CH714243B1 - Electroforming process and part or layer obtained by this method. - Google Patents

Electroforming process and part or layer obtained by this method. Download PDF

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Publication number
CH714243B1
CH714243B1 CH01583/06A CH15832006A CH714243B1 CH 714243 B1 CH714243 B1 CH 714243B1 CH 01583/06 A CH01583/06 A CH 01583/06A CH 15832006 A CH15832006 A CH 15832006A CH 714243 B1 CH714243 B1 CH 714243B1
Authority
CH
Switzerland
Prior art keywords
gold
weight
electroforming
zinc
copper
Prior art date
Application number
CH01583/06A
Other languages
French (fr)
Inventor
Grupp Joachim
Original Assignee
Swatch Group Res & Dev Ltd
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 Swatch Group Res & Dev Ltd filed Critical Swatch Group Res & Dev Ltd
Priority to CH01583/06A priority Critical patent/CH714243B1/en
Priority to KR1020097008807A priority patent/KR101326883B1/en
Priority to CNA2007800368276A priority patent/CN101611176A/en
Priority to JP2009530878A priority patent/JP2010506040A/en
Priority to EP07820883A priority patent/EP2079859A2/en
Priority to US12/444,046 priority patent/US20100024930A1/en
Priority to PCT/EP2007/060506 priority patent/WO2008040761A2/en
Publication of CH714243B1 publication Critical patent/CH714243B1/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
    • C25D1/00—Electroforming
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Abstract

L’invention concerne une pièce électroformée en alliage d’or, dans laquelle l’alliage d’or est composé de 88 à 94% en poids d’or, x% de cuivre et/ou d’argent en poids, et 2x% de zinc en poids, x étant compris entre 2 et 4. L’invention concerne aussi un procédé d’électroformage dans lequel la variation de tension avec le bain revendiqué permet d’obtenir une couche à base d’un alliage d’or, de zinc, et exempt de cadmium, ayant une épaisseur de plusieurs centaines de micromètres.The invention relates to an electroformed piece made of gold alloy, in which the gold alloy is composed of 88 to 94% by weight of gold, x% of copper and / or silver by weight, and 2x% zinc composition by weight, x being between 2 and 4. The invention also relates to an electroforming process in which the variation of tension with the claimed bath makes it possible to obtain a layer based on a gold alloy, zinc, and free of cadmium, having a thickness of several hundred micrometers.

Description

Description [0001] La présente invention concerne un procédé d’électroformage destiné à réaliser des pièces ou des couches à base d’un alliage d’or contenant du zinc, du cuivre et/ou de l’argent, ainsi que des pièces ou couches obtenues par ce procédé. Plus particulièrement, l’invention concerne un tel procédé permettant de déposer sur des substrats des couches épaisses dudit alliage, typiquement de l’ordre de 300 pm.Description: [0001] The present invention relates to an electroforming process for producing parts or layers based on a gold alloy containing zinc, copper and / or silver, as well as parts or layers. obtained by this method. More particularly, the invention relates to such a method for depositing on substrates thick layers of said alloy, typically of the order of 300 pm.

[0002] On connaît déjà des procédés d’électrodéposition d’alliage d’or par une électrolyse dans un bain galvanique alcalin contenant, en plus de l’or et du cuivre, du cadmium. Comme le cadmium est un métal toxique, il est désormais interdit d’utilisation par de nombreuses législations.[0002] Gold alloy electrodeposition processes are already known by electrolysis in an alkaline galvanic bath containing, in addition to gold and copper, cadmium. As cadmium is a toxic metal, it is now banned from use by many laws.

[0003] Pour pallier ce problème, il a déjà été proposé par le document CH 680 927 de remplacer, dans le procédé de dépôt électrolytique d’un alliage d’or classique (Au, Cu, Cd), le cadmium par du zinc.To overcome this problem, it has already been proposed by CH 680 927 to replace, in the electroplating process of a conventional gold alloy (Au, Cu, Cd), cadmium with zinc.

[0004] Toutefois, ce procédé ne décrit que le dépôt de couches d’alliage d’or, de zinc et de cuivre de l’ordre de 10 pm. Par ailleurs, ce document ne fournit aucune information précise sur la composition de l’alliage final déposé.However, this method only describes the deposition of gold, zinc and copper alloy layers of the order of 10 .mu.m. Moreover, this document does not provide any precise information on the composition of the final alloy deposited.

[0005] La présente invention a donc pour but principal de fournir un procédé d’électroformage d’une pièce ou d’une couche à base d’un alliage d’or, de zinc et de cuivre exempt de cadmium, ayant des épaisseurs de plusieurs centaines de micromètres.The present invention therefore has the main purpose of providing a method of electroforming a part or a layer based on a gold alloy, zinc and cadmium-free copper, having thicknesses of several hundred micrometers.

[0006] La présente invention a également pour but de fournir un tel procédé permettant de réaliser de telles couches présentant une dureté améliorée tout en maintenant une bonne ductilité.The present invention also aims to provide such a method for producing such layers having improved hardness while maintaining good ductility.

[0007] A cet effet, l’invention a pour objet un procédé d’électroformage d’une couche d’un alliage d’or comprenant 88 à 94% en poids d’or, x% de cuivre et/ou d’argent en poids, et 2x% de zinc en poids, x étant compris entre 2 et 4 consistant à: - plonger un substrat métallique dans un bain électrolytique alcalin contenant une anode, ledit bain contenant au moins des sels d’or sous forme de cyanure d’or et de potassium, des sels de cuivre sous forme de cyanure de cuivre et/ou des sels d’argent sous forme d’oxyde d’agent, des sels de zinc sous forme d’oxyde de zinc, du cyanure de sodium, de l’hydroxyde de sodium, de l’acide, par exemple de l’acide imminodiacétique et un tensio-actif, ledit substrat formant une cathode, - électroformer ladite couche en créant une tension entre l’anode et la cathode pour réaliser le dépôt des ions métalliques à la surface du substrat - interrompre la tension une fois que l’épaisseur de la couche électrodéposée désirée est atteinte, et dans lequel on fait varier la tension durant l’étape d’électroformage de ladite couche, ce qui permet d’obtenir une cristallisation de la phase a l’or non homogène dans la couche au moment du dépôt. Cette non homogénéité permet notamment de diminuer les défauts de surface de la couche déposée par une superstructure cristalline.For this purpose, the subject of the invention is a process for electroforming a layer of a gold alloy comprising 88 to 94% by weight of gold, x% of copper and / or silver. by weight, and 2x% zinc by weight, x being between 2 and 4 consisting in: - immersing a metal substrate in an alkaline electrolytic bath containing an anode, said bath containing at least gold salts in the form of cyanide d gold and potassium, copper salts in the form of copper cyanide and / or silver salts in the form of oxide agents, zinc salts in the form of zinc oxide, sodium cyanide, sodium hydroxide, acid, for example imminodiacetic acid and a surfactant, said substrate forming a cathode, - electroforming said layer by creating a voltage between the anode and the cathode to make the deposit metal ions on the surface of the substrate - interrupting the voltage once the thickness of the electro layer The desired deposit is reached, and in which the voltage is varied during the electroforming step of said layer, which makes it possible to obtain crystallization of the non-homogeneous gold phase in the layer at the time of deposition. This inhomogeneity makes it possible in particular to reduce the surface defects of the layer deposited by a crystalline superstructure.

[0008] Selon un mode de réalisation préféré du procédé de l’invention, on diminue la tension entre l’anode et la cathode dans la phase finale de l’étape d’électroformage pour augmenter la concentration en or de la zone superficielle de la couche déposée et ainsi renforcer la coloration dorée de la couche déposée.According to a preferred embodiment of the method of the invention, the voltage is reduced between the anode and the cathode in the final phase of the electroforming step to increase the gold concentration of the superficial zone of the deposited layer and thus enhance the golden color of the deposited layer.

[0009] Selon un autre aspect avantageux du procédé de l’invention, l’étape d’électroformage est suivie d’un traitement thermique de recuit compris entre 420 °C et 700 °C pendant au moins 30 minutes et d’une trempe rapide.According to another advantageous aspect of the process of the invention, the electroforming step is followed by an annealing heat treatment of between 420 ° C. and 700 ° C. for at least 30 minutes and rapid quenching. .

[0010] On notera à ce propos qu’il ne faut en aucun cas dépasser la température de la courbe «liquidus» du diagramme de phase Au Zn pour l’alliage considéré car lors de la solidification dans l’eutectique, à partir de la phase liquide, on provoquerait une solidification selon deux phases a, ß ce qui aurait pour conséquence une forte dégradation des propriétés mécaniques après refroidissement. Au cours de ce traitement, la structure cristalline de la couche est partiellement homogénéisée et est ensuite figée dans cette conformation par la trempe rapide qui évite la formation des phases cristallines intermédiaires a1 ou a2 pour l’alliage en question.It should be noted in this connection that in no case should the temperature of the "liquidus" curve of the Au Zn phase diagram be exceeded for the alloy in question because during solidification in the eutectic, starting from liquid phase, it would cause a solidification in two phases a, ß which would result in a sharp degradation of the mechanical properties after cooling. During this treatment, the crystalline structure of the layer is partially homogenized and is then frozen in this conformation by rapid quenching which avoids the formation of the intermediate crystalline phases a1 or a2 for the alloy in question.

[0011] L’invention a également pour objet une pièce électroformée en alliage d’or, caractérisée en ce que l’alliage d’or est composé de 88 à 94% en poids d’or, x% de cuivre et/ou d’argent en poids, et 2x% de zinc en poids, x étant compris entre 2 et 4.The invention also relates to an electroformed piece of gold alloy, characterized in that the gold alloy is composed of 88 to 94% by weight of gold, x% of copper and / or silver by weight, and 2x% zinc by weight, x being between 2 and 4.

[0012] Selon un mode préféré de l’invention, l’alliage est composé de 88% en poids d’or, 8% en poids de zinc et 4% en poids de cuivre.According to a preferred embodiment of the invention, the alloy is composed of 88% by weight of gold, 8% by weight of zinc and 4% by weight of copper.

[0013] L’électroformage est effectué à une température comprise entre 50° et 80°.The electroforming is performed at a temperature between 50 ° and 80 °.

[0014] Selon un mode de réalisation avantageux, le tensio-actif utilisé est un ester phosphonique d’un alcool linéaire ou un ester phosphorique d’un alcool linéaire ou un de ses sels.According to an advantageous embodiment, the surfactant used is a phosphonic ester of a linear alcohol or a phosphoric ester of a linear alcohol or a salt thereof.

Claims (8)

Revendicationsclaims 1. Procédé d’électroformage d’une couche d’un alliage d’or comprenant 88 à 94% en poids d’or, x% de cuivre et/ou d’argent en poids, et 2x% de zinc en poids, x étant compris entre 2 et 4 consistant à: - plonger un substrat métallique dans un bain électrolytique alcalin contenant une anode, ledit bain contenant au moins des sels d’or sous forme de cyanure d’or et de potassium, des sels de cuivre sous forme de cyanure de cuivre et/ou des sels d’argent sous forme d’oxyde d’agent, des sels de zinc sous forme d’oxyde de zinc, du cyanure de sodium, de Phydroxyde de sodium, de l’acide et un tensio-actif, ledit substrat formant une cathode, - électroformer ladite couche en créant une tension entre l’anode et la cathode pour réaliser le dépôt des ions métalliques à la surface du substrat, - interrompre la tension une fois que l’épaisseur de la couche électrodéposée désirée est atteinte, et dans lequel on fait varier la tension durant l’étape d’électroformage de ladite couche.1. A process for electroforming a layer of a gold alloy comprising 88 to 94% by weight of gold, x% of copper and / or silver by weight, and 2x% of zinc by weight, x being between 2 and 4 consisting of: - immersing a metal substrate in an alkaline electrolytic bath containing an anode, said bath containing at least gold salts in the form of cyanide of gold and potassium, copper salts in the form of of copper cyanide and / or silver salts in the form of oxide of agent, zinc salts in the form of zinc oxide, sodium cyanide, sodium hydroxide, acid and a surfactant. said substrate forming a cathode; electroforming said layer by creating a voltage between the anode and the cathode to deposit the metal ions on the surface of the substrate; interrupting the voltage once the thickness of the layer electrodeposition is reached, and in which the voltage is varied during the step electroforming said layer. 2. Procédé selon la revendication 1, caractérisé en ce que l’on diminue la tension dans la phase finale de l’étape d’électroformage pour augmenter la concentration en or de la zone superficielle de la couche déposée.2. Method according to claim 1, characterized in that the voltage is reduced in the final phase of the electroforming step to increase the gold concentration of the surface area of the deposited layer. 3. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que l’étape d’électroformage est suivie d’un traitement thermique de recuit compris entre 420 °C et 700 °C pendant au moins 30 minutes et d’une trempe rapide.3. Method according to any one of the preceding claims, characterized in that the electroforming step is followed by an annealing heat treatment of between 420 ° C and 700 ° C for at least 30 minutes and quenching. fast. 4. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que le tensio-actif est un ester phosphorique d’un alcool linéaire ou, un ester phosphorique d’un alcool linéaire ou un de ses sels.4. Method according to any one of the preceding claims, characterized in that the surfactant is a phosphoric ester of a linear alcohol or a phosphoric ester of a linear alcohol or a salt thereof. 5. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que l’électroformage est effectué à une température comprise entre 40 °C et 80 °C.5. Method according to any one of the preceding claims, characterized in that the electroforming is carried out at a temperature between 40 ° C and 80 ° C. 6. Pièce électroformée en alliage d’or, caractérisée en ce que l’alliage d’or est composé de 88 à 94% en poids d’or, x% de cuivre et/ou d’argent en poids, et 2x% de zinc en poids, x étant compris entre 2 et 4.6. electroformed piece of gold alloy, characterized in that the gold alloy is composed of 88 to 94% by weight of gold, x% of copper and / or silver by weight, and 2x% of zinc by weight, x being between 2 and 4. 7. Pièce électroformée selon la revendication 6, caractérisée en ce que l’alliage est composé de 88% en poids d’or, 8% en poids de zinc et 4% en poids de cuivre.7. electroformed part according to claim 6, characterized in that the alloy is composed of 88% by weight of gold, 8% by weight of zinc and 4% by weight of copper. 8. Pièce électroformée selon la revendication 6 ou 7, caractérisée en ce que l’or dudit alliage est essentiellement formé de sa phase alpha.8. electroformed part according to claim 6 or 7, characterized in that the gold of said alloy is essentially formed of its alpha phase.
CH01583/06A 2006-10-03 2006-10-03 Electroforming process and part or layer obtained by this method. CH714243B1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CH01583/06A CH714243B1 (en) 2006-10-03 2006-10-03 Electroforming process and part or layer obtained by this method.
KR1020097008807A KR101326883B1 (en) 2006-10-03 2007-10-03 Electroforming method and part or layer obtained using said method
CNA2007800368276A CN101611176A (en) 2006-10-03 2007-10-03 Electrocasting method and the product or the layer that obtain by this method
JP2009530878A JP2010506040A (en) 2006-10-03 2007-10-03 Electroforming method and parts or layers obtained by this method
EP07820883A EP2079859A2 (en) 2006-10-03 2007-10-03 Electroforming method and part or layer obtained using said method
US12/444,046 US20100024930A1 (en) 2006-10-03 2007-10-03 Electroforming method and part or layer obtained via the method
PCT/EP2007/060506 WO2008040761A2 (en) 2006-10-03 2007-10-03 Electroforming method and part or layer obtained using said method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH01583/06A CH714243B1 (en) 2006-10-03 2006-10-03 Electroforming process and part or layer obtained by this method.

Publications (1)

Publication Number Publication Date
CH714243B1 true CH714243B1 (en) 2019-04-15

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Family Applications (1)

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CH01583/06A CH714243B1 (en) 2006-10-03 2006-10-03 Electroforming process and part or layer obtained by this method.

Country Status (7)

Country Link
US (1) US20100024930A1 (en)
EP (1) EP2079859A2 (en)
JP (1) JP2010506040A (en)
KR (1) KR101326883B1 (en)
CN (1) CN101611176A (en)
CH (1) CH714243B1 (en)
WO (1) WO2008040761A2 (en)

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CN112725653A (en) * 2020-12-21 2021-04-30 有研亿金新材料有限公司 Novel high-plasticity gold-based electric brush material and preparation method thereof

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Also Published As

Publication number Publication date
KR101326883B1 (en) 2013-11-11
WO2008040761A2 (en) 2008-04-10
US20100024930A1 (en) 2010-02-04
EP2079859A2 (en) 2009-07-22
KR20090069324A (en) 2009-06-30
WO2008040761A3 (en) 2008-11-06
JP2010506040A (en) 2010-02-25
CN101611176A (en) 2009-12-23

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