EP3112502A1 - Verfahren zum plattieren von metallischen drähten oder bändern und produkt hergestellt mittels dieses verfahrens - Google Patents

Verfahren zum plattieren von metallischen drähten oder bändern und produkt hergestellt mittels dieses verfahrens Download PDF

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Publication number
EP3112502A1
EP3112502A1 EP16176105.1A EP16176105A EP3112502A1 EP 3112502 A1 EP3112502 A1 EP 3112502A1 EP 16176105 A EP16176105 A EP 16176105A EP 3112502 A1 EP3112502 A1 EP 3112502A1
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EP
European Patent Office
Prior art keywords
plating
chromium
metallic product
electrolytic
nickel
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Granted
Application number
EP16176105.1A
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English (en)
French (fr)
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EP3112502B1 (de
Inventor
Evio VAZZOLER
Luca CIVATI
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Vazzoler Evio
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Vazzoler Evio
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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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium

Definitions

  • the present invention refers to a method for obtaining a laminated and/or drawn metallic product of wire or tape type, in coils or reels, which is plated by electroplating with layers of nickel and chromium.
  • the product obtained through the method hereof is, moreover, characterized by a low release of nickel.
  • the invention finds its application in the industrial production of objects having a high aesthetic quality, obtained from the processing of wire or metallic tape.
  • the nickel-plating process is used both as coating and as primer base for subsequent treatments, as it is enduring, ductile, fast clinging and also of attractive appearance, a characteristic that makes nickel-plating preferable over zinc-coating, being the latter less appealing in appearance.
  • the chromium-plating process makes it possible to obtain an especially hard surface layer of bright glossy white color, which is thus greatly appreciated in products or accessories requiring such characteristics of aesthetic finish.
  • the prior art galvanic treatments require the use of a tank, usually containing an aqueous solution of the metal salt to be deposited, in which are immersed two electrodes, a cathode and an anode respectively, both connected to an electrical circuit.
  • the cathode consists of the object to be plated, while the anode can consist of the metal that must be deposited, or it can be another inert metal or graphite.
  • the known treatments differ principally on the basis of the type and form of the pieces being processed, as they can be pieces that can be processed entirely in a bath in which they remain for a certain time or pieces that are processed only partially or at different times.
  • the conventional treatments, for pieces that are processed entire and simultaneously, include processing the whole piece through a static permanence of the same pieces in the different stations or tanks of the production process.
  • the phases that follow the cleaning and preparation of the piece and that make it possible to achieve the plating consist, therefore, of immersing the piece in the respective bath, so that an electric current can be applied that is functional to the type of plating metal, which progressively builds up on the piece being plated.
  • the single pieces such as for example car or motorcycle items, in fact remain substantially motionless inside the same tank until the completion of the galvanic process, while in the case of wires or tapes the treatment is applied in a continuous mode, depending on the tanks being crossed and on the time during which each portion remains immersed in the respective tank while moving through it.
  • GB 938192 Manson and others
  • a galvanic multilayer plating for metallic wire, bars or tape achieved in continuous cycle, in which the product being processed is given a helical shape and placed in rotation, so that it can pass through a bath of a first plating metal, and subsequently undergoes cold processing and is finally subjected to a further bath, in a second plating metal, to obtain a desired thickness.
  • an improved surface that is resistant and free of pores or flaws is achieved, in which the metals used in the two plating cycles can be the same or different, for example nickel, tin, copper, aluminum, steel or alloys.
  • the nickel-plating treatment itself has recently received particular attention from doctors, manufacturers and Congress, due to the proven high allergenic and irritating properties of nickel, which is thus classified as a harmful, polluting and also carcinogenic substance.
  • European Directive 94/27/CE has also introduced the ban on the sale of products designed to come in direct and prolonged contact with the skin of the wearer if they release a quantity of nickel (Ni) higher than a minimum established value, measured according to a specific measuring protocol.
  • nickel-free This characteristic is conventionally referred to as “nickel-free”, even though it does not necessarily imply the total absence of nickel in the component but only in the external coating, as is specifically the case foreseen in the present invention. Alternatively, it is possible to define such products as being “low nickel release products”.
  • the metallic articles used in the paper-transformation field may be prudentially likened to the products of the related field of costume jewelry, for the purposes of verifying the release of nickel according to norms.
  • a possible improvement may essentially result, at the technological level, from two solutions: the elimination and the substitution of the nickel or, alternatively, from a further protective coating applied on the nickel.
  • the first solution that is, the elimination and replacement of the nickel with other processes, used in the clothing field, for example in belt buckles, or also in costume jewelry, involves resorting to treatments that deposit substitute materials having an overall higher cost or being more intricate to make, which prevents their use in the paper-transformation field, where moderate costs and high volumes of production are required.
  • chromium plating is a more complex galvanic process to manage compared to nickel-plating, due to the process parameters and conditions required to achieve a satisfactory result, which makes it very problematic in the case of continuous processing of wires or tapes, so that it is not yet applied in known methods.
  • methods are known in which, after having performed nickel-plating in a continuous process and at a substantially constant speed, chromium plating is performed in a so-called "batch" or discontinuous process.
  • a problem found at the experimental level and not solved in the prior art is due to the quality of the surface finish, which proved to be strongly influenced by the vibrations, although very slight, suffered by one or more wires inside the relative electrolytic chromium-plating tank, tested with a bath of hexavalent chromium.
  • the main objective of the present invention is to overcome the shortcomings of the prior art by providing a method for metallic wire or tape that makes it possible to obtain in a continuous cycle a product coated with a nickel-plating layer and with a chromium-plating layer, with a finish that at least minimizes the so-called "scorchings".
  • one purpose of the present invention is to devise a method of galvanic treatment that is suitable for plating wires or metallic tapes in a continuous mode while avoiding finishing flaws.
  • a further objective of the present invention consists of providing a method of galvanic treatment, used in a continuous mode at a constant speed, that makes it possible to obtain a wire or a tape coated with nickel and chromium, by treating in a continuous mode a whole wire or tape wound in coils or reels.
  • a not secondary purpose is to realize a product for the paper transformation field that makes it possible to obtain a wire or tape coated with nickel and chromium and having a low nickel release.
  • a decoiler 20 holds a coil 12, from which is unwound a wire 10 that, in a continuous treatment line, runs through the following stations at a substantially constant speed and in series:
  • the wire 10 after having undergone the above treatments, is a treated wire 30 that is wound in a second coil 32 housed in a coiler 40 that also turns at a substantially constant speed.
  • the set of phases preceding the electrolytic nickel-plating E is referred to as the preparation phase, for example comprising phases A, B, C and D.
  • the intervals relating to the permanence times are, as described, obtained by adjusting the substantially constant wire feeding speed comprised between 10 and 100 meters a minute.
  • the tape is unwound from a reel housed in a relative decoiler, in order to be treated and turned into a treated tape that is rewound in a second reel housed in a relative rewinder, in a continuous-cycle mode and at a substantially constant speed.
  • the treated wire 30 or the treated tape is thus obtained from a drawn and/or rolled metallic product in reels and coils, obtained from a base material of ferrous type, that is nickel-plated and also coated in a continuous cycle, at a substantially constant speed, with a superficial metallic layer without nickel so as to substantially limit the release of nickel from the substrate.
  • the portion of wire or tape that is temporarily immersed in the electrolytic plating tank if subjected to vibration or false contacts, as previously described, incurs process shortcomings that lead to undesirable surface flaws, called “scorchings", as they appear more opaque than the typical finish of the chromium-plating operation.
  • the inventors were able to understand the problems at the basis of the formation of "scorchings", identified, as shown in figure 2 , in the trend of the voltage, indicated with V, applied to the wire or tape being processed in relation to the length of the chromium-plating tank.
  • the chromium-plating tank is schematically illustrated in figure 2 , with a length included between a first length L1 and a second length L2.
  • the voltage was in fact seen as being substantially decreasing, starting from an optimal value V1, representative of the difference of potential between the wire or tape to be treated and the anode, at the entrance of the chromium-plating tank, decreasing to a low value V2, representative of the difference of potential at the exit from the same chromium-plating tank according to the first configuration.
  • such restoring elements are placed in contact with the wire or tape in motion, when the latter is outside the chromium-plating bath, thus avoiding depositing chromium on the same restoring element.
  • two or more chromium-plating tanks are used, so that the total sum of the lengths of the two or more chromium-plating tanks is equal to the length of one chromium-plating tank according to the first configuration.
  • the schematic length from the first length L1 to the second length L2 of the chromium-plating station G is preferably subdivided into three operating lengths: of a first tank G1, a second tank G2 and a third tank G3, respectively.
  • each point of actuation singled out for example at the third length L3 and at the fourth length L4, is placed, in contact with one portion of processed product 110 on which to operate, a sliding contact 120, to which is applied a predetermined voltage, so as to restore the difference of potential toward the value V1.
  • the sliding contact 120 includes a sliding element 122 that comes into direct contact with a portion of the processed product 110.
  • the sliding element 122 is coupled to the free end of a boom 124 that is connected, at the opposite end, to an arm 126, itself connected to the frame of the machine or to another suitable support.
  • the chromium-plating bath is provided with trivalent chromium, which experimentally has made it possible to obtain better and less polluting results compared to a bath of hexavalent chromium.
  • the trivalent chromium bath is based on chlorides or sulfates.
  • the valuable and innovative result achieved thanks to the present invention has therefore allowed the mass-produced nickel-plating and chromium-plating treatment of wires or tapes, in a continuous cycle and at a substantially constant speed. It is thus possible to achieve the continuous processing, without interruptions, of a whole coil 12 of wire 10 or respective reel of tape, guaranteeing an optimal surface finish and avoiding "scorchings".
  • This solution is applicable, in particular, to the metallic wire or tapes that are subsequently processed by plastic deformation in order to obtain the finished product such as finds application, by way of example but without limits, in the paper-transformation field for the ring and lever mechanisms used in loose-leaf binders.
  • the invention therefore provides an innovative multilayer plating that consists of a first coating of nickel-plating type, as a substrate, to which is added an extremely thin second surface coating of the chromium-plating type; said surface coating has both protective purposes, being in contact with the skin of the final user, and aesthetic purposes, being superficial and visible.
  • the proposed innovative treatment is one with a low release of nickel responding to European Directive 94/27/CE and can be implemented at the industrial level starting from a conventional continuous-treatment line of the mono-wire or mono-tape type, or also of the multi-wire or multi-tape type; the invention also makes it possible to subsequently implement, without defectiveness, the ensuing processes that are typical of the conventional articles found in the paper-transformation field, and still more.
  • the coatings are considered to be of technical and functional type when the thickness exceeds an average value of about 6 or 8 micron, as for example in conventional nickel-platings and in chrome platings intended to increase the hardness and resistance to wear, while they are considered as being of decorative type when the thickness is smaller than this value.
  • the limitation in the release of nickel and the other purposes are achieved with a layer of nickel of 1 to 5 micron in thickness, additionally coated with an extremely thin layer of chromium, with a thickness of 0.01 to 1 micron.
  • the chromium layer although it is extremely thin, achieves the purpose of substantially limiting the transfer of nickel, increasing at the same time the resistance to corrosion of the processed wire or tape.

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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)
EP16176105.1A 2015-06-30 2016-06-24 Verfahren zum plattieren von metallischen drähten oder bändern und produkt hergestellt mittels diesem verfahren Not-in-force EP3112502B1 (de)

Applications Claiming Priority (1)

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ITUB20151869 2015-06-30

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EP3112502A1 true EP3112502A1 (de) 2017-01-04
EP3112502B1 EP3112502B1 (de) 2018-08-01

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110306220A (zh) * 2019-07-23 2019-10-08 淮阴工学院 接插件电镀工艺
DE102018132075A1 (de) * 2018-12-13 2020-06-18 thysenkrupp AG Verfahren zur Herstellung eines mit einer Beschichtung aus Chrom und Chromoxid beschichteten Metallbands auf Basis einer Elektrolytlösung mit einer dreiwertigen Chromverbindung
US11396713B2 (en) 2018-12-13 2022-07-26 Thyssenkrupp Rasselstein Gmbh Method for the production of a metal strip coated with a coating of chromium and chromium oxide using an electrolyte solution with a trivalent chromium compound

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB938192A (en) 1961-03-13 1963-10-02 Kenmore Foreign Corp Wire and rod plating process and product thereof
DE1496930A1 (de) * 1964-01-11 1969-12-18 Res Holland Nv Verfahren zum Aufbringen von korrosionsbestaendigen und verschleissbestaendigen Schichten
US3902974A (en) * 1971-11-12 1975-09-02 Olivetti & Co Spa Process for metallizing type heads of plastics materials for printing devices
US4764260A (en) * 1987-04-15 1988-08-16 Gay Ronald N Process for electroplating nickel over stainless steel
EP1010779A2 (de) * 1998-12-01 2000-06-21 Giovanna Angelini Verfahren und Vorrichtung für die kontinuierliche Chromium-Plattierung von langgestreckten Elementen
US20100167085A1 (en) 2008-12-26 2010-07-01 Byd Co. Ltd. Electroplating Method and Electroplated Product
EP2444530A1 (de) * 2009-06-19 2012-04-25 JX Nippon Mining & Metals Corporation Kupferfolie und herstellungsverfahren dafür
US20130216855A1 (en) * 2011-08-31 2013-08-22 Jx Nippon Mining & Metals Corporation Carrier-attached copper foil

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2961508C (en) * 2014-09-18 2024-04-09 Modumetal, Inc. A method and apparatus for continuously applying nanolaminate metal coatings

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB938192A (en) 1961-03-13 1963-10-02 Kenmore Foreign Corp Wire and rod plating process and product thereof
DE1496930A1 (de) * 1964-01-11 1969-12-18 Res Holland Nv Verfahren zum Aufbringen von korrosionsbestaendigen und verschleissbestaendigen Schichten
US3902974A (en) * 1971-11-12 1975-09-02 Olivetti & Co Spa Process for metallizing type heads of plastics materials for printing devices
US4764260A (en) * 1987-04-15 1988-08-16 Gay Ronald N Process for electroplating nickel over stainless steel
EP1010779A2 (de) * 1998-12-01 2000-06-21 Giovanna Angelini Verfahren und Vorrichtung für die kontinuierliche Chromium-Plattierung von langgestreckten Elementen
US20100167085A1 (en) 2008-12-26 2010-07-01 Byd Co. Ltd. Electroplating Method and Electroplated Product
EP2444530A1 (de) * 2009-06-19 2012-04-25 JX Nippon Mining & Metals Corporation Kupferfolie und herstellungsverfahren dafür
US20130216855A1 (en) * 2011-08-31 2013-08-22 Jx Nippon Mining & Metals Corporation Carrier-attached copper foil

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"PROPERTIES AND APPLICATIONS OF NI-RESIST AND DUCTILE NI-RESIST ALLOYS", NICKEL DEVELOPMENT INSTITUTE (NIDI) REFERENCE BOOK,, vol. 11.018, 1 January 1998 (1998-01-01), pages 41pp, XP009146151 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018132075A1 (de) * 2018-12-13 2020-06-18 thysenkrupp AG Verfahren zur Herstellung eines mit einer Beschichtung aus Chrom und Chromoxid beschichteten Metallbands auf Basis einer Elektrolytlösung mit einer dreiwertigen Chromverbindung
US11274373B2 (en) 2018-12-13 2022-03-15 Thyssenkrupp Rasselstein Gmbh Method for the production of a metal strip coated with a coating of chromium and chromium oxide using an electrolyte solution with a trivalent chromium compound
US11396713B2 (en) 2018-12-13 2022-07-26 Thyssenkrupp Rasselstein Gmbh Method for the production of a metal strip coated with a coating of chromium and chromium oxide using an electrolyte solution with a trivalent chromium compound
CN110306220A (zh) * 2019-07-23 2019-10-08 淮阴工学院 接插件电镀工艺
CN110306220B (zh) * 2019-07-23 2020-11-27 淮阴工学院 接插件电镀工艺

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