EP2230331B1 - Galvanisches Beschichtungsverfahren zur Aufbringung einer anthrazitfarbenen Beschichtung und mit dieser Beschichtung versehene Metallteile - Google Patents

Galvanisches Beschichtungsverfahren zur Aufbringung einer anthrazitfarbenen Beschichtung und mit dieser Beschichtung versehene Metallteile Download PDF

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Publication number
EP2230331B1
EP2230331B1 EP09155762A EP09155762A EP2230331B1 EP 2230331 B1 EP2230331 B1 EP 2230331B1 EP 09155762 A EP09155762 A EP 09155762A EP 09155762 A EP09155762 A EP 09155762A EP 2230331 B1 EP2230331 B1 EP 2230331B1
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EP
European Patent Office
Prior art keywords
acid
gold
coating
depositing
metal parts
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.)
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Application number
EP09155762A
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English (en)
French (fr)
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EP2230331A1 (de
Inventor
Christophe Henzirohs
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.)
Universo SA
Original Assignee
Universo 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 Universo SA filed Critical Universo SA
Priority to AT09155762T priority Critical patent/ATE530680T1/de
Priority to EP09155762A priority patent/EP2230331B1/de
Priority to JP2010057010A priority patent/JP5331038B2/ja
Priority to US12/727,095 priority patent/US8226810B2/en
Priority to CN201010139401.7A priority patent/CN101838829B/zh
Publication of EP2230331A1 publication Critical patent/EP2230331A1/de
Application granted granted Critical
Publication of EP2230331B1 publication Critical patent/EP2230331B1/de
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/52—After-treatment of electroplated surfaces by brightening or burnishing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12889—Au-base component

Definitions

  • the invention relates to the field of galvanic type deposition processes, from an electrolytic solution. More specifically, it relates to a process for depositing an anthracite-colored coating for metal parts intended, for example, for watchmaking or jewelery.
  • a bath called electrolyte
  • a potential difference is applied between two electrodes immersed in the electrolyte, so as to cause a reduction reaction of the ionic metal species at the anode.
  • parts to be treated arranged on a support or in a basket, are put at the potential of the anode, they are covered with a metal film under the effect of the reduction reaction.
  • This is the so-called 'black gold' process, using an electrolyte based on gold and nickel. This process does not require post-treatment, it is easy to use and stable over time.
  • the support element provided for the installation of parts can be reused several times without being cleaned.
  • the "black gold” process provides a similar appearance to the parts treated by the ruthenium black and black rhodium processes, the anthracite shade obtained being insufficiently supported.
  • the present invention aims to overcome the aforementioned drawbacks, by proposing a method of depositing a technically simple anthracite color coating and providing a sustained anthracite shade. More specifically, the invention relates to a galvanic process for depositing an anthracite coating for metal parts, comprising a first step of depositing a gold-nickel alloy by means of an electrolytic bath. According to the invention, the method comprises a second step of treating said gold-nickel alloy by means of a dilute acid bath, containing an acid chosen from hydrochloric, hydrofluoric, phosphoric, nitric and sulfuric acids.
  • the anthracite shade of the coating obtained increases in intensity and aesthetics.
  • the process has an additional step compared to the conventional gold-nickel process, but remains substantially simpler, robust and cheaper than the nickel-black, black ruthenium and black rhodium processes. It is also suitable for rooms of all sizes.
  • the invention also relates to metal parts provided with an anthracite color coating composed of a gold-nickel alloy whose nickel atom content is between 30 and 40 percent.
  • the metal parts to be treated are positioned on a support element, called a loop, or arranged in bulk in a basket.
  • the pieces are made of metal, such as brass, steel, bronze, gold or any other metal having the desired mechanical properties.
  • they are covered with an underlayer of a pure gold alloy or a gold alloy such as gold-cobalt, obtained by a galvanic or other process, of a thickness of about 0.35 micrometer.
  • the parts to be treated are bare metal.
  • the support element is immersed in the electrolytic bath and put at the potential of the anode. In a few minutes, a layer of a gold-nickel alloy of about 0.6 micrometer, is deposited on the parts to be treated, and they take the desired anthracite color. The parts are then rinsed and dried. At this stage of the process according to the invention, they have an anthracite color characteristic of the galvanic gold-black process.
  • the galvanic process for depositing an anthracite-colored coating for metal parts also comprises a step of treating the gold-nickel alloy thus deposited, by means of a diluted acid bath.
  • Said bath contains an acid chosen from sulfuric, hydrochloric, hydrofluoric, phosphoric or nitric acids.
  • the dilution is preferably between 1 and 50 ml / l of concentrated acid, and the temperature is 20 ° C.
  • a wetting agent is added to the acid bath.
  • the diluted acid bath contains a mixture of hydrochloric acid and hydrofluoric acid in the dilution range indicated above.
  • the diluted acid bath contains hydrochloric acid in the indicated dilution range, supplemented with a neutralizing salt, ammonium bifluoride, of chemical formula NH4HF2.
  • the acid bath contains hydrochloric acid diluted to 10 ml / l, the neutralizing salt mentioned above at a rate of 50 g / l and a wetting agent at a rate of 2 ml / l.
  • the parts coated with the gold-nickel alloy to be treated are placed on a support or in a basket, and then immersed in a dilute acid bath of the type described above, for a period of the order of a few seconds to a few minutes. They are then rinsed and dried.
  • the diluted acid bath has the effect of substantially intensifying the initial anthracite shade of the pieces.
  • the aesthetics of the parts are thus improved, simply and quickly, and cheap.
  • a chemical analysis of the gold-nickel alloy subjected to the acid treatment reveals a depletion of nickel metal of the order of 10 to 15 percent compared to the untreated alloy.
  • the gold-nickel alloy thus treated has a nickel atom content of between 30 and 40 percent, compared to a percentage of 45 percent for a gold-nickel alloy as deposited.
  • the remaining nickel has been at least partially oxidized by the acid treatment.

Landscapes

  • 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)
  • Chemical Treatment Of Metals (AREA)

Claims (5)

  1. Galvanisches Verfahren für den Niederschlag einer Anthrazitfarbbeschichtung für Metallteile, das einen ersten Schritt des Niederschlages einer Gold-Nickel-Legierung mittels eines Elektrolytbades umfasst, dadurch gekennzeichnet, dass es einen zweiten Schritt des Behandelns der Gold-Nickel-Legierung mittels eines verdünnten Säurebads, das eine Säure enthält, die aus Hydrochlorsäure, Hydrofluorsäure, Phosphorsäure, Salpetersäure und Schwefelsäure gewählt ist, umfasst.
  2. Galvanisches Niederschlagsverfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Verdünnung der Säure im Bereich von 1 bis 50 ml/l der konzentrieren Säure liegt.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das verdünnt Säurebad ein Gemisch aus hlydrochlorsäure und Hydrofiuorsäure enthält.
  4. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das verdünnte Säurebad Hydrochlorsäure, zu der Ammonbifluorid hinzugefügt ist, enthält.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das verdünnte Säurebad außerdem ein Benetzungsprodukt enthält.
EP09155762A 2009-03-20 2009-03-20 Galvanisches Beschichtungsverfahren zur Aufbringung einer anthrazitfarbenen Beschichtung und mit dieser Beschichtung versehene Metallteile Active EP2230331B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AT09155762T ATE530680T1 (de) 2009-03-20 2009-03-20 Galvanisches beschichtungsverfahren zur aufbringung einer anthrazitfarbenen beschichtung und mit dieser beschichtung versehene metallteile
EP09155762A EP2230331B1 (de) 2009-03-20 2009-03-20 Galvanisches Beschichtungsverfahren zur Aufbringung einer anthrazitfarbenen Beschichtung und mit dieser Beschichtung versehene Metallteile
JP2010057010A JP5331038B2 (ja) 2009-03-20 2010-03-15 電気化学堆積方法
US12/727,095 US8226810B2 (en) 2009-03-20 2010-03-18 Galvanic deposition method for an anthracite coloured coating and metallic parts provided with the coating
CN201010139401.7A CN101838829B (zh) 2009-03-20 2010-03-19 形成黑灰色涂层的电流沉积方法和带有该涂层的金属零件

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09155762A EP2230331B1 (de) 2009-03-20 2009-03-20 Galvanisches Beschichtungsverfahren zur Aufbringung einer anthrazitfarbenen Beschichtung und mit dieser Beschichtung versehene Metallteile

Publications (2)

Publication Number Publication Date
EP2230331A1 EP2230331A1 (de) 2010-09-22
EP2230331B1 true EP2230331B1 (de) 2011-10-26

Family

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EP09155762A Active EP2230331B1 (de) 2009-03-20 2009-03-20 Galvanisches Beschichtungsverfahren zur Aufbringung einer anthrazitfarbenen Beschichtung und mit dieser Beschichtung versehene Metallteile

Country Status (5)

Country Link
US (1) US8226810B2 (de)
EP (1) EP2230331B1 (de)
JP (1) JP5331038B2 (de)
CN (1) CN101838829B (de)
AT (1) ATE530680T1 (de)

Family Cites Families (23)

* Cited by examiner, † Cited by third party
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US1924439A (en) * 1932-04-18 1933-08-29 Harold J Kersten Process of forming alloy materials by electroplating
US3285699A (en) * 1964-05-07 1966-11-15 Amp Inc Porosity test method
US3342568A (en) * 1965-03-16 1967-09-19 Engelhard Ind Inc Composite material of a ceramic silver gold alloy, and a nickel alloy
US3502548A (en) * 1966-10-24 1970-03-24 Ernest H Lyons Jr Method of electroplating gold on chromium
US4274908A (en) * 1978-08-15 1981-06-23 United Technologies Corporation Cyanide free solution and process for removing gold-nickel braze
US4261738A (en) * 1979-10-01 1981-04-14 Arthur D. Little, Inc. Process for recovering precious metals from bimetallic material
US4302246A (en) * 1980-01-03 1981-11-24 Enthone, Incorporated Solution and method for selectively stripping alloys containing nickel with gold, phosphorous or chromium from stainless steel and related nickel base alloys
US4299864A (en) * 1980-02-28 1981-11-10 The United States Of America As Represented By The Secretary Of The Army Method of making visible light to far infrared transducer
JPS60181277A (ja) * 1984-02-27 1985-09-14 Sumitomo Metal Ind Ltd 黒色化鋼板とその製法
JPS6137980A (ja) * 1984-07-31 1986-02-22 Ishikawajima Harima Heavy Ind Co Ltd 金・ニツケルロ−付けの剥離方法
JPS61238979A (ja) * 1985-04-15 1986-10-24 Kobe Steel Ltd 着色亜鉛合金めつき鋼板の製造方法
JPS63121672A (ja) * 1986-11-12 1988-05-25 Nippon Mining Co Ltd 金属表面の着色方法
JPS63250487A (ja) * 1987-04-08 1988-10-18 Seiko Instr & Electronics Ltd 黒色金めつき液
JPH01188680A (ja) * 1987-11-10 1989-07-27 Anritsu Corp 黒色皮膜を有する基材及び黒色皮膜形成方法
JP2820451B2 (ja) * 1988-11-22 1998-11-05 シチズン時計株式会社 装身具
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DE69419310T2 (de) * 1993-12-28 1999-12-16 Citizen Watch Co., Ltd. Weisses dekoratives teil und verfahren zu dessen herstellung
FR2747400B1 (fr) * 1996-04-12 1998-05-22 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
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Also Published As

Publication number Publication date
JP2010222704A (ja) 2010-10-07
JP5331038B2 (ja) 2013-10-30
ATE530680T1 (de) 2011-11-15
US20100239881A1 (en) 2010-09-23
EP2230331A1 (de) 2010-09-22
CN101838829B (zh) 2014-05-07
US8226810B2 (en) 2012-07-24
CN101838829A (zh) 2010-09-22

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