EP3070182B1 - White-gold alloy - Google Patents

White-gold alloy Download PDF

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Publication number
EP3070182B1
EP3070182B1 EP15159421.5A EP15159421A EP3070182B1 EP 3070182 B1 EP3070182 B1 EP 3070182B1 EP 15159421 A EP15159421 A EP 15159421A EP 3070182 B1 EP3070182 B1 EP 3070182B1
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free
gold alloy
alloy
alloy according
expressed
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EP15159421.5A
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German (de)
French (fr)
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EP3070182A1 (en
Inventor
Denis Vincent
Polychronis Nakis Karapatis
Gregory Kissling
Stéphane Lauper
Gaëtan Villard
Alban Dubach
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Swatch Group Research and Development SA
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Swatch Group Research and Development SA
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Priority to EP15159421.5A priority Critical patent/EP3070182B1/en
Priority to US15/052,011 priority patent/US11591672B2/en
Priority to JP2016046671A priority patent/JP6280580B2/en
Priority to CN201610146929.4A priority patent/CN105986142B/en
Priority to RU2016109478A priority patent/RU2016109478A/en
Publication of EP3070182A1 publication Critical patent/EP3070182A1/en
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Publication of EP3070182B1 publication Critical patent/EP3070182B1/en
Priority to JP2017222556A priority patent/JP6827909B2/en
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    • 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
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • A44C5/18—Fasteners for straps, chains or the like
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Adornments (AREA)
  • Catalysts (AREA)

Description

Domaine de l'inventionField of the invention

La présente invention se rapporte à un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans cuivre, sans zirconium, sans niobium, sans chrome et sans manganèse. L'invention se rapporte également à une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé avec un tel alliage.The present invention relates to a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free, and manganese-free alloy. The invention also relates to a timepiece, jewelery or jewelery comprising at least one component made with such an alloy.

Arrière-plan de l'inventionBackground of the invention

Il existe sur le marché principalement deux sortes d'alliages d'or gris, les alliages dans lesquels le métal de blanchiment de l'or est le nickel et ceux où ce métal est le palladium. Toutefois les alliages au nickel sont toujours moins utilisés à cause de leurs propriétés allergènes au contact de la peau, ce qui conduit à les exclure de l'habillage horloger pour des composants externes. De ce fait les alliages au palladium sont utilisés pour cette fonction.There are mainly two types of white gold alloys on the market, the alloys in which the gold bleaching metal is nickel and those in which the metal is palladium. However, nickel alloys are still less used because of their allergenic properties in contact with the skin, which leads to their exclusion from the watchmaking for external components. As a result, palladium alloys are used for this function.

Les alliages d'or gris destinés à être utilisés dans les domaines horloger et de la bijouterie doivent répondre à deux contraintes relatives d'une part à leur éclat et blancheur et d'autre part à leur capacité de déformation. Ils doivent pour cela présenter une couleur et un éclat d'une blancheur pure ainsi qu'une excellente ductilité et résistance à la corrosion. Plus particulièrement, les alliages d'or gris recherchés doivent présenter des valeurs selon le modèle chromatique L*a*b (C.I.E. 1976) telles que L ≥ 80, a*<1.5 et b*<7, de préférence b*<6, et préférentiellement b*<5, ainsi qu'une dureté HV comprise entre 140 Hv et 225 Hv, les valeurs les plus basses étant les plus favorables à la déformation.The gray gold alloys for use in the watch and jewelery fields must meet two constraints relating, on the one hand, to their brightness and whiteness and, on the other hand, to their deformation capacity. They must have a color and a brightness of pure whiteness and excellent ductility and corrosion resistance. More particularly, the desired white gold alloys must have values according to the chromatic model L * a * b (CIE 1976) such that L ≥ 80, a * <1.5 and b * <7, preferably b * <6, and preferably b * <5, and an HV hardness of between 140 Hv and 225 Hv, the lowest values being the most favorable to the deformation.

L'effet de blanchiment du palladium étant moindre que celui du nickel, ces alliages ont nécessairement une haute teneur en palladium, ce qui réduit leurs propriétés mécaniques. De plus un rhodiage est souvent utilisé pour améliorer la couleur et la réflectivité des alliages, afin de favoriser l'éclat des pierres lorsque les alliages sont sertis.Since the bleaching effect of palladium is less than that of nickel, these alloys necessarily have a high palladium content, which reduces their mechanical properties. In addition a rhodium is often used to improve the color and reflectivity of alloys, to promote the brilliance of stones when the alloys are crimped.

Cette opération de rhodiage présente un inconvénient majeur à long terme car la couche de rhodium déposée de l'ordre de 1 à 5 microns finit toujours par s'user. Dès lors, le service après-vente se trouve confronté à une opération de rhabillage coûteuse, de part la nécessité de masquer la différence de couleur entre l'alliage et la couche de perfectionnement du rhodium.This rhodium-plating operation has a major disadvantage in the long term because the layer of rhodium deposited on the order of 1 to 5 microns always ends up wearing. As a result, the after-sales service is confronted with an expensive reworking operation because of the need to mask the difference in color between the alloy and the rhodium refining layer.

Ces couleurs peuvent être comparées au travers de quelques références mentionnées ci-dessous. Le brevet EP 0 346 595 se rapporte à des alliages ayant 60-85% Au, 4-20% Pt, 2-20% Pd, 1-11 Ag, et 0.1-3% Ir/Rh. Le brevet EP 1 010 768 se rapporte à des alliages d'or gris 18 carats ayant une teneur en palladium comprise entre 12 et 14 %, et comprenant également du cuivre, ce qui donne des valeurs chromatiques dans le système L, a*, b* telles que 1.8<a*<2.3 et 7<b*<10.These colors can be compared through some references mentioned below. The patent EP 0 346 595 refers to alloys having 60-85% Au, 4-20% Pt, 2-20% Pd, 1-11 Ag, and 0.1-3% Ir / Rh. The patent EP 1 010 768 refers to 18 carat white gold alloys having a palladium content of between 12 and 14%, and also including copper, which gives color values in the L, a *, b * system such that 1.8 <a * <2.3 and 7 <b * <10.

Le brevet EP 1 227 166 se rapporte à des alliages d'or gris 18 carats sans palladium, et comprenant du cuivre et du manganèse, ce qui donne des valeurs chromatiques dans le système L, a*, b* telles que 2.6<a*<6 et 10<b*<13.The patent EP 1 227 166 refers to palladium-free 18K white gold alloys, including copper and manganese, giving color values in the L, a *, b * system such that 2.6 <a * <6 and 10 <b * <13.

Le brevet EP 1 245 688 se rapporte à des alliages d'or gris 18 carats ayant une teneur en palladium comprise entre 5 et 7 %, comprenant également du cuivre et de l'argent, ce qui donne des valeurs chromatiques dans le système L, a*, b*telles que 1.5<a*<4.5 et 10.5<b*<15.2.The patent EP 1,245,688 refers to 18-carat white gold alloys having a palladium content of between 5 and 7%, also including copper and silver, giving chromatic values in the L, a *, b * system that 1.5 <a * <4.5 and 10.5 <b * <15.2.

Les alliages décrits dans ces trois brevets présentent chromatiquement des valeurs de a* et de b* trop élevées pour prétendre éviter une amélioration de la surface par un rhodiage.The alloys described in these three patents chromatically have values of a * and b * too high to claim to avoid an improvement of the surface by a rhodium.

La demande de brevet EP 2 546 371 se rapporte à des alliages d'or gris 18 carats ayant une teneur en palladium comprise entre 2 et 12 % et une teneur en chrome comprise entre 13 et 23 %, ce qui donne des valeurs chromatiques dans le système L, a*, b* telles que 0.25<a*<0.7 et 3<b*<4.2.The patent application EP 2 546 371 refers to gold alloys 18-carat gray with a palladium content between 2 and 12% and a chromium content of between 13 and 23%, which gives chromatic values in the system L, a *, b * such that 0.25 <a * <0.7 and 3 <b * <4.2.

La demande de brevet WO 2010/127458 se rapporte à des alliages d'or gris 18 carats ayant une teneur en palladium comprise entre 18 et 24 % et une teneur en divers éléments dont le Zr, Nb ou Mn comprise entre 1 et 6 %, ce qui donne des valeurs chromatiques dans le système L, a*, b* telles que 1.1 <a*<1.5 et 4.5<b*<5.7.The patent application WO 2010/127458 relates to 18-carat white gold alloys having a palladium content of between 18 and 24% and a content of various elements including Zr, Nb or Mn of between 1 and 6%, which gives chromatic values in the system L, a *, b * such that 1.1 <a * <1.5 and 4.5 <b * <5.7.

Les alliages décrits dans ces deux dernières demandes de brevet présentent chromatiquement des valeurs de a* et de b* suffisantes pour prétendre éviter une amélioration de la surface par un rhodiage. Toutefois ces alliages présentent une dureté trop élevée (cf. alliages N° 2 (370 Hv) et 3 (276 Hv) des tableaux 1 et 2 ci-dessous) pour assurer une facilité d'utilisation lors des déformations de fabrication.The alloys described in these last two patent applications chromatically have values of a * and b * sufficient to claim to avoid an improvement of the surface by a rhodium. However, these alloys have a hardness too high (see alloys No. 2 (370 Hv) and 3 (276 Hv) Tables 1 and 2 below) to ensure ease of use during manufacturing deformations.

Résumé de l'inventionSummary of the invention

La présente invention a donc pour but d'améliorer substantiellement les alliages d'or gris en fournissant un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans cuivre, sans zirconium, sans niobium, sans chrome, et sans manganèse, permettant d'éliminer le rhodiage sans réduire ses propriétés de déformabilité.The object of the present invention is therefore to substantially improve the gray-gold alloys by providing a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free alloy, and without manganese, to eliminate rhodium without reducing its deformability properties.

La présente invention a donc pour but d'améliorer substantiellement les alliages d'or gris en fournissant un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans cuivre, sans zirconium, sans niobium, sans chrome et sans manganèse dont la déformabilité permet sa transformation par les techniques de laminage et d'étirage à froid sans risque de fissuration et qui soit économique à réaliser.The object of the present invention is therefore to substantially improve the gray-gold alloys by providing a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free, and non-nickel free gold alloy. manganese whose deformability allows its transformation by rolling techniques and cold drawing without risk of cracking and which is economical to achieve.

Un autre de but de la présente invention est de fournir un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans cuivre, sans zirconium, sans niobium, sans chrome et sans manganèse présentant un compromis intéressant entre une couleur et un éclat d'une blancheur suffisante pour répondre aux exigences esthétiques du domaine de l'habillage horloger, évitant ainsi une opération de rhodiage, et la résistance à l'oxydation lors d'opérations de traitement thermiques, brasage, soudage, fusion et gravage laser.Another object of the present invention is to provide a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free, and manganese-free gold alloy. interesting compromise between a color and a brightness of a whiteness sufficient to meet the aesthetic requirements of the field of dressing clock, thus avoiding a rhodium-plating operation, and resistance to oxidation during heat treatment operations, soldering, welding, fusion and laser engraving.

Un autre but de la présente invention est de fournir un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans cuivre, sans zirconium, sans niobium, sans chrome et sans manganèse pouvant être facilement poli et d'une grande blancheur après polissage.Another object of the present invention is to provide a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free, and manganese-free gold alloy which can be easily polished and great whiteness after polishing.

A cet effet, la présente invention se rapporte à un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans cuivre, sans zirconium, sans niobium, sans chrome et sans manganèse, comprenant, exprimé en poids, de 75.0 à 76.5 % d'Au, de 15 à 23 % de Pd, de 0.5 à 5 % de Rh, de 0 à 7 % de Pt, et de 0 à 5% d'au moins un des éléments d'addition Ir, Ru, Ti, In, Ga, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.For this purpose, the present invention relates to a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free and manganese-free gold alloy comprising, expressed by weight, 75.0 to 76.5% Au, 15 to 23% Pd, 0.5 to 5% Rh, 0 to 7% Pt, and 0 to 5% of at least one of the Ir addition elements, Ru, Ti, In, Ga, B and Re, the respective percentages of all elements of the alloy completing up to 100%.

Avec un alliage répondant à la définition susmentionnée on obtient un alliage d'or gris répondant à l'ensemble des critères requis pour des alliages destinés à être utilisés dans le domaine horloger et de la bijouterie, notamment pour ce qui concerne sa couleur et son éclat ainsi que son aptitude à être déformé à froid sans risque de fissuration. A cela s'ajoute une excellente résistance à la corrosion.With an alloy as defined above, a gray gold alloy is obtained which satisfies all the criteria required for alloys intended to be used in the watch and jewelery fields, in particular with regard to its color and its brilliance. as well as its ability to be cold deformed without risk of cracking. In addition, there is excellent resistance to corrosion.

La présente invention concerne également une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé dans un alliage tel que défini ci-dessus. Ce composant est par exemple une boite de montre, un cadran, un bracelet, un fermoir de bracelet, un bijou, ou un accessoire.The present invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of an alloy as defined above. This component is for example a watch case, a dial, a bracelet, a bracelet clasp, a jewel, or an accessory.

La présente invention concerne également l'utilisation d'un alliage tel que défini ci-dessus dans une pièce d'horlogerie, de bijouterie ou de joaillerie.The present invention also relates to the use of an alloy as defined above in a timepiece, jewelery or jewelery.

Description détaillée de modes de réalisation préférésDetailed Description of Preferred Embodiments

L'alliage de la présente invention est un alliage d'or gris, sans nickel, sans cobalt, sans fer, sans argent, sans cuivre, sans manganèse, sans zirconium, sans chrome, et sans niobium.The alloy of the present invention is a gray gold alloy, nickel free, cobalt free, iron free, silver free, copper free, manganese free, zirconium free, chromium free, and niobium free.

Selon un premier mode de réalisation, l'alliage d'or est un alliage à 18 carats et comporte, exprimé en poids, de 75.0 à 76.5 % d'Au, de 15 à 23 % de Pd, de 0.5 à 5 % de Rh, de 0 à 7 % de Pt, et de 0 à 5% d'au moins un des éléments d'addition Ir, Ru, Ti, In, Ga, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%. Si le platine est présent, son pourcentage est compris entre 0.5 et 7%.According to a first embodiment, the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 15 to 23% of Pd, from 0.5 to 5% of Rh , from 0 to 7% of Pt, and from 0 to 5% of at least one of the Ir, Ru, Ti, In, Ga, B and Re additive elements, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 0.5 and 7%.

Selon un deuxième mode de réalisation, l'alliage d'or est un alliage à 18 carats et comporte, exprimé en poids, de 75.0 à 76.5 % d'Au, de 17 à 22.5 % de Pd, de 0.5 à 4 % de Rh, de 0 à 6 % de Pt, et de 0 à 5% d'au moins un des éléments d'addition Ir, Ru, Ti, In, Ga, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%. Si le platine est présent, son pourcentage est compris entre 0.5 et 6%.According to a second embodiment, the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 17 to 22.5% of Pd, from 0.5 to 4% of Rh , from 0 to 6% of Pt, and from 0 to 5% of at least one of the Ir, Ru, Ti, In, Ga, B and Re additive elements, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 0.5 and 6%.

Selon un troisième mode de réalisation, l'alliage d'or est un alliage à 18 carats et comporte, exprimé en poids, de 75.0 à 76.5 % d'Au, de 18 à 22.5 % de Pd, de 1,5 et 3 % de Rh, de 0 à 4 % de Pt, et de 0 à 4% d'au moins un des éléments d'addition Ir, Ru, Ti, In, Ga, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%. Si le platine est présent, son pourcentage est compris entre 1 et 4%.According to a third embodiment, the gold alloy is an 18-carat alloy and has, expressed by weight, 75.0 to 76.5% Au, 18 to 22.5% Pd, 1.5 and 3% of Rh, from 0 to 4% of Pt, and from 0 to 4% of at least one of the addition elements Ir, Ru, Ti, In, Ga, B and Re, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 1 and 4%.

Selon un quatrième mode de réalisation, l'alliage d'or est un alliage à 18 carats et comporte, exprimé en poids, de 75.0 à 76.5 % d'Au, de 19 à 22 % de Pd, de 1.5 à 3 % de Rh, de 0 à 4.5 % de Pt, et de 0 à 4.5% d'au moins un des éléments d'addition Ir, Ru, Ti, In, Ga, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%. Si le platine est présent, son pourcentage est compris entre 1 et 4.5%.According to a fourth embodiment, the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 19 to 22% of Pd, from 1.5 to 3% of Rh , from 0 to 4.5% of Pt, and from 0 to 4.5% of at least one of the Ir, Ru, Ti, In, Ga, B and Re addition elements, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 1 and 4.5%.

Selon un cinquième mode de réalisation, l'alliage d'or est un alliage à 18 carats et comporte, exprimé en poids, de 75.0 à 76.5 % d'Au, de 19 à 21.5 % de Pd, de 1.5 à 3 % de Rh, de 0 à 4 % de Pt, et de 0 à 4% d'au moins un des éléments d'addition Ir, Ru, Ti, In, Ga, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%. Si le platine est présent, son pourcentage est compris entre 1 et 4%.According to a fifth embodiment, the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 19 to 21.5% of Pd, from 1.5 to 3% of Rh , from 0 to 4% of Pt, and from 0 to 4% of at least one of the Ir, Ru, Ti, In, Ga, B and Re additive elements, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 1 and 4%.

Selon une variante des modes de réalisation ci-dessus, l'alliage d'or comporte au moins un des éléments Ir, Ti, dans une proportion pour chaque élément comprise entre 0,002 et 1 % en poids.According to a variant of the embodiments above, the gold alloy comprises at least one of the elements Ir, Ti, in a proportion for each element of between 0.002 and 1% by weight.

Dans une variante selon laquelle l'alliage comprend de l'Ir, la proportion d'Ir est de préférence comprise 0,01 et 1 % en poids.In a variant according to which the alloy comprises Ir, the proportion of Ir is preferably between 0.01 and 1% by weight.

Dans une variante selon laquelle l'alliage comprend du Ti, la proportion de Ti est de préférence comprise 20 et 500 ppm.In a variant according to which the alloy comprises Ti, the proportion of Ti is preferably between 20 and 500 ppm.

Dans une variante selon laquelle l'alliage comprend du Re, la proportion de Re est de préférence comprise entre 0,002 et 1 % en poids, et de préférence proche de 0,002% en poids.In a variant according to which the alloy comprises Re, the proportion of Re is preferably between 0.002 and 1% by weight, and preferably close to 0.002% by weight.

Dans une variante selon laquelle l'alliage comprend de l'In, la proportion d'indium est de préférence comprise entre 1 et 4% en poids.In a variant in which the alloy comprises In, the proportion of indium is preferably between 1 and 4% by weight.

Dans une variante selon laquelle l'alliage comprend du Ga, la proportion de Ga est de préférence comprise entre 0.2 et 2% en poids.In a variant in which the alloy comprises Ga, the proportion of Ga is preferably between 0.2 and 2% by weight.

Dans une variante selon laquelle l'alliage comprend du B, la proportion de B est de préférence comprise entre 0,002 et 1 % en poids, et plus préférentiellement comprise entre 0.005 et 0.03% en poids.In a variant in which the alloy comprises B, the proportion of B is preferably between 0.002 and 1% by weight, and more preferably between 0.005 and 0.03% by weight.

Dans une variante selon laquelle l'alliage comprend du Ru, la proportion de Ru est de préférence comprise entre 0,002 et 1 % en poids, et plus préférentiellement comprise entre 0.008 et 0.015% en poids.In a variant according to which the alloy comprises Ru, the proportion of Ru is preferably between 0.002 and 1% by weight, and more preferably between 0.008 and 0.015% by weight.

Les alliages d'or selon invention trouvent une application particulière pour la réalisation de pièce d'horlogerie de bijouterie ou de joaillerie. Dans cette application, cet alliage permet notamment d'éviter le dépôt galvanique de rhodium qui est couramment utilisé dans le domaine horloger et bijoutier pour conférer aux pièces traitées un éclat et une couleur d'une blancheur satisfaisante.The gold alloys according to the invention find a particular application for the realization of a timepiece of jewelery or jewelery. In this application, this alloy makes it possible in particular to avoid the galvanic deposition of rhodium which is commonly used in the watchmaking and jeweler field to give the treated parts a brightness and a color of satisfactory whiteness.

Pour préparer l'alliage d'or gris selon l'invention on procède de la façon suivante :

  • Les principaux éléments entrant dans la composition de l'alliage ont une pureté entre 999 et 999.9 pour mille et sont désoxydés.
To prepare the gray gold alloy according to the invention, the following procedure is carried out:
  • The main elements used in the composition of the alloy have a purity between 999 and 999.9 per thousand and are deoxidized.

On place les éléments de la composition de l'alliage dans un creuset que l'on chauffe jusqu'à fusion des éléments.The elements of the composition of the alloy are placed in a crucible which is heated until the elements are melted.

Le chauffage est réalisé dans un four à induction étanche sous pression partielle d'azote.The heating is carried out in a sealed induction furnace under partial pressure of nitrogen.

L'alliage fondu est coulé dans une lingotière.The molten alloy is cast in an ingot mold.

Après solidification, on fait subir au lingot une trempe à l'eau.After solidification, the ingot is subjected to quenching with water.

Le lingot trempé est ensuite laminé à froid puis recuit. Le taux d'écrouissage entre chaque recuit est de 66 à 80 %.The hardened ingot is then cold rolled and annealed. The hardening rate between each annealing is 66 to 80%.

Chaque recuit dure 20 à 30 minutes et se fait à 900°C sous une atmosphère réductrice composée de N2 et H2.Each anneal lasts 20 to 30 minutes and is at 900 ° C under a reducing atmosphere composed of N 2 and H 2 .

Le refroidissement entre les recuits se fait par une trempe à l'eau.The cooling between annealing is done by quenching with water.

Les exemples qui vont suivre ont été réalisés conformément aux conditions exposées dans le Tableau 1 ci-dessous et se rapportent tous à des alliages d'or gris de 18 carats ou à des références colorimétriques d'alliages du marché. Les proportions indiquées sont exprimées en pourcentage en poids. Tableau 1 N° Au. Pd. Pt. Rh. Ag. Ga. Fe. B. Cu. Ru. Ir. Cr. Mn. Zr. Nb. In. Ti. 1 (comp.) 75.1 24.9 2 (comp.) 75.1 7 3 14.9 3 (comp.) 75.1 19 1.9 2 2 4 (comp.) 75.1 15 6 3.9 5 (comp.) 75.1 21 0.5 3.4 6 (comp.) 75.5 15 9 0.5 7 (comp.) 75.5 14 5 0.5 5 8 (inv.) 76 16 7 1 9 (comp.) 75 24 1 0.01 10 (inv.) 75 23 2 0.01 11 (comp.) 75 23 2 0.01 12 (comp.) 76.5 7.5 15 1 0.01 13 (inv.) 75.1 20.9 2 2 0.01 14 (inv.) 75.1 22.9 2 0.01 15 (comp.) 75.1 20.9 4 16 (inv.) 75.1 17.9 5 2 0.01 17 (inv.) 75.1 21.9 3 0.01 18 (inv.) 75.1 18.9 3 3 0.01 19 (inv.) 75.1 18.3 5 1.6 0.01 20 (inv.) 75.1 21.3 2 1.6 0.01 21 (inv.) 75.5 20.5 1.99 2 0.01 0.01 22 (comp.) 100 The following examples have been made in accordance with the conditions set out in Table 1 below and all relate to 18-carat gray gold alloys or colorimetric references of market alloys. The proportions indicated are expressed as percentage by weight. Table 1 No. At. Pd. Pt. Rh. Ag. Ga. Fe. B. Cu. Ru. Ir. Cr. Min. Zr. Nb. In. Ti. 1 (comp.) 75.1 24.9 2 (comp.) 75.1 7 3 14.9 3 (comp.) 75.1 19 1.9 2 2 4 (comp.) 75.1 15 6 3.9 5 (comp.) 75.1 21 0.5 3.4 6 (comp.) 75.5 15 9 0.5 7 (comp.) 75.5 14 5 0.5 5 8 (inv.) 76 16 7 1 9 (comp.) 75 24 1 0.01 10 (inv.) 75 23 2 0.01 11 (comp.) 75 23 2 0.01 12 (comp.) 76.5 7.5 15 1 0.01 13 (inv.) 75.1 20.9 2 2 0.01 14 (inv.) 75.1 22.9 2 0.01 15 (comp.) 75.1 20.9 4 16 (inv.) 75.1 17.9 5 2 0.01 17 (inv.) 75.1 21.9 3 0.01 18 (inv.) 75.1 18.9 3 3 0.01 19 (inv.) 75.1 18.3 5 1.6 0.01 20 (inv.) 75.1 21.3 2 1.6 0.01 21 (inv.) 75.5 20.5 1.99 2 0.01 0.01 22 (comp.) 100

On trouvera dans le Tableau 2 ci-dessous différentes propriétés des alliages obtenus selon les exemples N °1 à N °22 du Tableau 1.Different properties of the alloys obtained according to Examples Nos. 1 to 22 of Table 1 are given in Table 2 below.

Le Tableau 2 donne en particulier les indications relatives à la dureté Vickers de l'alliage à l'état recuit, ainsi qu'à celles de la couleur mesurée dans un système de coordonnées à trois axes.Table 2 gives in particular the indications relating to the Vickers hardness of the alloy in the annealed state, as well as to those of the color measured in a three-axis coordinate system.

Ce système de mesure à trois dimensions dénommé CIELab, CIE étant le sigle de la Commission Internationale de l'Eclairage et Lab les trois axes de coordonnées, l'axe L mesurant la composante blanc-noir (noir=0 ; blanc =100), l'axa a mesurant la composante rouge-vert (rouge = valeurs positives +a ; vert =valeurs négatives -a) et l'axe b mesurant la composante jaune-bleu (jaune = valeurs positives +b ; bleu =valeurs négatives -b). (cf. norme ISO7724 établie par la Commission Internationale de l'Eclairage).This three-dimensional measuring system called CIELab, CIE being the acronym of the International Commission for Lighting and Lab the three coordinate axes, the L axis measuring the white-black component (black = 0, white = 100), the AXA measuring the red-green component (positive values = red + a; green = negative values -a) and the b-axis measuring the yellow-blue component (positive values = yellow + b; blue = negative value -b ). (see ISO7724 standard issued by the International Commission on Illumination).

Les valeurs colorimétriques sont mesurées avec un appareil MINOLTA CM 3610 d dans les conditions suivantes :

  • Illuminant : D65
  • Tilt : 10°
  • Mesure : SCI + SCE (spéculaire inclus + exclus)
  • UV : 100%
  • Focale de mesure : 4 mm
  • Etalonnage : corps noir et corps blanc
Tableau 2 N° L a* b* Hv 1 (comp.) 80.4 1.2 4.4 117 2 (comp.) 80.9 0.3 2.6 370 3 (comp.) 81.2 1.0 3.9 276 4 (comp.) 82.6 1.5 6.6 122 5 (comp.) 80.3 1.4 5.3 114 6 (comp.) 80.6 1.2 5.0 122 7 (comp.) 80.7 1.4 5.7 128 8 (inv.) 80.7 1.2 5.0 169 9 (comp.) 80.0 1.3 5.1 129 10 (inv.) 80.6 1.2 4.8 147 11 (comp.) 79.9 1.2 5.1 75 12 (comp.) 80.6 1.4 6.2 130 13 (inv.) 80.6 1.2 4.6 149 14 (inv.) 80.3 1.2 4.7 174 15 (comp.) 79.8 1.2 4.6 103 16 (inv.) 81.0 1.1 4.6 175 17 (inv.) 80.8 1.2 4.6 211 18 (inv.) 80.9 1.2 4.6 202 19 (inv.) 81.1 1.2 4.6 147 20 (inv.) 80.7 1.2 4.7 162 21 (inv.) 80.5 1.2 4.6 147 22 (comp.) 90.2 1.0 2.1 - The color values are measured with a MINOLTA CM 3610 d device under the following conditions:
  • Illuminant: D65
  • Tilt: 10 °
  • Measure: SCI + SCE (specular included + excluded)
  • UV: 100%
  • Focal length: 4 mm
  • Calibration: black body and white body
Table 2 No. The at* b * H v 1 (comp.) 80.4 1.2 4.4 117 2 (comp.) 80.9 0.3 2.6 370 3 (comp.) 81.2 1.0 3.9 276 4 (comp.) 82.6 1.5 6.6 122 5 (comp.) 80.3 1.4 5.3 114 6 (comp.) 80.6 1.2 5.0 122 7 (comp.) 80.7 1.4 5.7 128 8 (inv.) 80.7 1.2 5.0 169 9 (comp.) 80.0 1.3 5.1 129 10 (inv.) 80.6 1.2 4.8 147 11 (comp.) 79.9 1.2 5.1 75 12 (comp.) 80.6 1.4 6.2 130 13 (inv.) 80.6 1.2 4.6 149 14 (inv.) 80.3 1.2 4.7 174 15 (comp.) 79.8 1.2 4.6 103 16 (inv.) 81.0 1.1 4.6 175 17 (inv.) 80.8 1.2 4.6 211 18 (inv.) 80.9 1.2 4.6 202 19 (inv.) 81.1 1.2 4.6 147 20 (inv.) 80.7 1.2 4.7 162 21 (inv.) 80.5 1.2 4.6 147 22 (comp.) 90.2 1.0 2.1 -

L'alliage N° 1 est l'alliage binaire Au, Pd 18 carats.Alloy No. 1 is Au binary alloy, 18 carats Pd.

Les alliages N° 2 et 3 sont des alliages de l'art antérieur et présentent l'inconvénient de présenter une dureté trop élevée.Alloys Nos. 2 and 3 are alloys of the prior art and have the disadvantage of having too high a hardness.

Les alliages N° 4 (Or 18 carats à Pd15%) et 5 (Or 18 carats à Pd21 %) sont des références du marché.Alloys N ° 4 (18K gold at Pd15%) and 5 (18K gold at Pd21%) are market references.

L'alliage N° 22 est la référence colorimétrique du rhodiage.Alloy No. 22 is the colorimetric reference of rhodium.

Les alliages d'or gris 18 carats de l'invention ont été élaborés et testés en déformation pour répondre à la double contrainte d'éclat/blancheur et de capacité de déformation requise pour des alliages destinés à être utilisés dans le domaine horloger et de la bijouterie, soit pour présenter les valeurs chromatiques telles que L ≥ 80, a*<1.5 et b*<5, ainsi qu'une dureté HV comprise entre 140 Hv et 225 Hv, et de préférence comprise entre 140 Hv et 180 Hv.The 18-carat white gold alloys of the invention were developed and deformed to meet the dual brightness / whiteness and deformation capacity requirements for alloys for use in the watch and watchmaking industries. jewelery, or to present the color values such as L ≥ 80, a * <1.5 and b * <5, and a HV hardness of between 140 Hv and 225 Hv, and preferably between 140 Hv and 180 Hv.

Les alliages des exemples comparatifs ne permettent pas de répondre à cette double contrainte.The alloys of the comparative examples do not make it possible to respond to this double constraint.

Claims (17)

  1. Grey gold alloy, which is nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free and manganese-free, and comprises, expressed in weight percent, the following elements:
    75.0 to 76.5% of Au,
    15 to 23% of Pd,
    0.5 to 5% of Rh,
    0 to 7% of Pt,
    0 to 5% of at least one of the alloying elements Ir, Ru, Ti, In, Ga, B and Re,
    the respective percentages of all the elements of the alloy adding up to 100%.
  2. Grey gold alloy according to claim 1 comprising, expressed in weight percent, from 0.5 to 7% of Pt.
  3. Grey gold alloy according to claim 1, comprising, expressed in weight percent, from 75.0 to 76.5% of Au, from 17 to 22.5% of Pd, from 0.5 to 4% of Rh, from 0 to 6% of Pt, and from 0 to 5% of at least one of the alloying elements Ir, Ru, Ti, In, Ga, B and Re, the respective percentages of all the alloying elements adding up to 100%.
  4. Grey gold alloy according to claim 3 comprising, expressed in weight percent, from 0.5 to 6% of Pt.
  5. Grey gold alloy according to claim 1, comprising, expressed in weight percent, from 75.0 to 76.5% of Au, from 18 to 22.5% of Pd, from 1.5 to 3% of Rh, from 0 to 4% of Pt, and from 0 to 4% of at least one of the alloying elements Ir, Ru, Ti, In, Ga, B and Re, the respective percentages of all the alloying elements adding up to 100%.
  6. Grey gold alloy according to claim 5 comprising, expressed in weight percent, from 1 to 4% of Pt.
  7. Grey gold alloy according to claim 1, comprising, expressed in weight percent, from 75.0 to 76.5% of Au, from 19 to 22% of Pd, from 1.5 to 3% of Rh, from 0 to 4.5% of Pt, and from 0 to 4.5% of at least one of the alloying elements Ir, Ru, Ti, In, Ga, B and Re, the respective percentages of all the alloying elements adding up to 100%.
  8. Grey gold alloy according to claim 7 comprising, expressed in weight percent, from 1 to 4.5% of Pt.
  9. Grey gold alloy according to claim 1, comprising, expressed in weight percent, from 75.0 to 76.5% of Au, from 19 to 21.5% of Pd, from 1.5 to 3% of Rh, from 0 to 4% of Pt, and from 0 to 4% of at least one of the alloying elements Ir, Ru, Ti, In, Ga, B and Re, the respective percentages of all the alloying elements adding up to 100%.
  10. Grey gold alloy according to claim 9 comprising, expressed in weight percent, from 1 to 4% of Pt.
  11. Grey gold alloy according to any of the preceding claims, characterized in that the alloy comprises at least one of the elements Ir, Ti, in a proportion of each element comprised between 0.002 and 1% by weight.
  12. Grey gold alloy according to any of the preceding claims, characterized in that the alloy comprises between 20 and 500 ppm of Ti.
  13. Grey gold alloy according to any of the preceding claims, characterized in that the alloy comprises between 0.01 and 1% by weight of Ir.
  14. Grey gold alloy according to any of the preceding claims, characterized in that the alloy comprises between 1 and 4% by weight of In.
  15. Timepiece or piece of jewellery comprising at least one component made of a grey gold alloy according to any of claims 1 to 14.
  16. Timepiece or piece of jewellery according to claim 15, characterized in that the component is selected from the group comprising a watch case, a dial, a wristband, a bracelet, a bracelet clasp, a jewel and an accessory.
  17. Use of a grey gold alloy according to any of claims 1 to 14 in a timepiece or piece of jewellery.
EP15159421.5A 2015-03-17 2015-03-17 White-gold alloy Active EP3070182B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP15159421.5A EP3070182B1 (en) 2015-03-17 2015-03-17 White-gold alloy
US15/052,011 US11591672B2 (en) 2015-03-17 2016-02-24 Grey gold alloy
JP2016046671A JP6280580B2 (en) 2015-03-17 2016-03-10 Gray gold alloy
CN201610146929.4A CN105986142B (en) 2015-03-17 2016-03-15 Grey billon
RU2016109478A RU2016109478A (en) 2015-03-17 2016-03-16 GRAY GOLD ALLOY
JP2017222556A JP6827909B2 (en) 2015-03-17 2017-11-20 Gray gold alloy

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EP3339455B1 (en) * 2016-12-20 2020-02-05 Montres Breguet S.A. Grey-gold alloy
DE112018004518T5 (en) 2017-10-19 2020-06-04 Denso Corporation POSITIONING SYSTEM FOR VEHICLES
JP6789528B1 (en) * 2019-09-26 2020-11-25 田中貴金属工業株式会社 Medical Au-Pt-Pd alloy
EP3808865B1 (en) 2019-10-17 2023-01-18 Richemont International S.A. White gold alloy and method for manufacturing same

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US20160273077A1 (en) 2016-09-22
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JP2018048409A (en) 2018-03-29
CN105986142B (en) 2018-09-14
US11591672B2 (en) 2023-02-28
EP3070182A1 (en) 2016-09-21
CN105986142A (en) 2016-10-05
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JP6827909B2 (en) 2021-02-10
RU2016109478A (en) 2017-09-21

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