket (as described in application FR 2 646 174); screens were interposed between the nickel electrodes and the wire (as described in application FR 2 609 292).
• the activation and nickel-plating baths had the same composition, namely: 125 ⁇ 15 g / 1 of nickel chloride (NiCl 2 , 6 H 2 O), 12.5 ⁇ 2 g / 1 of orthoboric acid and 6 ⁇ 2 ml / 1 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.
• the activation and pre-nickel plating baths had the following composition: 125 ⁇ 15 g / 1 of nickel chloride (NiCl 2 , 6 HO), 12.5 ⁇ 2 g / 1 of orthoboric acid and 6 ⁇ 2 ml / 1 hydrofluoric acid.
• the nickel-plating bath had the following composition: 300 ⁇ 30 g / 1 of Ni (NH 2 SO 3 ) 2 (sulfamate), 30 ⁇ 5 g / 1 of NiCl 2 , 6H 2 O, 30 ⁇ 5 g / 1 of H 3 BO 3 .
• Table I below groups together the main treatment parameters used in these tests and certain characteristics of the treated yarns.
• the contact resistance was measured using a so-called "cross wire” method, at an intensity of 0.1 mA and with a pressing force of 0.2 N.
• the adhesion of the layer nickel on the wire was measured by winding the wire on its own diameter; she is considered as excellent if the nickel layer uniformly follows the deformation of the wire without detaching from the surface.
• the electrolytic pre-nickel plating layer was in the form of nodules which did not cover the entire surface of the conductor.
• the Applicant has observed that it was not necessary for said primary nickel deposit (or "pre-nickel plating layer") to be uniform or for it to completely cover the surface of the conductor; it has proved sufficient to achieve an equivalent recovery rate corresponding to approximately 0.1 of the final thickness of the nickel layer.
• the Applicant has hypothesized that such a recovery rate confers a quality of electrical contact sufficient to allow the transmission by mechanical contact of high nickel plating current intensities without degrading the surface of the conductor and ensures a high adhesion of the layer of final nickel.
• the term "primary nickel deposition” means a layer of nickel whose thickness is typically, on average, about 0.1 ⁇ m.
• the nickel layer obtained according to the invention therefore has great adhesion and low electrical contact resistance.
• the invention makes it possible to nickel effectively, and with great productivity, wires of different diameters.
• it allows easy adjustment of treatment parameters to production conditions, thanks to the decoupling between the pre-treatment and nickel-plating stages. It is in particular possible to independently adjust 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 nickel-plating stage.
• the invention makes it possible to benefit from the advantages of mechanical sockets, in particular the possibility of passing high intensities, and of avoiding the disadvantages thereof, in particular the propensity to form electric arcs which can damage the surface of the conductor.
• the low intensity of the pretreatment current required according to the invention leads to a significantly slower aluminum enrichment of the pretreatment bath, which makes it possible to considerably reduce the frequency of replacement of this bath.
• the low intensity of the pre-treatment current also limits the dissolution of the metal and, consequently, the formation of roughness 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 a defined roughness in order to obtain optimal mechanical properties.

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• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Electroplating Methods And Accessories (AREA)
• Conductive Materials (AREA)
• Superconductors And Manufacturing Methods Therefor (AREA)
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• 1999
  • 1999-07-22 FR FR9909690A patent/FR2796656B1/fr not_active Expired - Fee Related
• 2000
  • 2000-07-18 ES ES00953251T patent/ES2238300T3/es not_active Expired - Lifetime
  • 2000-07-18 WO PCT/FR2000/002061 patent/WO2001007685A2/fr not_active Ceased
  • 2000-07-18 DE DE60018764T patent/DE60018764T2/de not_active Expired - Lifetime
  • 2000-07-18 AT AT00953251T patent/ATE291111T1/de not_active IP Right Cessation
  • 2000-07-18 EP EP00953251A patent/EP1204787B1/de not_active Expired - Lifetime
• 2002
  • 2002-01-18 US US10/050,896 patent/US6780303B2/en not_active Expired - Lifetime

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