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EP2230331B1 - Galvanic method for depositing a charcoal grey coating and metal parts with such a coating - Google Patents

Galvanic method for depositing a charcoal grey coating and metal parts with such a coating 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
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EP09155762A
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German (de)
French (fr)
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EP2230331A1 (en
Inventor
Christophe Henzirohs
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Universo SA
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Universo SA
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Priority to EP09155762A priority Critical patent/EP2230331B1/en
Priority to AT09155762T priority patent/ATE530680T1/en
Priority to JP2010057010A priority patent/JP5331038B2/en
Priority to US12/727,095 priority patent/US8226810B2/en
Priority to CN201010139401.7A priority patent/CN101838829B/en
Publication of EP2230331A1 publication Critical patent/EP2230331A1/en
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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.

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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)
  • Chemical Treatment Of Metals (AREA)

Abstract

The galvanic process of deposition of an anthracite color coating for metal parts, comprises initially depositing a gold-nickel alloy on the metal parts using an electrolytic bath, and processing the gold-nickel alloy using a diluted acid bath. The acid bath is diluted using 1-50 ml/l of concentrated acid, and contains a wetting product. An independent claim is included for metal parts with an anthracite color coating.

Description

L'invention se rapporte au domaine des procédés de dépôt de type galvanique, à partir d'une solution électrolytique. Elle concerne plus précisément un procédé de dépôt d'un revêtement de couleur anthracite pour des pièces métalliques destinées, par exemple, à l'horlogerie ou à la bijouterie.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.

De tels procédés galvaniques sont bien connus de l'homme de métier et largement décrits dans la littérature scientifique. On se bornera à en rappeler le principe. Un bain, appelé électrolyte, contient des espèces métalliques sous forme ionique. Une différence de potentiel est appliquée entre deux électrodes plongées dans l'électrolyte, de manière à provoquer une réaction de réduction des espèces métalliques ioniques au niveau de l'anode. Lorsque des pièces à traiter, disposées sur un support ou dans un panier, sont mises au potentiel de l'anode, elles se recouvrent d'un film métallique sous l'effet de la réaction de réduction.Such galvanic methods are well known to those skilled in the art and widely described in the scientific literature. We will confine ourselves to recalling the principle. A bath, called electrolyte, contains metallic species in ionic form. 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. When 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.

Il existe plusieurs procédés, basés sur divers électrolytes, destinés à revêtir des pièces en métal, tel qu'en laiton, bronze, acier, or ou autre, d'une couche métallique de couleur anthracite.There are several methods, based on various electrolytes, for coating metal parts, such as brass, bronze, steel, gold or other, with a metallic layer of anthracite color.

L'un d'entre eux est un procédé de dépôt d'un alliage de nickel et zinc, appelé 'nickel noir', permettant l'obtention d'un dépôt d'une nuance anthracite intense. Il utilise un électrolyte contenant des espèces zinc, nickel et soufre. Bien qu'esthétiquement très performant, le procédé nickel noir n'est pas exempt d'inconvénients techniques. En premier lieu, les pièces ainsi revêtues d'un alliage nickel-zinc doivent être enduites d'une anthracite. Cette étape d'application d'une laque ajoute à la complexité et au coût du procédé. De plus, elle ne convient pas à des pièces de petites tailles, dont l'aspect est dégradé par la laque. En second lieu, l'électrolyte est chimiquement instable, ce qui pose des problèmes de reproductibilité du procédé. Enfin, l'élément de support utilisé pour le posage des pièces doit être longuement décapé entre deux bains.One of them is a process for depositing a nickel and zinc alloy, called 'black nickel', which makes it possible to obtain a deposit of an intense anthracite shade. It uses an electrolyte containing zinc, nickel and sulfur species. Although aesthetically very powerful, the black nickel process is not free of technical disadvantages. In the first place, the parts thus coated with a nickel-zinc alloy must be coated with anthracite. This lacquer application step adds to the complexity and cost of the process. In addition, it is not suitable for small parts, whose appearance is degraded by lacquer. In the second place, the electrolyte is chemically unstable, which poses problems of reproducibility of the process. Finally, the support element used for the laying of parts must be long stripped between two baths.

Deux autres procédés, connus sous l'appellation 'ruthénium noir' et 'rhodium noir', en référence aux espèces métalliques qu'ils contiennent majoritairement, sont également bien connus de l'homme de métier. Ils souffrent en parte des mêmes inconvénients que le procédé nickel noir.Two other processes, known as 'black ruthenium' and 'black rhodium', with reference to the metal species which they contain predominantly, are also well known to those skilled in the art. They suffer from the same disadvantages as the black nickel process.

Un procédé, bien connu de l'homme de métier, est utilisé pour le dépôt d'un revêtement de couleur anthracite. Il s'agit du procédé appelé 'or noir', utilisant un électrolyte à base d'or et de nickel. Ce procédé ne nécessite pas de post-traitement, il est simple d'emploi et stable dans le temps. De plus, l'élément de support prévu pour le posage des pièces peut être réutilisé plusieurs fois sans être nettoyé. Bien que techniquement avantageux par rapport aux procédés nickel noir, ruthénium noir et rhodium noir, le procédé « or noir » procure un aspect analogue aux pièces traitées par les procédés ruthénium noir et rhodium noir, la nuance anthracite obtenue étant insuffisamment soutenue.A method, well known to those skilled in the art, is used for the deposition of an anthracite color coating. 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. In addition, the support element provided for the installation of parts can be reused several times without being cleaned. Although technically advantageous compared to the black nickel, black ruthenium and black rhodium processes, 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.

On connait également du document EP 0686 706 un procédé de décoration d'une pièce décorative.We also know of the document EP 0686 706 a method of decorating a decorative piece.

La présente invention a pour but de remédier aux inconvénients précités, en proposant un procédé de dépôt d'un revêtement de couleur anthracite techniquement simple et procurant une nuance anthracite soutenue. Plus précisément, l'invention concerne un procédé galvanique de dépôt d'un revêtement de couleur anthracite pour des pièces métalliques, comportant une première étape de dépôt d'un alliage or-nickel au moyen d'un bain électrolytique. Selon l'invention, le procédé comprend une seconde étape de traitement dudit alliage or-nickel au moyen d'un bain d'acide dilué, contenant un acide choisi parmi les acides chlorhydrique, fluorhydrique, phosphorique, nitrique, et sulfurique.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.

Grâce à l'étape de traitement acide de l'alliage or-nickel, la nuance anthracite du revêtement obtenu gagne en intensité et en esthétique. Le procédé comporte une étape supplémentaire par rapport au procédé or-nickel classique, mais reste sensiblement plus simple, robuste et meilleur marché que les procédés nickel-noir, ruthénium noir et rhodium noir. Il est, en outre, adapté pour des pièces de toutes tailles.Thanks to the acid treatment step of the gold-nickel alloy, 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.

L'invention concerne également des pièces métalliques munies d'un revêtement de couleur anthracite composé d'un alliage d'or-nickel dont la teneur en atomes nickel est comprise entre 30 et 40 pourcents.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.

D'autre caractéristiques et avantages de la présente invention ressortiront plus clairement de la description détaillée qui suit d'un exemple d'exécution du procédé selon l'invention, cet exemple étant donné à titre purement illustratif et non limitatif seulement.Other features and advantages of the present invention will emerge more clearly from the detailed description which follows of an exemplary embodiment of the method according to the invention, this example being given for purely illustrative and non-limiting purposes only.

Le procédé galvanique de dépôt d'un revêtement de couleur anthracite pour des pièces métalliques selon l'invention, comporte classiquement une première étape de dépôt d'un alliage or-nickel au moyen d'un bain électrolytique contenant des espèces or et nickel. Les paramètres de dépôt de l'alliage or-nickel sont standard et bien connus de l'homme de métier. A titre d'exemple, on indique le mode opératoire suivant :

  • Teneur en or métal    :    2g/l
  • Teneur en nickel métal    :    5g/l
  • pH électrométrique    :    5.6
  • Densité en degré Baumé:    11 °Bé
  • Température    :    55°C
  • Densité de courant    :    2A/dm2
The galvanic process for depositing an anthracite-colored coating for metal parts according to the invention conventionally comprises a first step of depositing a gold-nickel alloy by means of an electrolytic bath containing gold and nickel species. The deposition parameters of the gold-nickel alloy are standard and well known to those skilled in the art. By way of example, the following procedure is indicated:
  • Gold metal content: 2g / l
  • Nickel metal content: 5g / l
  • Electrometric pH: 5.6
  • Density in degree Baumé: 11 ° Be
  • Temperature: 55 ° C
  • Current density: 2A / dm2

Bien entendu, les paramètres susmentionnés sont donnés à titre indicatif et peuvent être modifiés en fonction du résultat souhaité. Par exemple, une augmentation de la densité de courant permet d'augmenter la vitesse de dépôt de l'alliage or-nickel.Of course, the aforementioned parameters are given as an indication and can be modified according to the desired result. For example, an increase in the current density makes it possible to increase the deposition rate of the gold-nickel alloy.

Les pièces métalliques à traiter, par exemple des aiguilles de montres, des cadrans ou appliques pour cadrans, des boîtes ou des pièces de mouvement, sont positionnées sur un élément de support, appelé bouclard, ou disposées en vrac dans un panier. Les pièces sont en métal, tel qu'en laiton, en acier, en bronze, en or ou tout autre métal ayant les propriétés mécaniques souhaitées. Avantageusement, elles sont recouvertes d'une sous-couche d'un alliage d' or pur ou d'un alliage d'or tel que l'or-cobalt, obtenue par un procédé galvanique ou autre, d'une épaisseur d'environ 0.35 micromètre. En variante, les pièces à traiter sont en métal nu.The metal parts to be treated, for example watch hands, dials or dials, boxes or movement pieces, 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. Advantageously, 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. Alternatively, the parts to be treated are bare metal.

L'élément de support est plongé dans le bain électrolytique et mis au potentiel de l'anode. En quelques minutes, une couche d'un alliage d'or-nickel d'environ 0.6 micromètre, se dépose sur les pièces à traiter, et celles-ci prennent la couleur anthracite souhaitée. Les pièces sont ensuite rincées puis séchées. A ce stade du procédé selon l'invention, elles présentent une couleur anthracite caractéristique du procédé galvanique or-noir.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.

Selon l'invention, le procédé galvanique de dépôt d'un revêtement de couleur anthracite pour des pièces métalliques, comporte encore une étape de traitement de l'alliage or-nickel ainsi déposé, au moyen d'un bain d'acide dilué. Ledit bain contient un acide choisi parmi les acides sulfurique, chlorhydrique, fluorhydrique, phosphorique ou nitrique. La dilution est, de préférence, comprise entre 1 et 50ml/l d'acide concentré, et la température est de 20°C. Avantageusement, un produit mouillant est ajouté au bain acide.According to the invention, 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. Advantageously, a wetting agent is added to the acid bath.

Dans un premier mode d'exécution avantageux du procédé selon l'invention, le bain d'acide dilué contient un mélange d'acide chlorhydrique et d'acide fluorhydrique dans la fourchette de dilution indiquée précédemment. Dans un second mode d'exécution avantageux, le bain d'acide dilué contient de l'acide chlorhydrique dans la fourchette de dilution indiquée, additionné d'un sel neutralisant, le bifluorure d'amonium, de formule chimique NH4HF2. Dans un mode d'exécution particulièrement avantageux, le bain d'acide contient de l'acide chlorhydrique dilué à 10ml/l, le sel neutralisant susmentionné à raison de 50g/l et un produit mouillant à raison de 2ml/l.In a first advantageous embodiment of the process according to the invention, the diluted acid bath contains a mixture of hydrochloric acid and hydrofluoric acid in the dilution range indicated above. In a second advantageous embodiment, the diluted acid bath contains hydrochloric acid in the indicated dilution range, supplemented with a neutralizing salt, ammonium bifluoride, of chemical formula NH4HF2. In a particularly embodiment advantageously, 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.

Les pièces revêtues de l'alliage or-nickel à traiter sont disposées sur un support ou dans un panier, puis plongées dans un bain d'acide dilué du type décrit précédemment, pendant une durée de l'ordre de quelques secondes à quelques minutes. Elles sont ensuite rincées et séchées.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.

Le bain d'acide dilué a pour effet d'intensifier sensiblement la nuance anthracite initiale des pièces. L'esthétique des pièces est ainsi améliorée, de façon simple et rapide, et bon marché.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.

Une analyse chimique de l'alliage or-nickel soumis au traitement acide, met en évidence un appauvrissement en métal nickel de l'ordre de 10 à 15 pourcents par rapport à l'alliage non traité. L'alliage or-nickel ainsi traité présente une teneur en atomes nickel comprise entre 30 et 40 pourcent, contre un pourcentage de 45 pourcents pour un alliage or-nickel tel que déposé. De plus, le nickel subsistant a été au moins partiellement oxydé par le traitement acide. Ces modifications chimiques de l'alliage or-nickel sont à l'origine du changement de couleur observé.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. In addition, the remaining nickel has been at least partially oxidized by the acid treatment. These chemical modifications of the gold-nickel alloy are at the origin of the observed color change.

Ainsi a été présenté un procédé de dépôt d'un revêtement de couleur anthracite pour des pièces métalliques, techniquement simple, et procurant un résultat esthétique intéressant. Bien entendu, le procédé de dépôt selon l'invention ne se limite pas aux modes d'exécution qui viennent d'être décrits et diverses modifications et variantes simples peuvent être envisagées par l'homme du métier sans sortir du cadre de l'invention tel que défini par les revendications annexées.Thus was presented a method of depositing an anthracite color coating for metal parts, technically simple, and providing an interesting aesthetic result. Of course, the deposition method according to the invention is not limited to the embodiments that have just been described and various simple modifications and variants can be envisaged by those skilled in the art without departing from the scope of the invention such as defined by the appended claims.

Claims (5)

  1. Galvanic deposition method for an anthracite coloured coating for metallic parts, including a first step of depositing a gold-nickel alloy by means of an electrolytic bath, characterized in that it includes a second step of treating said gold-nickel alloy by means of a diluted acid bath, containing an acid selected from among hydrochloric, hydrofluoric, phosphoric, nitric and sulphuric acid.
  2. Galvanic deposition method according to claim 1, characterized in that the dilution of said acid is comprised between 1 and 50ml/l of concentrate acid.
  3. Method according to any of claims 1 and 2, characterized in that said diluted acid bath contains a mixture of hydrochloric acid and hydrofluoric acid.
  4. Method according to any of claims 1 and 2, characterized in that said diluted acid bath contains hydrochloric acid with the addition of ammonium bifluoride.
  5. Method according to any of claims 1 to 4, characterized in that said diluted acid bath further contains a wetting agent.
EP09155762A 2009-03-20 2009-03-20 Galvanic method for depositing a charcoal grey coating and metal parts with such a coating Active EP2230331B1 (en)

Priority Applications (5)

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EP09155762A EP2230331B1 (en) 2009-03-20 2009-03-20 Galvanic method for depositing a charcoal grey coating and metal parts with such a coating
AT09155762T ATE530680T1 (en) 2009-03-20 2009-03-20 GALVANIC COATING PROCESS FOR APPLYING AN ANTHRACITE-COLORED COATING AND METAL PARTS PROVIDED WITH THIS COATING
JP2010057010A JP5331038B2 (en) 2009-03-20 2010-03-15 Electrochemical deposition method
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 (en) 2009-03-20 2010-03-19 Galvanic method for depositing a charcoal grey coating and metal parts with such a coating

Applications Claiming Priority (1)

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EP09155762A EP2230331B1 (en) 2009-03-20 2009-03-20 Galvanic method for depositing a charcoal grey coating and metal parts with such a coating

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

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