EP0395542A1 - Verfahren und Vorrichtung zur kontinuierlichen elektrolytischen Beschichtung von elektrisch leitenden Gegenständen mit hoher Geschwindigkeit - Google Patents

Verfahren und Vorrichtung zur kontinuierlichen elektrolytischen Beschichtung von elektrisch leitenden Gegenständen mit hoher Geschwindigkeit Download PDF

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Publication number
EP0395542A1
EP0395542A1 EP90420200A EP90420200A EP0395542A1 EP 0395542 A1 EP0395542 A1 EP 0395542A1 EP 90420200 A EP90420200 A EP 90420200A EP 90420200 A EP90420200 A EP 90420200A EP 0395542 A1 EP0395542 A1 EP 0395542A1
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EP
European Patent Office
Prior art keywords
bath
nickel
baths
coating
compartments
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.)
Withdrawn
Application number
EP90420200A
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English (en)
French (fr)
Inventor
Gabriel Colombier
Jacques Lefèbvre
Jean Galand
Armand Golay
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rio Tinto France SAS
Original Assignee
Aluminium Pechiney SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Aluminium Pechiney SA filed Critical Aluminium Pechiney SA
Publication of EP0395542A1 publication Critical patent/EP0395542A1/de
Withdrawn legal-status Critical Current

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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires

Definitions

  • the present invention relates to a method and a device for continuously coating electrically conductive substrates by high speed electrolysis.
  • substrate is understood here to mean any product in the form of a round, bar, tube, flat or strip of great length and in particular of wire; said substrates being made of an electrically conductive material such as graphite, metals and more particularly aluminum and its alloys.
  • the coating it is any coating coating the substrate continuously even at low thickness and having a suitable adhesion to withstand handling and withstand stresses such as friction or clamping forces.
  • This process can be used to coat aluminum with brass, zinc, lead, nickel or copper by using coating baths of suitable composition.
  • the bath is composed of 300 g / l Sn (BF4) 2, 200 g / l HBF4, 25 g / l H3BO3, 30 g / l gelatin and 1 g / l ⁇ -naphthol. If we apply 1st process with a 3.2 mm diameter aluminum wire in a bath at 35 ° C where the wire is kept for 5 seconds under a current density of 100 to 120 A / dm2, a tin thickness of 5 ⁇ m with a passage speed of 36 m / min in baths 3 m long.
  • the liquid current outlet can consist, for example, of a bath containing 125 g / l NiCl2, 6 H2O; 12.5 g / l H3B03 and 6 cc / l HF, while the coating bath is composed of 300 g / l of Ni (NH2SO3) 2 (sulfamate), 30 g / l of NiCl2, 6 H2O and 30 g / l H3B03. These baths are used at respective temperatures of 40 and 65 ° C in order to achieve equivalent resistivities.
  • the cited documents all implement a method comprising an anodic etching step followed by a cathodic coating step.
  • the baths used to carry out these steps are always different from each other, which generally requires a step of intermediate rinsing to avoid bath mixtures.
  • the passages of the wires through the walls opposite the tanks containing the baths are not absolutely sealed and airlocks are generally provided to recover the entrained bath before rinsing so that it can be recycled.
  • these airlocks are generally empty rooms where the product is in contact with the ambient air.
  • the current densities which cross the product between the two tanks are those of the main current and that they can reach very high values of the order of 700 A / mm2 of section, this results under the action of the JOULE effect a very significant release of heat.
  • the maximum coating thicknesses that can be deposited are all the more limited as the wires are of small diameter.
  • these baths flow relative to the electrodes in the same direction or in opposite direction to that of the substrate in order to ensure better heat exchange.
  • a common bath which is divided into two portions, each of which can be heated or cooled at will and propelled towards the points of use then returned to a common collection place where it can also be subjected to heat treatments. or purification.
  • the substrate in order to optimize the process to allow, if necessary, to operate the activation and coating baths at different temperatures, can be passed between the two baths via a bath. stamp of the same composition as the other two.
  • This buffer bath also has the function of preventing substrates from suddenly changing from anodic polarity to cathodic polarity and therefore of having a gradual variation in the current from the activation bath to the coating bath so that the optimum electrical conditions of coating are carried out immediately upon entry of the substrate into the bath.
  • the single bath used is a mixture having the following composition: - nickel sulfamate which makes it possible to obtain deposits having the qualities required under high current density - nickel chloride which plays the role of protruding electrode, - nickel fluoborate which makes it possible to obtain, during activation, a very fine attack on the substrate and thus to create a large number of nickel germination sites and therefore a much finer deposit than that created on the germination sites obtained with a nickel chloride bath as described in the applicants' patents cited above, - fluoboric acid allowing the pH of the bath to be adjusted between 1.5 and 3, - optionally orthoboric acid, the function of which is to buffer the solution on surfaces subjected to electrochemical reactions.
  • the method according to the invention has the advantage in the case of substrates in the form of fine wires, by avoiding passage through the air, of being able to multiply the maximum admissible current intensities by a factor of 4.
  • an aluminum wire of the type 1310-50 according to the standards of the Aluminum Association with a diameter of 12/100 melted at an intensity of 8A according to the techniques of the prior art, which made it necessary to be limited to a scrolling speed of 32 m / min to obtain a nickel thickness of 1 ⁇ m at an intensity of 6 A.
  • the same wire can withstand an intensity of 24A without breaking, which makes it possible to nickel at speeds of the order of 130 m / min in an installation whose electrolytic part does not exceed 2.5 m long.
  • the diameter of the nickel nodules obtained is much smaller than in the prior art, hence a better coverage rate of the wire.
  • the contact resistance measured according to the cross-wire method gives values under 500 g of load between 0.2 and 0.7 m ⁇ whereas in US Pat. No. 4,741,811, these values were between 1.5 and 2 m ⁇ .
  • nickel lends itself well to the underlying deformation of the substrate. Indeed, the adhesion test consisting of winding the nickel-plated wire on its own diameter shows that the nickel film follows the deformation perfectly without detachment.
  • the invention also relates to a device for applying the method according to the invention which is characterized in that it is formed by a tank separated into two compartments by a partition made of electrically insulating material containing the baths of identical composition in one of which immerses at least one electrode connected to the positive pole of an at least partly continuous current source and in the other an electrode connected to the negative pole of the same source, said compartments and the partition being each provided with an inlet pipe and an outlet pipe each connected by a supply tank by means of a pump and heat exchanger and being traversed right through as well as the partition by at least one watertight opening through which the substrate to be coated passes.
  • the device differs from that of the prior art constituted by US 4492615 by the absence of a space between the "liquid outlet” or activation compartment and the coating compartment in order to avoid any contact of the substrate with air and ensure continuous cooling through the bath.
  • This tank is preferably of rectangular shape with a partition placed vertically which divides it into two compartments each having a length of approximately 1 m.
  • the walls of the tank parallel to this partition and said partition are pierced with several openings arranged so that a sheet of wires can be passed, for example at distances suitable for being in the best electrical treatment condition.
  • the dimensions of the openings are made so as to obtain a good seal with the tank and thus avoid any loss of bath.
  • the applicant also proposes a variant of the device, characterized in that it is formed by a tank separated into three compartments by two partitions of electrically insulating material containing baths of identical composition, one of the extreme compartments being equipped with at least one electrode immersed in the bath and connected to the positive pole of a current source at least partly continuous and the other of at least one electrode immersed in the bath and connected to the negative pole of the same current source; said compartments being each provided with a supply pipe and a bath outlet pipe each connected to a supply tank by means of a pump and heat exchanger and being traversed right through by at least one sealed opening through which the substrate to be coated passes.
  • This variant therefore consists in incorporating between the two compartments of the preceding device a buffer compartment containing the same bath as the other two.
  • All these compartments are connected to a common supply tank by two pipes in order to form circuits which can be partly independent and in which the bath can be conveyed by means of purification and heat exchange devices.
  • this length is between 50 and 200 mm.
  • FIG. 1 there is a tank 1 formed by an activation compartment 2 and a coating compartment 3 containing a bath 4 and into which a cathode 5 and an anode 6 respectively plunge.
  • This tank is crossed by a layer of five wires 7 passing through openings 8 in the direction of travel 9.
  • Each of the compartments is connected respectively by the pipes 10-11 and 12-13 to a supply tank not shown.
  • FIG. 2 the same elements are found as in FIG. 1, to which is added compartment 14 equipped with pipes 15 and 16.
  • the two compartments were separated by a simple partition.
  • Characteristics of the wires obtained - excellent adhesion of nickel, - contact resistance (m ⁇ ) under a load of 500 g: 0.19-0.25-0.28-0.24.
  • the invention finds its application in particular in the nickel plating of fine aluminum wires intended for the manufacture of flexible cables for aeronautics. These threads can be treated in layers and at high speed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP90420200A 1989-04-25 1990-04-23 Verfahren und Vorrichtung zur kontinuierlichen elektrolytischen Beschichtung von elektrisch leitenden Gegenständen mit hoher Geschwindigkeit Withdrawn EP0395542A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8906137 1989-04-25
FR8906137A FR2646174B1 (fr) 1989-04-25 1989-04-25 Procede et dispositif de revetement en continu de substrats conducteurs de l'electricite par electrolyse a grande vitesse

Publications (1)

Publication Number Publication Date
EP0395542A1 true EP0395542A1 (de) 1990-10-31

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Family Applications (1)

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EP90420200A Withdrawn EP0395542A1 (de) 1989-04-25 1990-04-23 Verfahren und Vorrichtung zur kontinuierlichen elektrolytischen Beschichtung von elektrisch leitenden Gegenständen mit hoher Geschwindigkeit

Country Status (4)

Country Link
US (1) US5015340A (de)
EP (1) EP0395542A1 (de)
JP (1) JPH03229889A (de)
FR (1) FR2646174B1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT399167B (de) * 1991-06-10 1995-03-27 Andritz Patentverwaltung Verfahren und vorrichtung zum elektrolytischen beizen von kontinuierlich durchlaufendem elektrisch leitendem gut
EP0801154A1 (de) * 1996-04-12 1997-10-15 Usinor Sacilor Verfahren zur Bearbeitung der aus Kupfer oder Kupferlegierung hergestellten Aussenoberfläche einer Strangguskokille welches aus einer Nickelplattierungstufe und einer Nickelentfernungstufe besteht
WO2001029289A1 (de) * 1999-10-20 2001-04-26 Atotech Deutschland Gmbh Verfahren und vorrichtung zum elektrolytischen behandeln von elektrisch gegeneinander isolierten, elektrisch leitfähigen strukturen auf oberflächen von elektrisch isolierendem folienmaterial sowie anwendungen des verfahrens
DE19951324A1 (de) * 1999-10-20 2001-05-03 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch leitfähigen Oberflächen von gegeneinander vereinzelten Platten- und Folienmaterialstücken sowie Anwendung des Verfahrens

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2671612B2 (ja) * 1991-01-30 1997-10-29 住友金属工業株式会社 アルミニウム帯への亜鉛系直接電気めっき方法
JP2725477B2 (ja) * 1991-02-07 1998-03-11 住友金属工業株式会社 アルミニウム帯への亜鉛系電気めっき方法
DE69226974T2 (de) * 1991-02-18 1999-05-12 Sumitomo Metal Ind Verwendung von plattiertem Aluminiumblech mit verbesserter Punktschweissbarkeit
FR2796656B1 (fr) * 1999-07-22 2001-08-17 Pechiney Aluminium Procede de nickelage en continu d'un conducteur en aluminium et dispositif correspondant
FR2881146B1 (fr) * 2005-01-27 2007-10-19 Snecma Moteurs Sa Procede de reparation d'une surface de frottement d'une aube a calage variable de turbomachine
WO2006086274A2 (en) * 2005-02-08 2006-08-17 Dyno Nobel Inc. Delay units and methods of making the same
EP1870496A1 (de) * 2006-06-20 2007-12-26 NV Bekaert SA Vorrichtung und Verfahren zum Galvanisieren eines Substrat im Durchlaufverfahren
WO2010006313A1 (en) * 2008-07-10 2010-01-14 Robert Norman Calliham Method for producing copper-clad aluminum wire
AU2011224469B2 (en) 2010-03-09 2014-08-07 Dyno Nobel Inc. Sealer elements, detonators containing the same, and methods of making
TWI414641B (zh) * 2011-06-20 2013-11-11 Intech Electronics Co Ltd 軟性銅箔基板電鍍裝置
US9393759B2 (en) * 2013-10-24 2016-07-19 General Electric Company Metal laminate structures with systems and methods for treating
DE102013022030B4 (de) * 2013-12-19 2017-10-05 Schlenk Metallfolien Gmbh & Co. Kg Verfahren zur elektrolytischen Oberflächenmodifizierung von flächigen Metallwerkstücken in sulfatometallhaltigen Kupfersulfat-Behandlungsflüssigkeiten, flächiges Metallwerkstück und dessen Verwendung
CA2957528A1 (en) * 2014-08-07 2016-02-11 Henkel Ag & Co. Kgaa Continuous coating apparatus for electroceramic coating of cable
DE102015121349A1 (de) * 2015-12-08 2017-06-08 Staku Anlagenbau Gmbh Vorrichtung zur Oberflächenbehandlung eines Endlosmaterials sowie deren Verwendung
JP6452912B1 (ja) * 2017-03-31 2019-01-16 古河電気工業株式会社 めっき線棒材及びその製造方法、並びにこれを用いて形成されたケーブル、電線、コイル及びばね部材

Citations (3)

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Publication number Priority date Publication date Assignee Title
US1645927A (en) * 1926-03-05 1927-10-18 Metals Prot Corp Chromium plating
US2513859A (en) * 1945-09-12 1950-07-04 Crown Cork & Seal Co Method of electroplating of tin on ferrous strip
FR2192873A1 (de) * 1972-07-13 1974-02-15 Kalle Ag

Family Cites Families (5)

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US2370973A (en) * 1941-11-22 1945-03-06 William C Lang Method and apparatus for producing coated wire
US3007854A (en) * 1957-06-14 1961-11-07 Nat Steel Corp Method of electrodepositing aluminum on a metal base
JPS5485129A (en) * 1977-12-20 1979-07-06 Furukawa Electric Co Ltd:The Surface reforming method for metal filament body
JPS5615794A (en) * 1979-07-20 1981-02-16 Hitachi Ltd Drum type full automatic washing machine
JPS5744760A (en) * 1980-08-27 1982-03-13 Mazda Motor Corp Exhaust gas recirculation device of engine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1645927A (en) * 1926-03-05 1927-10-18 Metals Prot Corp Chromium plating
US2513859A (en) * 1945-09-12 1950-07-04 Crown Cork & Seal Co Method of electroplating of tin on ferrous strip
FR2192873A1 (de) * 1972-07-13 1974-02-15 Kalle Ag

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 3, no. 104 (C-57), 4 septembre 1979, page 147 C 57; & JP-A-54 85 129 (FURUKAWA DENKI KOGYO K.K.) 07-06-1979 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT399167B (de) * 1991-06-10 1995-03-27 Andritz Patentverwaltung Verfahren und vorrichtung zum elektrolytischen beizen von kontinuierlich durchlaufendem elektrisch leitendem gut
EP0801154A1 (de) * 1996-04-12 1997-10-15 Usinor Sacilor Verfahren zur Bearbeitung der aus Kupfer oder Kupferlegierung hergestellten Aussenoberfläche einer Strangguskokille welches aus einer Nickelplattierungstufe und einer Nickelentfernungstufe besteht
FR2747400A1 (fr) * 1996-04-12 1997-10-17 Usinor Sacilor Procede de conditionnement de la surface externe en cuivre ou alliage de cuivre d'un element d'une lingotiere de coulee continue des metaux, du type comportant une etape de nickelage et une etape de denickelage
US5788824A (en) * 1996-04-12 1998-08-04 Usinor Sacilor (Societe Anonyme) Process for conditioning the copper or copper-alloy external surface of an element of a mold for the continuous casting of metals, of the type including a nickel plating step and a nickel removal step
WO2001029289A1 (de) * 1999-10-20 2001-04-26 Atotech Deutschland Gmbh Verfahren und vorrichtung zum elektrolytischen behandeln von elektrisch gegeneinander isolierten, elektrisch leitfähigen strukturen auf oberflächen von elektrisch isolierendem folienmaterial sowie anwendungen des verfahrens
DE19951324A1 (de) * 1999-10-20 2001-05-03 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch leitfähigen Oberflächen von gegeneinander vereinzelten Platten- und Folienmaterialstücken sowie Anwendung des Verfahrens
DE19951325A1 (de) * 1999-10-20 2001-05-10 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch gegeneinander isolierten, elektrisch leitenden Strukturen auf Oberflächen von elektrisch isolierendem Folienmaterial sowie Anwendungen des Verfahrens
DE19951325C2 (de) * 1999-10-20 2003-06-26 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch gegeneinander isolierten, elektrisch leitfähigen Strukturen auf Oberflächen von elektrisch isolierendem Folienmaterial sowie Anwendungen des Verfahrens
DE19951324C2 (de) * 1999-10-20 2003-07-17 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch leitfähigen Oberflächen von gegeneinander vereinzelten Platten- und Folienmaterialstücken sowie Anwendung des Verfahrens
US6939455B1 (en) 1999-10-20 2005-09-06 Atotech Deutschland Gmbh Method and device for the electrolytic treatment of electrically conducting surfaces separated plates and film material pieces in addition to uses of said method
US6979391B1 (en) 1999-10-20 2005-12-27 Atotech Deutschland Gmbh Method and device for the electrolytic treatment of electrically conducting structures which are insulated from each other and positioned on the surface of electrically insulating film materials and use of the method

Also Published As

Publication number Publication date
FR2646174A1 (fr) 1990-10-26
US5015340A (en) 1991-05-14
JPH03229889A (ja) 1991-10-11
FR2646174B1 (fr) 1992-04-30

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