EP3339455B1 - Grey-gold alloy - Google Patents

Grey-gold alloy Download PDF

Info

Publication number
EP3339455B1
EP3339455B1 EP16205419.1A EP16205419A EP3339455B1 EP 3339455 B1 EP3339455 B1 EP 3339455B1 EP 16205419 A EP16205419 A EP 16205419A EP 3339455 B1 EP3339455 B1 EP 3339455B1
Authority
EP
European Patent Office
Prior art keywords
alloy
free
elements
weight
expressed
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.)
Active
Application number
EP16205419.1A
Other languages
German (de)
French (fr)
Other versions
EP3339455A1 (en
Inventor
Denis Vincent
Stéphane Lauper
Gaëtan Villard
Polychronis Nakis Karapatis
Gregory Kissling
Alban Dubach
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.)
Montres Breguet SA
Original Assignee
Montres Breguet 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 Montres Breguet SA filed Critical Montres Breguet SA
Priority to EP16205419.1A priority Critical patent/EP3339455B1/en
Priority to US15/824,344 priority patent/US10458002B2/en
Priority to JP2017238323A priority patent/JP6740204B2/en
Priority to CN201711345377.0A priority patent/CN108203771B/en
Publication of EP3339455A1 publication Critical patent/EP3339455A1/en
Priority to HK18115041.7A priority patent/HK1255967A1/en
Application granted granted Critical
Publication of EP3339455B1 publication Critical patent/EP3339455B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
    • 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

Definitions

  • the present invention relates to an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese.
  • the invention also relates to a timepiece, a jewelery item comprising at least one component produced with such an alloy.
  • gray gold alloys There are mainly two kinds of gray gold alloys on the market, alloys in which the metal for bleaching gold is nickel and those in which this metal is palladium.
  • nickel alloys are still used less because of their allergenic properties in contact with the skin, which leads to excluding them from watchmaking clothing for external components. Therefore palladium alloys are used for this function.
  • Gray gold alloys intended for use in the watchmaking and jewelry fields must meet two constraints relating on the one hand to their brightness and whiteness and on the other hand to their capacity for deformation. For this, they must have a color and a sheen of pure whiteness as well as excellent ductility and corrosion resistance. More particularly, the gray gold alloys sought must have values according to the chromatic model La * b * (CIE 1976) such that L ⁇ 80, a * ⁇ 1.5 and b * ⁇ 7, preferably b * ⁇ 6, and preferably b * ⁇ 5, as well as a hardness HV of between 140 Hv and 225 Hv, the lowest values being the most favorable to the deformation.
  • La * b * CIE 1976
  • these alloys necessarily have a high palladium content, which limits their mechanical properties.
  • rhodium plating is often used to improve the color and reflectivity of the alloys, in order to promote the shine of the stones when the alloys are set.
  • This rhodium plating operation has a major long-term drawback because the layer of rhodium deposited of the order of 1 to 5 microns always ends up wearing out. Consequently, the after-sales service is faced with an expensive re-dressing operation, due to the need to mask the color difference between the alloy and the rhodium improvement layer.
  • the patent EP 1 010 768 relates to 18-carat white gold alloys with a palladium content of between 12 and 14%, and also comprising copper, which gives chromatic values in the L, a *, b * system such as 1.8 ⁇ a * ⁇ 2.3 and 7 ⁇ b * ⁇ 10.
  • the patent EP 1 227 166 refers to 18 carat white gold alloys without palladium, and comprising copper and manganese, which gives chromatic values in the L, a *, b * system such as 2.6 ⁇ a * ⁇ 6 and 10 ⁇ b * ⁇ 13.
  • the patent EP 1,245,688 relates to 18-carat white gold alloys with a palladium content of between 5 and 7%, also comprising copper and silver, which gives chromatic values in the L, a *, b * system that 1.5 ⁇ a * ⁇ 4.5 and 10.5 ⁇ b * ⁇ 15.2.
  • EP 2,546,371 A1 refers to 18 carat white gold alloys with a palladium content between 2 and 12% and a chromium content between 13 and 23 %, which gives chromatic values in the L, a *, b * system such as 0.25 ⁇ a * ⁇ 0.7 and 3 ⁇ b * ⁇ 4.2.
  • the patent EP 2,427,582 B1 refers to 18-carat white gold alloys with a palladium content between 18 and 24% and a content of various elements including Zr, Nb or Mn 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.
  • the patent application EP 3070182 A1 refers to a gray gold alloy without nickel, without cobalt, without iron, without silver, without copper, without zirconium, without niobium, without chromium and without manganese, comprising, expressed by weight, from 75.0 to 76.5 % of Au, 15 to 23% of Pd, 0.5 to 5% of Rh, 0 to 7% of Pt, and 0 to 5% 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 complementing up to 100%.
  • This alloy by virtue of its precious metal content, can only be exclusively dedicated to the manufacture of components for fine jewelry.
  • the present invention therefore aims to substantially improve gray gold alloys by providing a gray gold alloy without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and manganese-free, eliminating rhodium plating without reducing its deformability properties.
  • the object of the present invention is therefore to substantially improve gray gold alloys by providing a nickel-free gray gold alloy without cobalt, iron-free, silver-free, zirconium-free, niobium-free, chromium-free, indium-free, gallium-free and manganese-free whose deformability allows its transformation by cold rolling and drawing techniques without risk of cracking and which is economical to achieve.
  • Another object of the present invention is to provide an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese presenting an interesting compromise between a color, a brightness of whiteness sufficient to meet the aesthetic requirements of the field of watchmaking, thus avoiding a rhodium plating operation.
  • Another object of the present invention is to provide an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese which can be easily polished and very white after polishing.
  • Another object of the present invention is to provide an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese with costs of weaker elaboration.
  • the present invention relates to an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese, comprising, expressed in weight, from 75.0 to 76.5% of Au, from 15 to 23% of Pd, from 1 to 7% of Cu, and from 0 to 5% of at least one of the addition elements Ir, Ru, B and Re , the respective percentages of all the elements of the alloy complementing up to 100%.
  • the present invention also relates to a timepiece, a jewelery item 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 piece of jewelry, or an accessory.
  • the present invention also relates to the use of an alloy as defined above in a timepiece, of jewelry or of fine jewelry.
  • the alloy of the present invention is a gray gold alloy, nickel free, cobalt free, iron free, silver free, indium free, gallium free, manganese free, zirconium free, chrome free, and niobium free.
  • 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 1 to 7% of Cu , and from 0 to 5% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all of the elements of the alloy complementing up to 100%.
  • 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 2 to 7% of Cu and from 0 to 5% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all of the elements of the alloy complementing up to 100%.
  • the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 18 to 22.5% of Pd, from 2 to 6.5% of Cu , and from 0 to 4% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy complementing up to 100%.
  • the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% Au, from 18.5 to 22% Pd, 2.5 to 6.5% Cu and 0 to 3% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy are supplementing up to 100%.
  • the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 18.5 to 21.5% of Pd, from 3 to 6% of Cu , and from 0 to 2.5% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy complementing up to 100%.
  • 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% of Pd, from 3.5 to 5.5% of Cu , and from 0 to 1.8% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all of the elements of the alloy complementing up to 100%.
  • the gold alloy can also be rhodium-free.
  • the gold alloy can comprise at least one of the elements Ir, B, in a proportion for each element of between 0.002 and 1% by weight.
  • the proportion of B is preferably between 0.002 and 0.2%, and more preferably between 0.08 and 0.2%.
  • the proportion of Ir is preferably between 0.002 and 0.13% by weight.
  • the proportion of Re is preferably between 0.001 and 0.05% by weight, and preferably between 0.001 and 0.002% by weight .
  • the proportion of Ru is preferably between 0.002 and 1% by weight, and more preferentially between 0.008 and 0.015% by weight .
  • the gold alloy according to the invention is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% Au, from 19 to 21% Pd, from 3.5 to 5.5 % of Cu, and from 0.08 to 0.2% of B, the respective percentages of all the elements of the alloy complementing up to 100%.
  • the gold alloys according to the invention find a particular application for the production of timepieces for jewelery or fine jewelry.
  • 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 shine and a color of satisfactory whiteness.
  • the main elements used in the composition of the alloy have a purity between 999 and 999.9 per thousand and are deoxidized.
  • the elements of the composition of the alloy are placed in a crucible which is heated until the elements are melted.
  • the heating is carried out in a sealed induction furnace under partial nitrogen pressure.
  • the molten alloy is poured into an ingot mold.
  • the ingot After solidification, the ingot is subjected to water quenching.
  • the hardened ingot is then cold rolled and then annealed.
  • the rate of work hardening between each annealing is from 66 to 80%.
  • Each annealing lasts 20 to 30 minutes and is carried out at 900 ° C under a reducing atmosphere composed of N 2 and H 2 .
  • Cooling between anneals is done by quenching with water.
  • Table 4 below shows different properties of the alloys obtained according to Examples No. 1 to No. 5 of Table 1.
  • Table 4 gives in particular the indications relating to the Vickers hardness of the alloy in the annealed state, as well as those of the color measured in a coordinate system with three axes.
  • the 18-carat white gold alloys of the invention (examples 4 and 5) were developed and tested in deformation to meet the triple brightness / whiteness constraint, deformation capacity and production cost required for alloys intended for use in the watchmaking and jewelry sector.
  • the alloys therefore have chromatic values such as L ⁇ 80, a * ⁇ 1.5 and b * ⁇ 5.5, a hardness between 140 Hv and 225 Hv, and preferably between 140 Hv and 180 Hv, as well as at a reduced production cost.
  • alloys of the prior art and comparative examples do not make it possible to respond to this triple constraint.

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 zirconium, sans niobium, sans chrome, sans indium, sans gallium 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 an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese. The invention also relates to a timepiece, a jewelery item comprising at least one component produced with such an alloy.

Arrière-plan de l'inventionInvention background

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 kinds of gray gold alloys on the market, alloys in which the metal for bleaching gold is nickel and those in which this metal is palladium. However, nickel alloys are still used less because of their allergenic properties in contact with the skin, which leads to excluding them from watchmaking clothing for external components. Therefore 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 La*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.Gray gold alloys intended for use in the watchmaking and jewelry fields must meet two constraints relating on the one hand to their brightness and whiteness and on the other hand to their capacity for deformation. For this, they must have a color and a sheen of pure whiteness as well as excellent ductility and corrosion resistance. More particularly, the gray gold alloys sought must have values according to the chromatic model La * b * (CIE 1976) such that L ≥ 80, a * <1.5 and b * <7, preferably b * <6, and preferably b * <5, as well as a hardness HV 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 limite 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.As the bleaching effect of palladium is less than that of nickel, these alloys necessarily have a high palladium content, which limits their mechanical properties. In addition, rhodium plating is often used to improve the color and reflectivity of the alloys, in order to promote the shine of the stones when the alloys are set.

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 par 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 long-term drawback because the layer of rhodium deposited of the order of 1 to 5 microns always ends up wearing out. Consequently, the after-sales service is faced with an expensive re-dressing operation, due to the need to mask the color difference between the alloy and the rhodium improvement layer.

Ces couleurs peuvent être comparées au travers de quelques références mentionnées ci-dessous.These colors can be compared through a few references mentioned below.

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.The patent EP 1 010 768 relates to 18-carat white gold alloys with a palladium content of between 12 and 14%, and also comprising copper, which gives chromatic values in the L, a *, b * system such as 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 18 carat white gold alloys without palladium, and comprising copper and manganese, which gives chromatic values in the L, a *, b * system such as 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 relates to 18-carat white gold alloys with a palladium content of between 5 and 7%, also comprising copper and silver, which gives 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 have chromatically too high a * and b * values to claim to avoid an improvement in the surface by rhodium plating.

La demande de brevet publiée sous le numéro EP 2 546 371 A1 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 published under the number EP 2,546,371 A1 refers to 18 carat white gold alloys with a palladium content between 2 and 12% and a chromium content between 13 and 23 %, which gives chromatic values in the L, a *, b * system such as 0.25 <a * <0.7 and 3 <b * <4.2.

Le brevet EP 2 427 582 B1 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 EP 2,427,582 B1 refers to 18-carat white gold alloys with a palladium content between 18 and 24% and a content of various elements including Zr, Nb or Mn 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 370 Hv et 276 Hv
Les tableaux 1 et 2, résument la situation des alliages précédemment décrits dans l'art antérieur -Tableau 1- Au Pd Ag Ga Fe Cu Cr Mn Zr Nb In Zn Si HV A 751 130 3.5 101 15 145 B 751 179 50 19 1 165 C 751 70 10 129 40 188 D 751 70 30 149 370 E 751 190 19 20 20 276 F 751 210 20 19 184 -Tableau 2- L a* b* A 80.0 2.1 7.7 B 86.3 3.5 12.9 C 80.6 3.2 12.2 D 80.9 0.3 2.6 E 81.2 1.0 3.9 F 81.4 1.1 4.3 The alloys described in these last two patent applications have chromatically sufficient values of a * and b * to pretend to avoid an improvement in the surface by rhodium plating. However, these alloys have too high a hardness of 370 Hv and 276 Hv
Tables 1 and 2 summarize the situation of the alloys previously described in the prior art -Table 1- At Pd Ag ga Fe Cu Cr mn Zr Nb in Zn Yes H V AT 751 130 3.5 101 15 145 B 751 179 50 19 1 165 VS 751 70 10 129 40 188 D 751 70 30 149 370 E 751 190 19 20 20 276 F 751 210 20 19 184 The at* b * AT 80.0 2.1 7.7 B 86.3 3.5 12.9 VS 80.6 3.2 12.2 D 80.9 0.3 2.6 E 81.2 1.0 3.9 F 81.4 1.1 4.3

La demande de brevet EP 3070182 A1 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%.The patent application EP 3070182 A1 refers to a gray gold alloy without nickel, without cobalt, without iron, without silver, without copper, without zirconium, without niobium, without chromium and without manganese, comprising, expressed by weight, from 75.0 to 76.5 % of Au, 15 to 23% of Pd, 0.5 to 5% of Rh, 0 to 7% of Pt, and 0 to 5% 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 complementing up to 100%.

Cet alliage, de par sa teneur en métaux précieux, ne peut être exclusivement dédié qu'à la fabrication de composants de haute joaillerie.This alloy, by virtue of its precious metal content, can only be exclusively dedicated to the manufacture of components for fine jewelry.

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 zirconium, sans niobium, sans chrome, sans indium, sans gallium et sans manganèse, permettant d'éliminer le rhodiage sans réduire ses propriétés de déformabilité.The present invention therefore aims to substantially improve gray gold alloys by providing a gray gold alloy without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and manganese-free, eliminating rhodium plating 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 zirconium, sans niobium, sans chrome, sans indium, sans gallium 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 gray gold alloys by providing a nickel-free gray gold alloy without cobalt, iron-free, silver-free, zirconium-free, niobium-free, chromium-free, indium-free, gallium-free and manganese-free whose deformability allows its transformation by cold rolling and drawing techniques 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 zirconium, sans niobium, sans chrome, sans indium, sans gallium et sans manganèse présentant un compromis intéressant entre une couleur, un éclat d'une blancheur suffisante pour répondre aux exigences esthétiques du domaine de l'habillage horloger, évitant ainsi une opération de rhodiage.Another object of the present invention is to provide an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese presenting an interesting compromise between a color, a brightness of whiteness sufficient to meet the aesthetic requirements of the field of watchmaking, thus avoiding a rhodium plating operation.

Un autre but de la présente invention est de fournir un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans zirconium, sans niobium, sans chrome, sans indium, sans gallium et sans manganèse pouvant être facilement poli et d'une grande blancheur après polissage.Another object of the present invention is to provide an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese which can be easily polished and very white after polishing.

Un autre but de la présente invention est de fournir un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans zirconium, sans niobium, sans chrome, sans indium, sans gallium et sans manganèse avec des coûts d'élaboration plus faibles.Another object of the present invention is to provide an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese with costs of weaker elaboration.

A cet effet, la présente invention se rapporte à un alliage d'or gris sans nickel, sans cobalt, sans fer, sans argent, sans zirconium, sans niobium, sans chrome, sans indium, sans gallium et sans manganèse, comprenant, exprimé en poids, de 75.0 à 76.5 % d'Au, de 15 à 23 % de Pd, de 1 à 7 % de Cu, et de 0 à 5% d'au moins un des éléments d'addition Ir, Ru, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.To this end, the present invention relates to an alloy of gray gold without nickel, without cobalt, without iron, without silver, without zirconium, without niobium, without chromium, without indium, without gallium and without manganese, comprising, expressed in weight, from 75.0 to 76.5% of Au, from 15 to 23% of Pd, from 1 to 7% of Cu, and from 0 to 5% of at least one of the addition elements Ir, Ru, B and Re , the respective percentages of all the elements of the alloy complementing 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, son éclat, ses coûts d'élaboration, 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 corresponding to the above definition, a gray gold alloy is obtained which meets all the criteria required for alloys intended for use in the watchmaking and jewelry sector, in particular with regard to its color and its luster. , its development costs, as well as its ability to be deformed cold without risk of cracking. Added to this 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, a jewelery item 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 piece of jewelry, 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, of jewelry or of fine jewelry.

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 indium, sans gallium 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, indium free, gallium free, manganese free, zirconium free, chrome 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 1 à 7% de Cu, et de 0 à 5% d'au moins un des éléments d'addition Ir, Ru, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.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 1 to 7% of Cu , and from 0 to 5% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all of the elements of the alloy complementing up to 100%.

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 2 à 7% de Cu et de 0 à 5% d'au moins un des éléments d'addition Ir, Ru, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.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 2 to 7% of Cu and from 0 to 5% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all of the elements of the alloy complementing up to 100%.

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 2 à 6.5% de Cu, et de 0 à 4% d'au moins un des éléments d'addition Ir, Ru, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.According to a third embodiment, the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 18 to 22.5% of Pd, from 2 to 6.5% of Cu , and from 0 to 4% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy complementing up to 100%.

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 18.5 à 22 % de Pd, de 2.5 à 6.5% de Cu et de 0 à 3% d'au moins un des éléments d'addition Ir, Ru, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.According to a fourth embodiment, the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% Au, from 18.5 to 22% Pd, 2.5 to 6.5% Cu and 0 to 3% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy are supplementing up to 100%.

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 18.5 à 21.5 % de Pd, de 3 à 6 % de Cu, et de 0 à 2.5% d'au moins un des éléments d'addition Ir, Ru, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.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 18.5 to 21.5% of Pd, from 3 to 6% of Cu , and from 0 to 2.5% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy complementing up to 100%.

Selon un sixième 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 % de Pd, de 3.5 à 5.5 % de Cu, et de 0 à 1.8% d'au moins un des éléments d'addition Ir, Ru, B et Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.According to a sixth 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% of Pd, from 3.5 to 5.5% of Cu , and from 0 to 1.8% of at least one of the addition elements Ir, Ru, B and Re, the respective percentages of all of the elements of the alloy complementing up to 100%.

Selon une variante des modes de réalisation ci-dessus, l'alliage d'or peut en outre être sans rhodium.According to a variant of the above embodiments, the gold alloy can also be rhodium-free.

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

Dans l'une quelconque des variantes des modes de réalisation ci-dessus selon laquelle l'alliage comprend du B, la proportion de B est de préférence comprise entre 0,002 et 0.2 %, et plus préférentiellement comprise entre 0.08 et 0.2%.In any one of the variants of the above embodiments according to which the alloy comprises B, the proportion of B is preferably between 0.002 and 0.2%, and more preferably between 0.08 and 0.2%.

Dans l'une quelconque des variantes des modes de réalisation ci-dessus selon laquelle l'alliage comprend de l'Ir, la proportion d'Ir est de préférence comprise entre 0,002 et 0.13 % en poids.In any one of the variants of the above embodiments according to which the alloy comprises Ir, the proportion of Ir is preferably between 0.002 and 0.13% by weight.

Dans l'une quelconque des variantes des modes de réalisation ci-dessus selon laquelle l'alliage comprend du Re, la proportion de Re est de préférence comprise entre 0,001 et 0.05 % en poids, et de préférence comprise entre 0.001 et 0,002% en poids.In any one of the variants of the above embodiments according to which the alloy comprises Re, the proportion of Re is preferably between 0.001 and 0.05% by weight, and preferably between 0.001 and 0.002% by weight .

Dans l'une quelconque des variantes des modes de réalisation ci-dessus 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 any one of the variants of the above embodiments according to which the alloy comprises Ru, the proportion of Ru is preferably between 0.002 and 1% by weight, and more preferentially between 0.008 and 0.015% by weight .

Selon une composition particulièrement préférée, l'alliage d'or selon l'invention est un alliage à 18 carats et comporte, exprimé en poids, de 75.0 à 76.5 % d'Au, de 19 à 21 % de Pd, de 3.5 à 5.5 % de Cu, et de 0.08 à 0.2% de B, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.According to a particularly preferred composition, the gold alloy according to the invention is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% Au, from 19 to 21% Pd, from 3.5 to 5.5 % of Cu, and from 0.08 to 0.2% of B, the respective percentages of all the elements of the alloy complementing up to 100%.

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 production of timepieces for jewelery or fine jewelry. 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 shine 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 procedure is as follows:
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 nitrogen pressure.

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

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

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 then annealed. The rate of work hardening between each annealing is from 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 annealing lasts 20 to 30 minutes and is carried out 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.Cooling between anneals is done by quenching with water.

Les exemples qui vont suivre ont été réalisés conformément aux conditions exposées dans le Tableau 3 ci-dessous et se rapportent tous à des alliages d'or gris de 18 carats, réalisés à titre comparatif (exemples 1 à 3) et conformément à l'invention (exemples 4 et 5). Les proportions indiquées sont exprimées en pourcentage en poids. -Tableau 3 - Au Pd B Cu N° % % % % 1 (comp.) 75.1 15 0 9.9 2 (comp.) 75.1 17.5 0 7.4 3 (comp.) 75.1 24.9 0 0 4 (inv.) 75.2 20 0.13 4.67 5 (inv.) 75.1 19.5 0.08 5.31 The examples which follow were carried out in accordance with the conditions set out in Table 3 below and all relate to 18-carat white gold alloys, produced for comparison (examples 1 to 3) and in accordance with the invention (examples 4 and 5). The proportions indicated are expressed as a percentage by weight. -Table 3 - At Pd B Cu No. % % % % 1 (comp.) 75.1 15 0 9.9 2 (comp.) 75.1 17.5 0 7.4 3 (comp.) 75.1 24.9 0 0 4 (inv.) 75.2 20 0.13 4.67 5 (inv.) 75.1 19.5 0.08 5.31

On trouvera dans le Tableau 4 ci-dessous différentes propriétés des alliages obtenus selon les exemples N°1 à N°5 du Tableau 1.Table 4 below shows different properties of the alloys obtained according to Examples No. 1 to No. 5 of Table 1.

Le Tableau 4 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 4 gives in particular the indications relating to the Vickers hardness of the alloy in the annealed state, as well as those of the color measured in a coordinate system with three axes.

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 measurement system called CIELab, CIE being the acronym of the International Lighting Commission and Lab the three coordinate axes, the L axis measuring the white-black component (black = 0; white = 100), axa a measuring the red-green component (red = values positive + a; green = negative values -a) and axis b measuring the yellow-blue component (yellow = positive values + b; blue = negative values -b). (cf. ISO7724 standard established by the International Commission on Lighting).

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 4 - N° L a* b* Dureté Hv 1 (comp.) 80.15 1.72 6.28 128 2 (comp.) 80.31 1.50 5.79 122 3 (comp.) 80.44 1.19 4.41 117 4 (inv.) 80.49 1.46 5.21 174 5 (inv.) 80.70 1.41 5.25 163 The colorimetric values are measured with a MINOLTA CM 3610 d instrument 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 4 - No. The at* b * Hv hardness 1 (comp.) 80.15 1.72 6.28 128 2 (comp.) 80.31 1.50 5.79 122 3 (comp.) 80.44 1.19 4.41 117 4 (inv.) 80.49 1.46 5.21 174 5 (inv.) 80.70 1.41 5.25 163

Les alliages d'or gris 18 carats de l'invention (exemples 4 et 5) ont été élaborés et testés en déformation pour répondre à la triple contrainte d'éclat/blancheur, de capacité de déformation et de coût d'élaboration requise pour des alliages destinés à être utilisés dans le domaine horloger et de la bijouterie. Les alliages présentent dès lors des valeurs chromatiques telles que L ≥ 80, a*<1.5 et b*<5.5, une dureté comprise entre 140 Hv et 225 Hv, et de préférence comprise entre 140 Hv et 180 Hv, ainsi qu'à un coût d'élaboration réduit.The 18-carat white gold alloys of the invention (examples 4 and 5) were developed and tested in deformation to meet the triple brightness / whiteness constraint, deformation capacity and production cost required for alloys intended for use in the watchmaking and jewelry sector. The alloys therefore have chromatic values such as L ≥ 80, a * <1.5 and b * <5.5, a hardness between 140 Hv and 225 Hv, and preferably between 140 Hv and 180 Hv, as well as at a reduced production cost.

Les alliages de l'art antérieur et des exemples comparatifs (exemples 1 à 3) ne permettent pas de répondre à cette triple contrainte.The alloys of the prior art and comparative examples (examples 1 to 3) do not make it possible to respond to this triple constraint.

Claims (14)

  1. Grey gold alloy, which is nickel-free, cobalt-free, iron-free, silver-free, zirconium-free, niobium-free, chromium-free, indium-free, gallium-free and manganese-free, comprising, expressed in weight percent, the following elements:
    75.0 to 76.5% of Au,
    15 to 23% of Pd,
    1 to 7% of Cu,
    0 to 5% of at least one of the alloying elements Ir, Ru, 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 75.0 to 76.5% of Au, from 17 to 22.5% of Pd, from 2 to 7% of Cu, and from 0 to 5% of at least one of the alloying elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy adding up to 100%.
  3. 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 2 to 6.5% of Cu, and from 0 to 4% of at least one of the alloying elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy adding up to 100%.
  4. Grey gold alloy according to claim 1, comprising, expressed in weight percent, from 75.0 to 76.5% of Au, from 18.5 to 22.5% of Pd, from 2 to 6.5% of Cu, and from 0 to 3% of at least one of the alloying elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy adding up to 100%.
  5. Grey gold alloy according to claim 1, comprising, expressed in weight percent, from 75.0 to 76.5% of Au, from 18.5 to 21.5% of Pd, from 3 to 6% of Cu, and from 0 to 2.5% of at least one of the alloying elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy adding up to 100%.
  6. Grey gold alloy according to claim 1, comprising, expressed in weight percent, from 75.0 to 76.5% of Au, from 19 to 21% of Pd, from 3.5 to 5.5% of Cu, and from 0 to 1.8% of at least one of the alloying elements Ir, Ru, B and Re, the respective percentages of all the elements of the alloy adding up to 100%.
  7. Alloy according to any of the preceding claims, characterized in that the alloy comprises at least one of the elements Ir, B, each element being in a proportion comprised between 0.002 and 1% by weight.
  8. Alloy according to any of the preceding claims, characterized in that the alloy comprises between 0.002 and 0.2% by weight of B.
  9. Alloy according to any of the preceding claims, characterized in that the alloy comprises between 0.002 and 0.13% by weight of Ir.
  10. Alloy according to any of the preceding claims, characterized in that the alloy comprises between 0.001 and 0.05% by weight of Re.
  11. Alloy according to any of the preceding claims, characterized in that the alloy comprises between 0.002 and 1% by weight of Ru.
  12. Timepiece or piece of jewellery comprising at least one component made of an alloy according to any of claims 1 to 11.
  13. Timepiece or piece of jewellery according to claim 12, characterized in that the component is selected from the group comprising a watch case, a dial, a bracelet or wristband, a bracelet clasp, a jewel and an accessory.
  14. Use of an alloy according to any of claims 1 to 11 in a timepiece or piece of jewellery.
EP16205419.1A 2016-12-20 2016-12-20 Grey-gold alloy Active EP3339455B1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP16205419.1A EP3339455B1 (en) 2016-12-20 2016-12-20 Grey-gold alloy
US15/824,344 US10458002B2 (en) 2016-12-20 2017-11-28 Grey gold alloy
JP2017238323A JP6740204B2 (en) 2016-12-20 2017-12-13 Gray gold alloy
CN201711345377.0A CN108203771B (en) 2016-12-20 2017-12-15 Gray gold alloy
HK18115041.7A HK1255967A1 (en) 2016-12-20 2018-11-23 Grey gold alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP16205419.1A EP3339455B1 (en) 2016-12-20 2016-12-20 Grey-gold alloy

Publications (2)

Publication Number Publication Date
EP3339455A1 EP3339455A1 (en) 2018-06-27
EP3339455B1 true EP3339455B1 (en) 2020-02-05

Family

ID=57609721

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16205419.1A Active EP3339455B1 (en) 2016-12-20 2016-12-20 Grey-gold alloy

Country Status (5)

Country Link
US (1) US10458002B2 (en)
EP (1) EP3339455B1 (en)
JP (1) JP6740204B2 (en)
CN (1) CN108203771B (en)
HK (1) HK1255967A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3604626A1 (en) * 2018-08-03 2020-02-05 COVENTYA S.p.A. Electroplating bath for depositing a black alloy, method for the electrochemical deposition of a black alloy on a substrate, a black alloy and an article coated with such black alloy
EP3812477B1 (en) * 2019-10-21 2023-01-11 Richemont International SA Metal alloy comprising gold

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2751547C2 (en) * 1977-11-18 1979-11-08 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Gold alloy for firing porcelain for dental purposes
JP3126926B2 (en) * 1996-09-09 2001-01-22 新日本製鐵株式会社 Gold alloy fine wire for semiconductor element and semiconductor device
ES2195300T3 (en) 1998-12-14 2003-12-01 Metalor Technologies Int GRAY GOLD ALLOY WITHOUT NICKEL.
JP2001207226A (en) * 2000-01-25 2001-07-31 Kyocera Corp 18-carat gold alloy
DE60141941D1 (en) 2001-01-26 2010-06-10 Metalor Technologies Int Gray gold alloy
US6913656B2 (en) * 2003-08-11 2005-07-05 Ivoclar Vivadent, Inc. High gold alloy for porcelain fused to metal dental restorations
JP2006233233A (en) * 2005-02-22 2006-09-07 Ijima Kingin Kogyo Kk Gold alloy
US7959855B2 (en) * 2006-10-19 2011-06-14 Heru Budihartono White precious metal alloy
EP2251444A1 (en) * 2009-05-06 2010-11-17 Rolex Sa Grey gold alloy with no nickel and no copper
DE102009053567A1 (en) * 2009-11-10 2011-05-12 Wieland Dental + Technik Gmbh & Co. Kg White gold jewelry alloy useful for producing a semi-finished product for jewelry industry, comprises gold, palladium, copper, tantalum/niobium, first further metal such as silver and platinum, and a second further metal such as gallium
CN101921925B (en) * 2010-09-08 2011-11-23 深圳市金福珠宝首饰有限公司 Gold alloy and preparation method thereof
DK2546371T3 (en) 2011-07-12 2017-04-03 Cendres + Métaux Sa 18 carat gray gold
JP5825482B2 (en) * 2011-11-08 2015-12-02 福井めがね工業株式会社 White Au alloy
JP2014530962A (en) * 2011-11-08 2014-11-20 ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド Gold watch or jewelry
EP3020835B1 (en) * 2014-11-17 2021-04-21 Omega SA Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy
EP3070182B1 (en) * 2015-03-17 2017-08-30 The Swatch Group Research and Development Ltd. White-gold alloy
EP3315620B1 (en) * 2016-10-25 2020-06-24 Nivarox-FAR S.A. Non-magnetic precious alloy for clockmaking applications

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
HK1255967A1 (en) 2019-09-06
US20180171436A1 (en) 2018-06-21
CN108203771A (en) 2018-06-26
JP6740204B2 (en) 2020-08-12
CN108203771B (en) 2021-04-20
US10458002B2 (en) 2019-10-29
JP2018100448A (en) 2018-06-28
EP3339455A1 (en) 2018-06-27

Similar Documents

Publication Publication Date Title
EP3070182B1 (en) White-gold alloy
EP2427582B1 (en) Grey gold alloy with no nickel and no copper
EP3502286B1 (en) Platinum alloy
EP3339455B1 (en) Grey-gold alloy
EP2546371B1 (en) 18-carat grey gold
EP1227166B1 (en) Grey gold alloy
CH714477A2 (en) Platinum alloy.
EP3020835B1 (en) Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy
CH710877B1 (en) Gray gold alloy.
CH709923A2 (en) gold alloy.
CH713263A2 (en) White gold alloy.
CH684616B5 (en) gray gold alloy and use of this alloy.
JP2009057625A (en) White gold alloy, method for producing the same, and jewel using white gold alloy
EP3808865B1 (en) White gold alloy and method for manufacturing same
CH710389A2 (en) Palladium-based alloy.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190102

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 5/02 20060101AFI20190516BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

INTG Intention to grant announced

Effective date: 20190628

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190628

INTG Intention to grant announced

Effective date: 20190709

INTG Intention to grant announced

Effective date: 20190718

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20190729

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: ICB INGENIEURS CONSEILS EN BREVETS SA, CH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1229946

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016029065

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200505

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200628

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200605

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200506

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200505

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016029065

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1229946

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200205

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20201106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201220

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20230101

Year of fee payment: 7

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230611

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231124

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231122

Year of fee payment: 8

Ref country code: DE

Payment date: 20231121

Year of fee payment: 8