EP0693141B1 - Method of manufacture of a silvery aluminium conductor, device for carrying out said method and conductor so obtained - Google Patents

Abstract

Method of continuous manufacture of a conductor comprising an aluminium-based core (S) coated with at least one electrodeposited silver layer. The following operations are performed successively together with intermediate rincing stages (r): a) degreasing the conductor; b) subjecting the core to an etching bath; c) treating the conductor's surface by immersion in an adhesion bath; d) electrodepositing a first layer by immersion of the conductor in a first electrolytic bath; and e) electrodepositing a second silver layer by immersion of the conductor in a second electrolytic bath.

Description

The present invention relates to a process for manufacturing a silver aluminum conductor, the silver conductor obtained and a device for carrying out the process.

Patent FR-A-2650696 describes a process for manufacturing aluminum conductor wires coated with silver successively comprising degreasing, pickling, surface treatment for the attachment of metallic germs, the deposition of a first layer and then d 'a second layer of silver.

However, the yield and the kinetics of this process are not satisfactory. Furthermore, it does not produce silver conductors whose qualities (appearance, adhesion of the coating, solderability) are stable and this all the more so since the aluminum core has a small diameter. In addition, the manufacturing costs are still too high and the effluents from the process are toxic and difficult to treat.

• a) le dégraissage du conducteur par immersion pendant 3 à 100 s dans un bain maintenu à une température comprise entre 45°C et 75°C et comprenant :
  • de 1 à 100 g/l de NaOH
  • de 1 à 100 g/l de Na₂CO₃
  • de 0 à 50 g/l de Na₂SiO₃
  • de 1 à 100 g/l de NaC₆H₁₁O₇
• b) le décapage du conducteur par immersion pendant 2 à 90 s dans un bain à température ambiante comprenant de l'acide nitrique de concentration comprise entre 10 et 60 %
• c) le traitement de la surface du conducteur par immersion pendant 3 à 100 s dans un bain d'accrochage maintenu à une température comprise entre 30° et 70°C comprenant de 50 à 200 ml/l de Ni(BF₄)₂ et de 10 à 80 ml/l de Zn(BF₄)₂
• d)l'électrodéposition d'une première couche d'argent par immersion dans un premier bain à température ambiante comprenant de 50 à 200 g/l de KCN et de 1 à 19 g/l de AgCN avec une densité de courant comprise entre 0,1 et 10 A/dm² et avec des anodes en acier inoxydable
• e) l'électrodéposition d'une seconde couche d'argent par immersion dans un second bain comprenant :
  • de 80 à 300 g/l de KCN
  • de 45 à 180 g/l de AgCN
  • de 10 à 75 g/l de K₂CO₃
  • de 0 à 50 g/l de KOH

dont la température est comprise entre 30° et 60°C avec une densité de courant comprise entre 1 et 10 A/dm² et avec des anodes en argent.The aim of the present invention is to solve the above technical problems by means of a process characterized in that one carries out successively with intermediate rinses:

• a) degreasing the conductor by immersion for 3 to 100 s in a bath maintained at a temperature between 45 ° C and 75 ° C and comprising:
  • from 1 to 100 g / l NaOH
  • from 1 to 100 g / l Na ₂ CO ₃
  • from 0 to 50 g / l Na ₂ SiO ₃
  • from 1 to 100 g / l NaC ₆ H ₁₁ O ₇
• b) pickling of the conductor by immersion for 2 to 90 s in a bath at room temperature comprising nitric acid of concentration between 10 and 60%
• c) treating the surface of the conductor by immersion for 3 to 100 s in a bonding bath maintained at a temperature between 30 ° and 70 ° C comprising from 50 to 200 ml / l of Ni (BF ₄ ) ₂ and from 10 to 80 ml / l of Zn (BF ₄ ) ₂
• d) the electrodeposition of a first layer of silver by immersion in a first bath at room temperature comprising from 50 to 200 g / l of KCN and from 1 to 19 g / l of AgCN with a density of current between 0.1 and 10 A / dm ² and with stainless steel anodes
• e) the electrodeposition of a second layer of silver by immersion in a second bath comprising:
  • from 80 to 300 g / l of KCN
  • from 45 to 180 g / l of AgCN
  • from 10 to 75 g / l of K ₂ CO ₃
  • 0 to 50 g / l KOH

whose temperature is between 30 ° and 60 ° C with a current density between 1 and 10 A / dm ² and with silver anodes.

• 220 g/l de KCN
• 115 g/l de AgCN
• 50 g/l de K₂CO₃
• 30 g/l de KOH.

According to advantageous characteristics, the first layer of silver is obtained by immersion of 6 s with a current density of 3 A / dm ² in a bath comprising 80 g / l of KCN and 5 g / l of AgCN and the second layer silver is obtained by immersion of 40 s with a current density of 2.9 A / dm ² in a bath at 47 ° C comprising:

• 220 g / l KCN
• 115 g / l AgCN
• 50 g / l K ₂ CO ₃
• 30 g / l KOH.

• 15 g/l de NaOH
• 10 g/l de Na₂CO₃
• 5 g/l de Na₂SiO₃
• 15 g/l de NaC₆H₁₁O₇

et le décapage est effectué par une immersion de 6s dans un bain d'acide nitrique à 50 %.According to other characteristics, degreasing is carried out by immersion of 8.5 s in a bath at 60 ° C comprising:

• 15 g / l NaOH
• 10 g / l Na ₂ CO ₃
• 5 g / l Na ₂ SiO ₃
• 15 g / l NaC ₆ H ₁₁ O ₇

and pickling is carried out by immersion for 6 s in a bath of 50% nitric acid.

Furthermore, the attachment bath preferably comprises 95 ml / l of Ni (BF ₄ ) ₂ and 30 ml / l of Zn (BF ₄ ) ₂ and the surface treatment is carried out by immersion of 8.5 s in said bath maintained at 43 ° C.

The process of the invention makes it possible to multiply by five the manufacturing speed compared to previous processes for the same quality of electrolytic deposition.

The silver aluminum conductors obtained according to the processes of the prior art do not have good properties of Brazability due to the poor adhesion of the silver coating on the aluminum core. This drawback is all the more evident the smaller the diameter of the core.

Another object of the invention is therefore a conductor comprising an aluminum-based core coated with at least one layer of silver, characterized in that for a diameter of the core comprised between 0.08 and 0.5 mm and a total thickness of silver coating of between 1 and 2 μm the wetting angle is between 25 ° and 42 °.

The brazability of a conductive wire is expressed by its ability to be wetted by a weld in the molten state. In other words, the attachment of the filler metal in the molten state to the conductor is carried out correctly when the surface of the latter is sufficiently wetted by said liquefied filler metal. Wettability is linked to the so-called wetting angle formed by the respective surfaces of the conductor and the meniscus of the solder at their junction point. The smaller the wetting angle, the better the wettability of the conductor in the solder used.

The wetting angle is therefore a parameter reflecting the solderability of the conductor and a wetting angle of between 20 ° and 45 ° corresponds to very satisfactory solderability according to official standards (see French standardization A 89-400-Nov 91 published by the Welding Standardization Committee and AFNOR).

The conductor obtained by the process of the invention has, for a very small diameter core, silver coatings of small thickness, the mechanical properties of which and in particular the solderability are therefore entirely satisfactory.

Patent FR-A-2650696 also describes a device for the continuous coating of a conductor at least partially based on aluminum by electrodeposition of a metal layer.

However, this device is not suitable for implementing the method of the invention because it poses technical problems both electrical and mechanical in particular due to the small diameter of the aluminum core.

From an electrical point of view, during the electrolytic silver deposition step on a continuous wire of small diameter, the fall ohmic along the wire immersed in the electrolysis bath can become very important and create a cathode voltage gradient.

In general, the current density in the upstream section is higher than in the downstream section compared to the bath. Insofar as it is desired to accelerate the speed of electroplating, the average current density will have to be increased, which is likely to cause the evolution of hydrogen.

However, this gaseous release decreases the electrodeposition yield and weakens the adhesion of the coating to the wire forming the substrate and this all the more so when the diameter of the wire is smaller.

From a mechanical point of view, the thin aluminum wire constituting the core of the conductor has a low breaking strength. However, to ensure a good electrical connection of the wire, it is necessary to establish a sufficient mechanical tension, especially when the electrical contact is obtained by sliding the wire over the connector.

It has also been found that contact by immersion of the wire in a liquid creates additional ohmic drops which are particularly harmful.

The device according to the present invention aims to solve the above technical problems by providing an electrical contact made by means of a device for the continuous coating of a conductor whose core is at least partially based on aluminum by electrodeposition of at least one silver layer of the type comprising at least one current generator electrically connected on the one hand to the continuous conductor to be coated by means of at least one connector in contact with said conductor and on the other to at least one electrode forming an anode immersed in the electrodeposition bath, a chain of tanks intended to contain the various baths in which the conductor is successively immersed, a reel arranged at one end of the chain of tanks intended to cooperate with a unwinder arranged at the other end to move the conductor from one bath to the next with a determined running speed, character rised in that the connectors consist of two bars between which the conductor slides and whose relative position is adjustable so that a voltage can be obtained optimal mechanics for establishing an electrical contact determined as a function of the diameter of the conductor and of its running speed and in that the connectors are arranged along the conductor at predetermined intervals as a function of its electrical resistance so as to avoid any release of hydrogen from electroplating baths.

• la figure 1 représente une vue schématique du dispositif pour la mise en oeuvre du procédé de l'invention ;
• la figure 2 représente une vue en perspective du connecteur utilisé dans le dispositif de l'invention.

The invention will be better understood on reading the description and examples which follow, accompanied by the drawings in which:

• FIG. 1 represents a schematic view of the device for implementing the method of the invention;
• FIG. 2 represents a perspective view of the connector used in the device of the invention.

The device shown schematically in FIG. 1 comprises a chain of tanks (1-5, R) intended to contain the various baths (ae, r) and in which the aluminum core of the conductor S is successively immersed to treat its surface and make the silver coating.

• le bac 1 avec le bain de dégraissage (a) maintenu entre 45°C et 75°C et comprenant :
  • de 1 à 100 g/l de NaOH
  • 1 à 100 g/l de Na₂CO₃
  • 0 à 50 g/l de Na₂SiO₃
  • 1 à 100 g/l de NaC₆H₁₁O₇
• le bac 2 avec le bain de décapage (b) à température ambiante comprenant de l'acide nitrique dont la concentration est comprise entre 10 et 60 %
• le bac 3 avec le bain d'accrochage (c) maintenu entre 30°C et 70°C, comprenant :
  • de 50 à 200 ml/l de Ni(BF₄)₂ et de
  • 10 à 80 ml/l de Zn(BF₄)₂
• le bac 4 avec le bain (d) à température ambiante pour l'électrodéposition de la première couche d'argent (pré-argenture) comprenant :
  • de 50 à 200 g/l de KCN et de
  • 1 à 19 g/l de AgCN
• le bac 5 avec le bain (e) maintenu entre 30°C et 60°C pour l'électrodéposition de la seconde couche d'argent comprenant :
  • de 80 à 300 g/l de KCN
  • 45 à 180 g/l de AgCN
  • 10 à 75 g/l de K₂CO₃
  • 0 à 50 g/l de KOH.

Thus, there are successively from upstream to downstream with intermediate rinsing rinses (r):

• tank 1 with the degreasing bath (a) maintained between 45 ° C and 75 ° C and comprising:
  • from 1 to 100 g / l NaOH
  • 1 to 100 g / l Na ₂ CO ₃
  • 0 to 50 g / l Na ₂ SiO ₃
  • 1 to 100 g / l NaC ₆ H ₁₁ O ₇
• tank 2 with the pickling bath (b) at room temperature comprising nitric acid whose concentration is between 10 and 60%
• tank 3 with the attachment bath (c) maintained between 30 ° C and 70 ° C, comprising:
  • from 50 to 200 ml / l of Ni (BF ₄ ) ₂ and
  • 10 to 80 ml / l Zn (BF ₄ ) ₂
• tray 4 with the bath (d) at room temperature for the electrodeposition of the first layer of silver (pre-silvering) comprising:
  • from 50 to 200 g / l of KCN and
  • 1 to 19 g / l AgCN
• tray 5 with the bath (e) maintained between 30 ° C and 60 ° C for the electrodeposition of the second silver layer comprising:
  • from 80 to 300 g / l of KCN
  • 45 to 180 g / l AgCN
  • 10 to 75 g / l K ₂ CO ₃
  • 0 to 50 g / l KOH.

The device further comprises two current generators 14, 15. The generator 14 is associated with tray 4 with the bath (d) for the electrodeposition of the first layer of silver while the generator 15 is associated with tray 5 with the bath (e) for the electrodeposition of the second layer of silver. Of course, one could conceive of supplying the electrolysis circuits of the two tanks 4, 5 with the same generator, but it is in any case necessary to be able to adjust the current density to different values for the two tanks. Each generator 14, 15 is electrically connected on the one hand to the continuous conductor S to be coated by at least one connector and preferably two connectors 141, 142, 151, 152 disposed in contact with the conductor S respectively upstream and downstream of the tanks 4 , 5 relative to the direction of travel F and on the other hand to electrodes 140, 150, forming anodes, which are immersed in the electrodeposition baths (d) (e). The anode or anodes 140 corresponding to the bath (d) are preferably made of stainless steel while the anodes 150 corresponding to the bath (e) are made of silver. The distance separating the upstream connectors 141, 151 and downstream 142,152 is determined as a function of the electrical resistance of the conductor S so as to reduce the cathodic potential gradient and thus avoid a release of hydrogen from the baths (d) (e) .

Indeed, the potential from which the evolution of hydrogen begins is not far enough from that at which the silver plating takes place. This means that if, for whatever reason, the cathode voltage varies from one point to another on the wire to be coated, the electroplating would be disturbed by the evolution of hydrogen. However, the latter, even partial, not only reduces the yield of the electrodeposition but also harms the adhesion of the deposit silver on the substrate as well as its good crystallization. Knowing that the average electrical density is obtained by the ratio of the overall current intensity on the surface of the submerged wire, a cathode voltage gradient is equivalent to a lower electrical density than the average in the downstream part of the submerged wire then that it is more important in the upstream part where the release of hydrogen is therefore likely to occur.

Under these conditions, the gradient of cathode potential along the submerged wire is reduced by increasing the number of points of electrical contact with the generator and therefore the number of connectors.

Thus, by calculating the ohmic drop due to the electrical resistance of the wire and by estimating the limit value of tension not to be exceeded so that the evolution of hydrogen cannot occur, one can deduce from it the limit length L _M at the end of which an electrical contact point must be established. Experience has shown that the problem due to the evolution of hydrogen can be perfectly eliminated if the distance between two connectors is kept less than L _M.

The device further comprises a reel 7 arranged at the downstream end of the chain of tubs and intended to cooperate with a reel 6 arranged at the upstream end to move the conductor S from one bath to the next through the chain of bins.

Figure 2 shows a perspective view of the connector of the invention.

The upstream connectors 141, 151 are identical to the downstream connectors 142, 152. Each connector comprises two bars 142a, 142b made of brass, mounted in free rotation about their longitudinal axis, on an insulating support 142c (PVC). The two bars are adjacent and their longitudinal axes are parallel while their lateral faces are spaced by a distance corresponding substantially to the diameter of the conductive wire S.

In this way, a good compromise is achieved between the mechanical tension of the wire S and the stability of the electrical contact between the wire and the lateral faces of the bars without causing the wire to break.

In addition, an optimum mechanical tension of the conductive wire S can be obtained as a function of its diameter and of its running speed by adjusting the relative position of the bars. The conducting wire S travels in the direction F by sliding between the two bars 142a, 142b which are connected to the current generator 14,15.

Example I

An aluminum alloy core is used, the diameter of which is between 0.08 and 0.5 mm.

• a) Dégraissage pendant 8,5 s dans un bain à 60°C comprenant :
  • 15 g/l de NaOH
  • 10 g/l de Na₂CO₃
  • 5 g/l de Na₂SiO₃
  • 15 g/l de NaC₆H₁₁O₇
• b) Décapage pendant 6s dans l'acide nitrique 50 % à température ambiante.
• c) Pré-traitement pendant 8,5 s dans un bain à 43°C comprenant :
  • 95 ml/l de Ni(BF₄)₂
  • 30 ml/l de Zn(BF₄)₂
• d) Pré-argenture par immersion pendant 6 s avec une densité de courant de 3A/dm² dans un bain à température ambiante comprenant :
  • 80 g/l de KCN
  • 5 g/l de AgCN
  
  L'épaisseur de la première couche d'argent qui en résulte représente approximativement 13 % de l'épaisseur totale d'argent.
• e) Argenture par immersion pendant 40 s avec une densité de courant de 2,9 A/dm² dans un bain à 47°C comprenant :
  • 220 g/l de KCN
  • 115 g/l de AgCN
  • 50 g/l de K₂CO₃
  • 30 g/l de KOH.

The following operations are carried out successively with intermediate rinses:

• a) Degreasing for 8.5 s in a 60 ° C bath comprising:
  • 15 g / l NaOH
  • 10 g / l Na ₂ CO ₃
  • 5 g / l Na ₂ SiO ₃
  • 15 g / l NaC ₆ H ₁₁ O ₇
• b) Pickling for 6s in 50% nitric acid at room temperature.
• c) Pretreatment for 8.5 s in a 43 ° C bath comprising:
  • 95 ml / l Ni (BF ₄ ) ₂
  • 30 ml / l Zn (BF ₄ ) ₂
• d) Pre-silvering by immersion for 6 s with a current density of 3A / dm ² in a bath at room temperature comprising:
  • 80 g / l KCN
  • 5 g / l AgCN
  
  The thickness of the resulting first layer of silver is approximately 13% of the total thickness of silver.
• e) Silver plating by immersion for 40 s with a current density of 2.9 A / dm ² in a bath at 47 ° C comprising:
  • 220 g / l KCN
  • 115 g / l AgCN
  • 50 g / l K ₂ CO ₃
  • 30 g / l KOH.

Examples II to IX of implementation of the process are carried out in the same way as Example I.

The parameters of Examples I to IX are summarized in the following Table A:
Table B presents various samples of conductors manufactured according to the method of the invention with their wetting angle.

The silver conductors obtained according to the method of the invention are particularly suitable for applications as an electric cable in the aeronautical and space industries.

Claims (10)

1. A method of continuously manufacturing a conductor comprising a core (S) based on aluminum coated by electroplating at least one layer of silver thereon, the method being characterized in that the following steps are performed in succession with intermediate rinsing steps (r):

   a) the conductor is degreased by being immersed for 3 s to 100 s in a bath maintained at a temperature lying in the range 45°C to 75°C and comprising:

   1 gram per liter (g/l) to 100 g/l of NaOH

   1 g/l to loo g/l of Na₂CO₃

   0 to 50 g/l of Na₂SiO₃

   1 g/l to 100 g/l of NaC₆H₁₁O₇;

   b) removing oxide from the conductor by immersion for 2 s to 90 s in a bath at ambient temperature comprising nitric acid at a concentration lying in the range 10% to 60%;

   c) treating the surface of the conductor by immersing it for 3 s to 100 s in an adhesion bath maintained at a temperature lying in the range 30°C to 70°C and comprising 50 milliliters per liter (ml/l) to 200 ml/l of Ni(BF₄)₂ and 10 ml/l to 80 ml/l of Zn(BF₄)₂;

   d) electroplating a first layer of silver by immersion in a first bath at ambient temperature and comprising 50 g/l to 200 g/l of KCN and 1 g/l to 19 g/l of AgCN using a current density lying in the range 0.1 amps per square decimeter (A/dm²) to 10 A/dm² and anodes made of stainless steel; and

   e) electroplating a second layer of silver by immersion in a second bath comprising:

   80 g/l to 300 g/l of KCN

   45 g/l to 180 g/l of AgCN

   10 g/l to 75 g/l of K₂CO₃

   0 to 50 g/l of KOH

   at a temperature lying in the range 30°C to 60°C and using a current density lying in the range 1 A/dm² to 10 A/dm² and silver anodes.
2. The method according to claim 1, characterized in that the first layer of silver is obtained by immersion for 6 s at a current density of 3 A/dm² in a bath comprising 80 g/l of KCN and 5 g/l of AgCN.
3. The method according to one of claims 1 or 2, characterized in that the second layer of silver is obtained by immersion for 40 s at a current density of 2.9 A/dm² in a bath at 47°C and comprising:

   220 g/l of KCN

   115 g/l of AgCN

   50 g/l of K₂CO₃

   30 g/l of KOH.
4. The method according to one of the preceding claims, characterized in that degreasing is performed by immersion for 8.5 s in a bath at 60°C and comprising:

   15 g/l of NaOH

   10 g/l of Na₂CO₃

   5 g/l of Na₂SiO₃

   15 g/l of NaC₆H₁₁O₇.
5. The method according to one of the preceding claims, characterized in that oxide removal is performed by immersion for 6 s in a bath of nitric acid at 50%.
6. The method according to one of the preceding claims, characterized in that the adhesion bath comprises 95 ml/l of Ni(BF₄)₂ and 30 ml/l of Zn(BF₄)₂ and the surface treatment is performed by immersion for 8.5 s in a bath maintained at 43°C.
7. A conductor comprising an aluminum-based core S coated with at least one layer of silver, characterized in that for a core diameter lying in the range 0.08 mm to 0.5 mm and for a total thickness of silver coating lying in the range 1 µm to 2 µm, the wetting angle formed between the respective surfaces of the conductor and of the solder meniscus in the molten state at their connection point, determined according to French standard A 89-400-Nov 91 lies in the range 25° to 42°.
8. Apparatus for continuously coating a conductor whose core is based at least partially on aluminum, by electroplating at least one layer of silver, the apparatus being of the type comprising a line of tanks (1-5,R) for containing various baths (a-e,r) in which the conductor (S) is immersed in succession, at least one current generator (14, 15) electrically connected firstly to the continuous conductor (S) to be coated via at least one connector (141, 142, 151, 152) in contact with said conductor, and secondly to at least one anode-forming electrode (140, 150) immersed in the electroplating bath (d, e), a winder (7) disposed at one of the ends of the line of tanks to co-operate with a payout reel (6) disposed at the other end so as to displace the conductor from one bath to the next at a determined travel speed (F), the apparatus being characterized in that the connectors (141, 142, 151, 152) are constituted by pairs of rods (141a, 141b, ...) between which the conductor (S) slides and whose relative positions are adjustable so that it is possible to obtain optimum mechanical tension for establishing determined electrical contact as a function of the diameter of the conductor (S) and as a function of its travel speed (F), and in that the connectors are disposed along the conductor at intervals that are predetermined as a function of its electrical resistance so as to avoid any evolution of hydrogen in the electroplating baths (d, e).
9. Apparatus according to claim 8, characterized in that it includes two tanks (4, 5) respectively containing a pre-silvering bath (d) and a silver-plating bath (e).
10. Apparatus according to claim 9, characterized in that the anode (140) of the pre-silvering bath (d) is made of stainless steel and the anode (150) of the silver-plating bath (e) is made of silver.

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