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EP0552097B1 - Verfahren und Vorrichtung zur Nickel-Elektroplattierung - Google Patents

Verfahren und Vorrichtung zur Nickel-Elektroplattierung Download PDF

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Publication number
EP0552097B1
EP0552097B1 EP93400070A EP93400070A EP0552097B1 EP 0552097 B1 EP0552097 B1 EP 0552097B1 EP 93400070 A EP93400070 A EP 93400070A EP 93400070 A EP93400070 A EP 93400070A EP 0552097 B1 EP0552097 B1 EP 0552097B1
Authority
EP
European Patent Office
Prior art keywords
nickel
anode
cathode
bath
semi
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.)
Expired - Lifetime
Application number
EP93400070A
Other languages
English (en)
French (fr)
Other versions
EP0552097A1 (de
Inventor
Béatrice Sala
Laurent Guerin
Bernard Michaut
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.)
Institut de Recherches de la Siderurgie Francaise IRSID
Areva NP SAS
Original Assignee
Institut de Recherches de la Siderurgie Francaise IRSID
Framatome 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 Institut de Recherches de la Siderurgie Francaise IRSID, Framatome SA filed Critical Institut de Recherches de la Siderurgie Francaise IRSID
Publication of EP0552097A1 publication Critical patent/EP0552097A1/de
Application granted granted Critical
Publication of EP0552097B1 publication Critical patent/EP0552097B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002—Cell separation, e.g. membranes, diaphragms

Definitions

  • the present invention relates to an improved apparatus and a method of electrolytically coating nickel. It concerns the field of nickel plating by electrolytic coating of metallic or non-metallic parts, using baths nickel plating using nickel sulfamate as input of nickel.
  • nickel plating elements of electrical connectors and more generally to any nickel plating operation using a nickel sulfamate either by a static process (bath in a tank with fixed electrodes), either by a process dynamic (bath circulation or circulation of parts to nickel).
  • a third important application concerns the purification of the nickel-plating baths used during the said coatings.
  • complex compounds compounds resulting from the modification of the sulfamate ligand such as by example azodisulfonate.
  • Nickel electroplating cell page 500, collar. 2 of Chemical Abstracts, vol. 102, n ° 18, May 1985, also makes known a coating device nickel electrolytic according to the preamble of the claim 1.
  • the invention proposes, however, a device in accordance with the characterizing part of the claim 1.
  • the semi-permeable wall of inert sintered material or polymer prevents the passage of oxidized compounds formed to the anode, from the anode compartment to the cathode compartment.
  • the invention also aims to provide a method preventing or preventing the degradation of nickel plating baths and use these baths until exhaustion their nickel content, without risking incidents due to the early passivation of the anode in the case where it is made of soluble nickel, i.e. depolarized nickel sulfur, such as for example the products sold by the INCO Company (pellets, beads, etc.).
  • the invention provides a method of electrolytic coating of a part according to claim 5.
  • the cathode can consist of the part to coating, this part being in contact with the bath of the cathode compartment.
  • the method may include a step preliminary to the nickel plating operation in which the cathode consists of a simple electrode allowing electrolysis nickel plating baths, to prevent and prevent their degradation and thus allow their use up to depletion of their nickel content.
  • Figure 1 and Figure 2 show modes individuals implementing the invention, given as non-limiting examples.
  • Figure 3 shows the evolution of the parameters electrochemical during electrolysis as performed in the prior art.
  • Figure 4 shows the evolution of the parameters electrochemicals during an electrolysis performed according to the invention.
  • the schematic representation of Figure 1 includes a container 1 formed of two vertical tanks communicating by a transverse channel, intended to receive the bath 2 to be electrolyzed.
  • a cathode 3 is immersed in one of the vertical tanks and an anode 4 is immersed in the other vertical tank.
  • a semi-permeable wall 5 closes the channel transverse which connects the two vertical tanks and separates thus the anode compartment of the cathode compartment.
  • FIG. 2 schematically represents a tank 6 intended to receive the bath 7 to be purified.
  • a cathode 8 and an anode 9 isolated from the rest of the bath by a semi-permeable wall 10 thus delimiting, around the anode, a compartment inside the nickel plating bath.
  • the semi-permeable wall can be a frit or a polymer membrane.
  • the electrolysis carried out is in itself known both for the connection of the electrodes as for the control of different parameters.
  • the anode and the cathode could be connected, via a rheostat, to the terminals of a direct current source for supplying voltage U of a few volts at an intensity I of a few amps .
  • a tension measurement device can be mounted between the anode and a reference electrode and will provide the potential (Ea) of the anode relative to the reference electrode.
  • cathode cathode
  • anode anode
  • reference electrode the three electrodes: cathode, anode and reference electrode
  • FIG 3 shows that, until time T 1 , the three parameters I, U, Ea are constant and the electrolysis process takes place normally, beyond T 1 we have shown the passivation phenomenon of the anode which not only generates an increase in the potential of the anode relative to the reference electrode Ea, but above all which causes a sudden drop in the nickel-plating current I with rapid degradation of the bath by oxidation and formation of a non-homogeneous nickel deposit .
  • This passivation of the anode also produces a deterioration of the bath by acidification with, consequently, the formation of a fragile nickel deposit.
  • the cathode is placed in one of the two vertical tanks of a device of the kind of that schematically represented in Figure 1, the anode and the reference electrode are placed in the other vertical tank, the semi-permeable wall being placed between the two tanks in the transverse channel.
  • FIG. 4 shows that, until time T 1 , the electrolysis evolves in the same way as in the previous case represented in FIG. 3. As in the previous case, the passivation phenomenon of the anode causes a increase in potential Ea.
  • two nickel plating operations are carried out, one according to the prior art, the other in separate compartments by a semi-permeable wall, in two nickel plating baths of identical starting composition.
  • the three electrodes cathode, anode and reference electrode for mercury sulfamate, are placed in a non-compartmentalized tank; in in the case of an apparatus according to the invention, the cathode is placed in one of the two vertical tanks of a device of the kind schematically shown in the figure 1, the anode and the reference electrode are placed in the other vertical tank, the semi-permeable wall being a sintered in pyrex n ° 4, 3 mm thick, marketed by SOVIREL company placed between the two tanks in the canal transverse.
  • the passivation anode intervened after 30 minutes about and was highlighted by the rise of his surface potential with an Ea value of approximately 300 mV up to a value exceeding 1000 mV.
  • the initial nickel plating bath has been greatly enriched by complex compounds such as by example azidosulfonate in one of the compartments making impossible any electrolysis, while the bath contained in the other compartment remains capable of ensuring effective nickel plating after 9 hours of using the original bath.
  • Maintaining the oxidized compound in a compartment specific so as not to pollute the bath allows to perform purification of sulfamate baths by electrolysis (extraction of traces of cobalt for example) without pollution azodisulfonate.

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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)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (5)

  1. Vorrichtung zum elektrolytischen Überziehen eines Gegenstands mit Nickel, ausgehend von einem Vernicklungsbad, das als Nickellieferant die Verbindung Nickelsulfamat verwendet, mit einem Behälter, der das Vernicklungsbad und eine halbdurchlässige Wand (5, 10) enthält, die eine Kathodenzelle von einer Anodenzelle trennt, in der jeweils eine Kathode (8) und eine Nickelanode (9) eingetaucht sind,
    dadurch gekennzeichnet, daß
    die Wand aus einem Polymer oder einem inerten Sintermaterial besteht, mit der Eigenschaft, daß die Wand den Durchgang der Oxidverbindungen, die an der Anode gebildet werden, verhindert.
  2. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß der Behälter aus zwei vertikalen Küvetten gebildet ist, die durch einen horizontalen Kanal verbunden sind, der durch die halbdurchlässige Wand verschlossen ist.
  3. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß, die halbdurchlässige Wand im Inneren des Vernicklungsbads um die Anode oder der Kathode herum eine Zelle begrenzt.
  4. Verfahren zum elektrolytischen Überziehen eines Gegenstands, bei dem man an ein Verbindungsbad, in dem als Nickellieferant die Verbindung Nickelsulfamat benutzt wird, einen Elektrolysestrom zwischen einer Kathode, die aus dem zu überziehenden Gegenstand gebildet ist, und einer löslichen Nickelanode anlegt, die in einem Bad eingetaucht und durch eine halbdurchlässige Wand getrennt sind, dadurch gekennzeichnet, daß man den einfachen Austausch zwischen den komplexen Verbindungen, die an der Kathode entstanden sind, und denen, die an der Anode entstanden sind, verhindert, indem man die Wand aus einem inerten Sintermaterial oder aus einem Polymer bildet, die den Durchgang des Elektrolysestroms erlaubt.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß es eine Vorbereitungsphase für den Durchgangsstrom umfaßt, während dieser die Kathode aus einer einfachen Elektrode gebildet ist.
EP93400070A 1992-01-16 1993-01-13 Verfahren und Vorrichtung zur Nickel-Elektroplattierung Expired - Lifetime EP0552097B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9200407A FR2686352B1 (fr) 1992-01-16 1992-01-16 Appareil et procede de revetement electrolytique de nickel.
FR9200407 1992-01-16

Publications (2)

Publication Number Publication Date
EP0552097A1 EP0552097A1 (de) 1993-07-21
EP0552097B1 true EP0552097B1 (de) 1998-03-11

Family

ID=9425680

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93400070A Expired - Lifetime EP0552097B1 (de) 1992-01-16 1993-01-13 Verfahren und Vorrichtung zur Nickel-Elektroplattierung

Country Status (5)

Country Link
US (1) US5403460A (de)
EP (1) EP0552097B1 (de)
DE (1) DE69317315T2 (de)
FR (1) FR2686352B1 (de)
ZA (1) ZA93264B (de)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19834353C2 (de) 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkalisches Zink-Nickelbad
DE19848467C5 (de) * 1998-10-21 2006-04-27 Walter Hillebrand Gmbh & Co. Kg Galvanotechnik Alkalisches Zink-Nickelbad
US6482298B1 (en) * 2000-09-27 2002-11-19 International Business Machines Corporation Apparatus for electroplating alloy films
KR100603130B1 (ko) * 2001-08-01 2006-07-20 닛코킨조쿠 가부시키가이샤 고순도 니켈의 제조방법, 고순도 니켈, 동 고순도 니켈로부터 이루어진 스퍼터링 타겟트 및 이 스퍼터링 타겟트에 의해 형성된 박막
US7195702B2 (en) * 2003-06-06 2007-03-27 Taskem, Inc. Tin alloy electroplating system
US7063628B2 (en) * 2004-03-23 2006-06-20 Callaway Golf Company Plated magnesium golf club head
US7087268B2 (en) * 2004-03-30 2006-08-08 Callaway Golf Company Method of plating a golf club head
US20060096867A1 (en) * 2004-11-10 2006-05-11 George Bokisa Tin alloy electroplating system
US7311615B2 (en) * 2005-07-01 2007-12-25 Charles Hsu Golf club head with ceramic layer
US20110226613A1 (en) 2010-03-19 2011-09-22 Robert Rash Electrolyte loop with pressure regulation for separated anode chamber of electroplating system
US8980068B2 (en) 2010-08-18 2015-03-17 Allen R. Hayes Nickel pH adjustment method and apparatus
US9404194B2 (en) 2010-12-01 2016-08-02 Novellus Systems, Inc. Electroplating apparatus and process for wafer level packaging
US8425751B1 (en) 2011-02-03 2013-04-23 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Systems and methods for the electrodeposition of a nickel-cobalt alloy
US9534308B2 (en) 2012-06-05 2017-01-03 Novellus Systems, Inc. Protecting anodes from passivation in alloy plating systems
US10465307B2 (en) * 2015-11-19 2019-11-05 Fabric8Labs, Inc. Apparatus for electrochemical additive manufacturing
CN111630211B (zh) 2017-11-01 2024-05-24 朗姆研究公司 控制在电化学镀敷设备上的镀敷电解液浓度
US10914000B1 (en) 2019-08-23 2021-02-09 Fabric8Labs, Inc. Method for manufacturing a printhead of an electrochemical additive manufacturing system
US11512404B2 (en) 2019-08-23 2022-11-29 Fabric8Labs, Inc. Matrix-controlled printhead for an electrochemical additive manufacturing system
US11680330B2 (en) 2021-07-22 2023-06-20 Fabric8Labs, Inc. Electrochemical-deposition apparatuses and associated methods of electroplating a target electrode
US11795561B2 (en) 2021-08-02 2023-10-24 Fabric8Labs, Inc. Electrochemical-deposition system, apparatus, and method using optically-controlled deposition electrodes
US11920251B2 (en) 2021-09-04 2024-03-05 Fabric8Labs, Inc. Systems and methods for electrochemical additive manufacturing of parts using multi-purpose build plate
US11970783B2 (en) 2021-09-23 2024-04-30 Fabric8Labs, Inc. Systems and methods for manufacturing electrical components using electrochemical deposition
US11745432B2 (en) 2021-12-13 2023-09-05 Fabric8Labs, Inc. Using target maps for current density control in electrochemical-additive manufacturing systems
US12104264B2 (en) 2021-12-17 2024-10-01 Fabric8Labs, Inc. Systems and methods for electrochemical additive manufacturing of parts using capacitive sensing

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE925264C (de) * 1952-11-15 1955-03-17 Hesse & Co Dr Verfahren zum Vernickeln ohne Nickelanoden
JPS563692A (en) * 1979-06-23 1981-01-14 Kooken:Kk Method and apparatus for high speed plating
US4902388A (en) * 1989-07-03 1990-02-20 United Technologies Corporation Method for electroplating nickel onto titanium alloys
JPH03120390A (ja) * 1989-09-29 1991-05-22 Toshiba Corp 低応力ニッケルめっき浴
JP2764337B2 (ja) * 1990-05-10 1998-06-11 新日本製鐵株式会社 Ｎｉ又はＮｉ―Ｚｎ合金又はＮｉ―Ｚｎ―Ｃｏ合金メッキ方法

Also Published As

Publication number Publication date
FR2686352A1 (fr) 1993-07-23
DE69317315T2 (de) 1998-10-15
DE69317315D1 (de) 1998-04-16
EP0552097A1 (de) 1993-07-21
US5403460A (en) 1995-04-04
ZA93264B (en) 1994-07-15
FR2686352B1 (fr) 1995-06-16

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