EP3502286A1 - Platinum alloy - Google Patents

Platinum alloy Download PDF

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Publication number
EP3502286A1
EP3502286A1 EP17208872.6A EP17208872A EP3502286A1 EP 3502286 A1 EP3502286 A1 EP 3502286A1 EP 17208872 A EP17208872 A EP 17208872A EP 3502286 A1 EP3502286 A1 EP 3502286A1
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EP
European Patent Office
Prior art keywords
alloy
elements
platinum
alloys
jewelery
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.)
Granted
Application number
EP17208872.6A
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German (de)
French (fr)
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EP3502286B1 (en
Inventor
Edwina Leoni
Gregory Kissling
Denis Vincent
Stéphane Lauper
Alban Dubach
Gaëtan Villard
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Omega SA
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Omega SA
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Publication date
Application filed by Omega SA filed Critical Omega SA
Priority to EP17208872.6A priority Critical patent/EP3502286B1/en
Priority to US16/211,268 priority patent/US10870906B2/en
Priority to JP2018228754A priority patent/JP6778732B2/en
Priority to CN201811492444.6A priority patent/CN109943744B/en
Publication of EP3502286A1 publication Critical patent/EP3502286A1/en
Application granted granted Critical
Publication of EP3502286B1 publication Critical patent/EP3502286B1/en
Active legal-status Critical Current
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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
    • C22C5/04—Alloys based on a platinum group metal
    • 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
    • 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
    • G04B19/00—Indicating the time by visual means
    • G04B19/04—Hands; Discs with a single mark or the like
    • 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
    • G04B3/00—Normal winding of clockworks by hand or mechanically; Winding up several mainsprings or driving weights simultaneously
    • G04B3/04—Rigidly-mounted keys, knobs or crowns
    • 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
    • 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

Definitions

  • the present invention relates to a nickel-free, cobalt-free platinum alloy.
  • the invention also relates to a timepiece, jewelery or jewelery comprising at least one component made with such an alloy.
  • the elements of addition will thus answer a technical constraint specific to the element.
  • the first conventional addition elements are ruthenium, cobalt, copper, iridium. They can be associated with a second element such as gallium, indium, tin, gold, rhodium, tungsten or palladium.
  • Ruthenium platinum alloys are universally used for jewelery and watchmaking, especially for machined products.
  • Cobalt platinum alloys are based on the technique of lost wax casting. Copper alloys meet an economic demand of the market. Iridium alloys are used in jewelery for their brilliance. As a result, each alloy only responds to a very limited number of constraints.
  • the disadvantage of a platinum alloy with iridium is that at 95%, the alloy is very soft and does not meet the watchmaking constraints. To meet these constraints, some use platinum / iridium alloys at lower platinum titers such as 90%, 85% or even 80%. The disadvantage of this situation is that they are no longer punishable under 95%.
  • the patent FR 2381832 A1 refers to alloys of at least 95% platinum, including iridium and gallium between 1.5% and 3.5% or indium between 0.5 and 3.5% by weight, which lowers the melting point of alloys and allows them to flow more easily.
  • the patent JP1515724C relates to alloys comprising 80-85% of platinum, 0.05% to 5% of mischmetal and 1 to 15% in total of elements including inter alia iridium, the introduction of mischmetal improving the hardness and flowability of the alloy.
  • the patent JP1509078C refers to alloys comprising 90-95% platinum, 0.01% to 3% Ca or calcium boride and 1 to 15% total elements including inter alia iridium.
  • the introduction of boron and calcium boride is useful for improving the flowability as well as for refining the grain size of the alloy.
  • the patent JP S61134134A refers to alloys comprising 84% to 96% platinum, 1 to 15% palladium, 0.5 to 5% Co and 0.1 to 5% iridium, the combination Pd-Co increasing the hardness of the alloys.
  • alloys described in these four patents may chromatically have too high values of a * and b * and a platinum titre sometimes less than 95%, these two characteristics not making it possible to claim to use said alloys in the field of watchmaking and jewelery.
  • Another object of the present invention is to provide a 95% platinum-free nickel-cobalt-free iridium alloy exhibiting an interesting compromise between good machinability, casting, crimping and polishing properties. .
  • the present invention relates to a nickel-free, cobalt-free platinum alloy comprising, expressed by weight, from 95.0 to 96.0% of Pt, from 0.5 to 4.5% of Ir, from 0.01 to 2% of Au, from 0 to 2% of Ge, and from 0 to 1% of at least one of the addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy complementing up to 100%.
  • a platinum alloy is obtained which satisfies all the criteria required for alloys intended to be used in the watchmaking and jewelery fields, particularly with regard to its color and its brilliance. as its ability to be machined, cast, polished and crimped.
  • 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 crown, an index, a wall, a needle, a jewel, or an accessory.
  • the present invention also relates to the use of an alloy such as defined above in a timepiece, jewelery or jewelery.
  • the alloy of the present invention is a 95% nickel-free, cobalt-free platinum alloy.
  • the platinum alloy comprises, expressed by weight, from 95.0 to 96.0% of Pt, from 0.5 to 4.5% of Ir, from 0.01 to 2% of Au, from 0 to 2% of Ge, and from 0 to 1% of at least one of the Ru, Rh, Pd, Sn, Ga, Re additive elements, the respective percentages of all elements of the alloy being up to 100% complete.
  • the platinum alloy comprises, expressed by weight, from 95.0 to 96.0% of Pt, from 2.2 to 4.4% of Ir, from 0.01 to 0.8% of Au, from 0.01 to 1.5% of Ge, and from 0 to 1% of at least one of the Ru, Rh, Pd, Sn, Ga, Re additive elements, the respective percentages of all elements of the alloy being up to 100% complete.
  • the platinum alloy comprises, expressed by weight, from 95.0 to 96.0% of Pt, from 2.9 to 4.3% of Ir, from 0.05 to 0.6% of Au, from 0.01 to 1% of Ge, and from 0 to 1% of at least one of the Ru, Rh, Pd, Sn, Ga, Re additive elements, the respective percentages of all elements of the alloy being up to 100% complete.
  • the platinum alloy comprises, expressed by weight, from 95.0 to 96.0% of Pt, from 3.5 to 4.2% of Ir, from 0.05 to 0.6% of Au, from 0.06 to 0.5% of Ge, and from 0 to 1% of at least one of the Ru, Rh, Pd, Sn, Ga, Re additive elements, the respective percentages of all elements of the alloy being up to 100% complete.
  • Addition elements such as Ru, Rh and Ga can be used to improve the hardness, Sn allows to lower the melting temperature, Re and Pd have the same behavior as the platinum elements.
  • the platinum alloys according to the invention find particular application for the realization of a timepiece of jewelery or jewelry.
  • this alloy allows in particular to have a bright color and hardness sufficient to be machined, cast, crimped and polished.
  • 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 pressure of nitrogen.
  • the molten alloy is cast in an ingot mold.
  • the ingot After solidification, the ingot is subjected to quenching with water.
  • the hardened ingot is then cold rolled and annealed.
  • the hardening rate between each annealing is 66 to 80%.
  • Each anneal lasts 20 to 30 minutes and is between 900 ° C and 1100 ° C under a reducing atmosphere composed of N 2 and H 2 .
  • Cooling after annealing is done by quenching with water.
  • Table 3 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.
  • CIELab CIE being the acronym of the International Commission for Lighting and Lab the three coordinate axes
  • AXA measuring the red-green component
  • blue negative value -b
  • Alloys Nos. 1 to 3 are binary alloys Ptlr of the market which have the drawback of having no internationally recognized legal title.
  • Alloy No. 4 is Pt950lr50 alloy which has the drawback of having a hardness too low to be used in the watchmaking field,
  • the alloys Nos. 5 to 9 of the invention have been developed and tested in deformation to meet the double stress of brightness / whiteness and of the deformation capacity required for alloys intended to be used in the watchmaking and jewelery field. or to present the color values such that L ⁇ 87, a * ⁇ 0.7 and b * ⁇ 4.3, and a hardness between 140 Hv and 220 Hv, and preferably between 140 Hv and 160 Hv.
  • the alloys of the comparative examples do not make it possible to respond to this double constraint.

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

Abstract

L'invention se rapporte à un alliage de platine sans nickel, sans cobalt comprenant, exprimé en poids, de 95.0 à 96.0 % de Pt, de 0.5 à 4.5 % d'Ir, de 0.01 à 2% d'Au, de 0 à 2 % de Ge, et de 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.The invention relates to a nickel-free, cobalt-free platinum alloy comprising, expressed by weight, from 95.0 to 96.0% of Pt, from 0.5 to 4.5% of Ir, from 0.01 to 2% of Au, from 0 to 2% of Ge, and from 0 to 1% of at least one of the addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.

Description

Domaine de l'inventionField of the invention

La présente invention se rapporte à un alliage de platine sans nickel, sans cobalt. 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 platinum 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 plusieurs familles d'alliages à base de platine utilisées en horlogerie et bijouterie. Ces alliages ont la particularité d'être principalement utilisés par un titre internationalement reconnu de 95%, ce qui limite fortement la teneur des éléments d'addition. Les éléments d'addition vont donc répondre à une contrainte technique spécifique à l'élément. Les premiers éléments d'addition classiques sont le ruthénium, le cobalt, le cuivre, l'iridium. Ils peuvent être associés à un deuxième élément tel que le gallium, l'indium, l'étain, l'or, le rhodium, le tungstène ou le palladium. Les alliages de platine au ruthénium ont une utilisation universelle pour la bijouterie et l'horlogerie notamment pour les produits usinés. Les alliages de platine au cobalt répondent à la technique de la coulée par cire perdue. Les alliages au cuivre répondent à une demande économique du marché. Les alliages à l'iridium sont utilisés en bijouterie pour leur éclat. De ce fait, chaque alliage ne répond qu'à un nombre très limité de contraintes.There are several families of platinum-based alloys on the market that are used in watchmaking and jewelery. These alloys have the distinction of being mainly used by an internationally recognized 95% title, which strongly limits the content of the additive elements. The elements of addition will thus answer a technical constraint specific to the element. The first conventional addition elements are ruthenium, cobalt, copper, iridium. They can be associated with a second element such as gallium, indium, tin, gold, rhodium, tungsten or palladium. Ruthenium platinum alloys are universally used for jewelery and watchmaking, especially for machined products. Cobalt platinum alloys are based on the technique of lost wax casting. Copper alloys meet an economic demand of the market. Iridium alloys are used in jewelery for their brilliance. As a result, each alloy only responds to a very limited number of constraints.

L'inconvénient d'un alliage de platine à l'iridium est qu'au titre de 95%, l'alliage est très mou et ne répond pas aux contraintes horlogères. Pour répondre à ces contraintes, certains utilisent des alliages platine/iridium à des titres plus bas en platine tels que 90%, 85%, voire 80%. L'inconvénient de cette situation est qu'ils ne sont plus poinçonnables au titre de 95 %.The disadvantage of a platinum alloy with iridium is that at 95%, the alloy is very soft and does not meet the watchmaking constraints. To meet these constraints, some use platinum / iridium alloys at lower platinum titers such as 90%, 85% or even 80%. The disadvantage of this situation is that they are no longer punishable under 95%.

Le Tableau 1 ci-après mentionne les duretés des alliages de platine en fonction de la teneur en iridium à l'état recuit. Tableau 1 : Dureté à l'état recuit des alliages au platine. Pt80Ir20 Pt85Ir15 Pt900Ir10 Pt95Ir50 242 HV 172 HV 120 HV 76 HV Table 1 below mentions the hardness of platinum alloys as a function of the annealed iridium content. <b> Table 1 </ b>: Annealed Hardness of Platinum Alloys. Pt80Ir20 Pt85Ir15 Pt900Ir10 Pt95Ir50 242 HV 172 HV 120 HV 76 HV

Plusieurs alliages au platine à l'iridium existent sur le marché décrits ci-dessous.Several platinum-to-iridium alloys exist on the market described below.

Le brevet FR 2381832 A1 se rapporte à des alliages d'au moins 95% de platine, comprenant de l'iridium ainsi que du gallium entre 1.5% et 3.5% ou de l'indium entre 0.5 et 3.5% en poids, ce qui baisse le point de fusion des alliages et permet de les couler plus facilement.The patent FR 2381832 A1 refers to alloys of at least 95% platinum, including iridium and gallium between 1.5% and 3.5% or indium between 0.5 and 3.5% by weight, which lowers the melting point of alloys and allows them to flow more easily.

Le brevet JP1515724C se rapporte à des alliages comprenant 80-85% de platine, 0.05% à 5% de mischmétal et 1 à 15 % en total d'éléments comprenant entre autre de l'iridium, l'introduction de mischmétal améliorant la dureté et la coulabilité de l'alliage.The patent JP1515724C relates to alloys comprising 80-85% of platinum, 0.05% to 5% of mischmetal and 1 to 15% in total of elements including inter alia iridium, the introduction of mischmetal improving the hardness and flowability of the alloy.

Le brevet JP1509078C se rapporte à des alliages comprenant 90-95% de platine, 0.01% à 3% de Ca ou borure de calcium et 1 à 15 % en total d'éléments comprenant entre autre de l'iridium. L'introduction de bore et borure de calcium est utile pour améliorer la coulabilité ainsi que pour affiner la taille des grains de l'alliage.The patent JP1509078C refers to alloys comprising 90-95% platinum, 0.01% to 3% Ca or calcium boride and 1 to 15% total elements including inter alia iridium. The introduction of boron and calcium boride is useful for improving the flowability as well as for refining the grain size of the alloy.

Le brevet JP S61134134A se rapporte à des alliages comprenant 84% à 96% de platine, 1 à 15% de palladium, 0.5 à 5% de Co et 0.1 à 5% d'iridium, la combinaison Pd-Co augmentant la dureté des alliages.The patent JP S61134134A refers to alloys comprising 84% to 96% platinum, 1 to 15% palladium, 0.5 to 5% Co and 0.1 to 5% iridium, the combination Pd-Co increasing the hardness of the alloys.

Les alliages décrits dans ces quatre brevets peuvent présenter chromatiquement des valeurs de a* et de b* trop élevées et un titre platine parfois inférieur à 95%, ces deux caractéristiques ne permettant pas de prétendre d'utiliser lesdits alliages dans le domaine de l'horlogerie et bijouterie.The alloys described in these four patents may chromatically have too high values of a * and b * and a platinum titre sometimes less than 95%, these two characteristics not making it possible to claim to use said alloys in the field of watchmaking and jewelery.

Résumé de l'inventionSummary of the invention

La présente invention a donc pour but d'améliorer substantiellement les alliages de platine au titre de 95 % à l'iridium en fournissant un alliage de platine sans nickel, sans cobalt, ayant des caractéristiques mécaniques répondants aux critères horlogers tout en gardant la couleur et la luminosité propres aux alliages de platine à l'iridium.It is therefore an object of the present invention to substantially improve platinum alloys by 95% iridium by providing a nickel-free, cobalt-free platinum alloy having mechanical characteristics that meet the watchmaking criteria while maintaining color and stability. the brightness characteristic of platinum alloys with iridium.

Un autre de but de la présente invention est de fournir un alliage platine au titre de 95% à l'iridium sans nickel, sans cobalt, présentant un compromis intéressant entre une bonne aptitude à l'usinage, au casting, au sertissage et au polissage.Another object of the present invention is to provide a 95% platinum-free nickel-cobalt-free iridium alloy exhibiting an interesting compromise between good machinability, casting, crimping and polishing properties. .

A cet effet, la présente invention se rapporte à un alliage de platine sans nickel, sans cobalt, comprenant, exprimé en poids, de 95.0 à 96.0 % de Pt, de 0.5 à 4.5 % d'Ir, de 0.01 à 2% d'Au, de 0 à 2% de Ge, et de 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, 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 platinum alloy comprising, expressed by weight, from 95.0 to 96.0% of Pt, from 0.5 to 4.5% of Ir, from 0.01 to 2% of Au, from 0 to 2% of Ge, and from 0 to 1% of at least one of the addition elements Ru, Rh, Pd, Sn, Ga, 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 de platine 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 usiné, coulé, poli et serti.With an alloy as defined above, a platinum alloy is obtained which satisfies all the criteria required for alloys intended to be used in the watchmaking and jewelery fields, particularly with regard to its color and its brilliance. as its ability to be machined, cast, polished and crimped.

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, une couronne, un index, une applique, une aiguille, 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 crown, an index, a wall, a needle, 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 such 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 de platine au titre de 95% sans nickel, sans cobalt.The alloy of the present invention is a 95% nickel-free, cobalt-free platinum alloy.

Selon l'invention, l'alliage de platine comporte, exprimé en poids, de 95.0 à 96.0 % de Pt, de 0.5 à 4.5 % d'Ir, de 0.01 à 2% d'Au, de 0 à 2 % de Ge, et de 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.According to the invention, the platinum alloy comprises, expressed by weight, from 95.0 to 96.0% of Pt, from 0.5 to 4.5% of Ir, from 0.01 to 2% of Au, from 0 to 2% of Ge, and from 0 to 1% of at least one of the Ru, Rh, Pd, Sn, Ga, Re additive elements, the respective percentages of all elements of the alloy being up to 100% complete.

Selon une première variante, l'alliage de platine comporte, exprimé en poids, de 95.0 à 96.0 % de Pt, de 2.2 à 4.4 % d'Ir, de 0.01 à 0.8 % d'Au, de 0.01 à 1.5 % de Ge, et de 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.According to a first variant, the platinum alloy comprises, expressed by weight, from 95.0 to 96.0% of Pt, from 2.2 to 4.4% of Ir, from 0.01 to 0.8% of Au, from 0.01 to 1.5% of Ge, and from 0 to 1% of at least one of the Ru, Rh, Pd, Sn, Ga, Re additive elements, the respective percentages of all elements of the alloy being up to 100% complete.

Selon une deuxième variante, l'alliage de platine comporte, exprimé en poids, de 95.0 à 96.0 % de Pt, de 2.9 à 4.3 % d'Ir, de 0.05 à 0.6% d'Au, de 0.01 à 1 % de Ge, et de 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.According to a second variant, the platinum alloy comprises, expressed by weight, from 95.0 to 96.0% of Pt, from 2.9 to 4.3% of Ir, from 0.05 to 0.6% of Au, from 0.01 to 1% of Ge, and from 0 to 1% of at least one of the Ru, Rh, Pd, Sn, Ga, Re additive elements, the respective percentages of all elements of the alloy being up to 100% complete.

Selon une troisième variante, l'alliage de platine comporte, exprimé en poids, de 95.0 à 96.0 % de Pt, de 3.5 à 4.2 % d'Ir, de 0.05 à 0.6 % d'Au, de 0.06 à 0.5 % de Ge, et de 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.According to a third variant, the platinum alloy comprises, expressed by weight, from 95.0 to 96.0% of Pt, from 3.5 to 4.2% of Ir, from 0.05 to 0.6% of Au, from 0.06 to 0.5% of Ge, and from 0 to 1% of at least one of the Ru, Rh, Pd, Sn, Ga, Re additive elements, the respective percentages of all elements of the alloy being up to 100% complete.

Les éléments d'addition, tel que Ru, Rh et Ga peuvent être utilisés pour améliorer la dureté, Sn permet d'abaisser la température de fusion, Re et Pd possèdent le même comportement que les éléments platineux.Addition elements, such as Ru, Rh and Ga can be used to improve the hardness, Sn allows to lower the melting temperature, Re and Pd have the same behavior as the platinum elements.

Les alliages de platine 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'avoir une couleur éclatante ainsi qu'une dureté suffisante pour être usiné, coulé, serti et poli.The platinum alloys according to the invention find particular application for the realization of a timepiece of jewelery or jewelry. In this application, this alloy allows in particular to have a bright color and hardness sufficient to be machined, cast, crimped and polished.

Pour préparer l'alliage de platine 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 platinum 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 entre 900°C et 1100°C sous une atmosphère réductrice composée de N2 et H2.Each anneal lasts 20 to 30 minutes and is between 900 ° C and 1100 ° C under a reducing atmosphere composed of N 2 and H 2 .

Le refroidissement après les recuits se fait par une trempe à l'eau.Cooling after annealing is done by quenching with water.

Les exemples qui vont suivre ont été réalisés conformément aux conditions exposées dans le Tableau 2 ci-dessous et se rapportent tous à des alliages de platine 95% ou à des références d'alliages au platine du marché. Les proportions indiquées sont exprimées en pourcentage en poids. Tableau 2 : Tableau des compositions des alliages testés. Pt Ir Au Ge 1 (comp) 80 20 2 (comp) 85 15 3 (comp) 90 10 4 (comp) 95 5 5 (inv) 95.3 3.5 1 0.2 6 (inv) 95.3 4 0.5 0.2 7 (inv) 95.3 4.5 0.01 0.19 8 (inv) 95.3 4.2 0.01 0.49 9 (inv) 95.3 3.7 0.01 0.99 The following examples have been made in accordance with the conditions set out in Table 2 below and all relate to 95% platinum alloys or platinum alloy references on the market. The proportions indicated are expressed as percentage by weight. <b> Table 2 </ b>: Table of alloy compositions tested. Pt Ir the Ge 1 (comp) 80 20 2 (comp) 85 15 3 (comp) 90 10 4 (comp) 95 5 5 (inv) 95.3 3.5 1 0.2 6 (inv) 95.3 4 0.5 0.2 7 (inv) 95.3 4.5 0.01 0.19 8 (inv) 95.3 4.2 0.01 0.49 9 (inv) 95.3 3.7 0.01 0.99

On trouvera dans le Tableau 3 ci-dessous différentes propriétés des alliages obtenus selon les exemples N°1 à N°9 du Tableau 2.Different properties of the alloys obtained according to Examples Nos. 1 to 9 of Table 2 are given in Table 3 below.

Le Tableau 3 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 3 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 : SCl + SCE (spéculaire inclus + exclus)
  • UV : 100%
  • Focale de mesure : 4 mm
  • Etalonnage : corps noir et corps blanc
Tableau 3 : Tableau des couleurs et de dureté des alliages testés. L a* b* HV 1 (comp) 88.4 0.6 3.4 242 2 (comp) 88.4 0.6 3.7 172 3 (comp) 87.6 0.6 4.0 130 4 (comp) 88.1 0.7 4.0 76 5 (inv) 87.6 0.7 4.2 145 6 (inv) 87.8 0.7 4.1 149 7 (inv) 87.5 0.7 4.3 145 8 (inv) 87.9 0.7 4 200 9 (inv) 87.7 0.7 4.1 210 The color values are measured with a MINOLTA CM 3610 d device under the following conditions:
  • Illuminant: D65
  • Tilt: 10 °
  • Measure: SCl + SCE (specular included + excluded)
  • UV: 100%
  • Focal length: 4 mm
  • Calibration: black body and white body
<b> Table 3 </ b>: Table of colors and hardness of the tested alloys. The at* b * H V 1 (comp) 88.4 0.6 3.4 242 2 (comp) 88.4 0.6 3.7 172 3 (comp) 87.6 0.6 4.0 130 4 (comp) 88.1 0.7 4.0 76 5 (inv) 87.6 0.7 4.2 145 6 (inv) 87.8 0.7 4.1 149 7 (inv) 87.5 0.7 4.3 145 8 (inv) 87.9 0.7 4 200 9 (inv) 87.7 0.7 4.1 210

Les alliages N° 1 à 3 sont des alliages binaires Ptlr du marché qui présentent l'inconvénient de n'avoir pas de titre légal reconnu internationnalement.Alloys Nos. 1 to 3 are binary alloys Ptlr of the market which have the drawback of having no internationally recognized legal title.

L'alliage N°4 est l'alliage Pt950lr50 qui présente l'inconvénient d'avoir une dureté trop faible pour être utilisé dans le domaine horloger,Alloy No. 4 is Pt950lr50 alloy which has the drawback of having a hardness too low to be used in the watchmaking field,

Les alliages N° 5 à 9 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 ≥ 87, a* ≤ 0.7 et b* ≤ 4.3, ainsi qu'une dureté comprise entre 140 Hv et 220 Hv, et de préférence comprise entre 140 Hv et 160 Hv.The alloys Nos. 5 to 9 of the invention have been developed and tested in deformation to meet the double stress of brightness / whiteness and of the deformation capacity required for alloys intended to be used in the watchmaking and jewelery field. or to present the color values such that L ≥ 87, a * ≤ 0.7 and b * ≤ 4.3, and a hardness between 140 Hv and 220 Hv, and preferably between 140 Hv and 160 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 (7)

Alliage de platine sans nickel et sans cobalt, comprenant, exprimé en poids, les éléments suivants : 95.0 à 96 % de Pt, 0.5 à 4.5 % d'Ir 0.01 à 2% d'Au 0 à 2 % de Ge 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%. A nickel-free and cobalt-free platinum alloy, comprising, by weight, the following elements: 95.0 to 96% of Pt, 0.5 to 4.5% of Ir 0.01 to 2% Au 0 to 2% of Ge 0 to 1% of at least one of the addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy completing up to 100%. Alliage de platine selon la revendication 1 comprenant, exprimé en poids, de 95.0 à 96.0 % de Pt, de 2.2 à 4.4 % d'Ir, de 0.01 à 0.8 % d'Au, de 0.01 à 1.5 % de Ge, et de 0 à 1 % d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.Platinum alloy according to claim 1 comprising, expressed by weight, 95.0 to 96.0% of Pt, 2.2 to 4.4% of Ir, 0.01 to 0.8% of Au, 0.01 to 1.5% of Ge, and 0 at 1% of at least one of the addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy completing up to 100%. Alliage de platine selon la revendication 1 comprenant, exprimé en poids, de 95.0 à 96.0 % de Pt, de 2.9 à 4.3 % d'Ir, de 0.05 à 0.6 % d'Au, de 0.01 à 1 % de Ge, et de 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.A platinum alloy according to claim 1 comprising, expressed by weight, 95.0 to 96.0% Pt, 2.9 to 4.3% Ir, 0.05 to 0.6% Au, 0.01 to 1% Ge, and 0 at 1% of at least one of the addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy completing up to 100%. Alliage de platine selon la revendication 1 comprenant, exprimé en poids, de 95.0 à 96.0 % de Pt, de 3.5 à 4.2 % d'Ir, de 0.05 à 0.6 % d'Au, de 0.06 à 0.5 % de Ge, et de 0 à 1% d'au moins un des éléments d'addition Ru, Rh, Pd, Sn, Ga, Re, les pourcentages respectifs de l'ensemble des éléments de l'alliage se complétant jusqu'à 100%.Platinum alloy according to claim 1 comprising, expressed by weight, 95.0 to 96.0% of Pt, 3.5 to 4.2% of Ir, 0.05 to 0.6% of Au, 0.06 to 0.5% of Ge, and 0 at 1% of at least one of the addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy completing up to 100%. Pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé dans un alliage selon l'une des revendications de 1 à 4.Timepiece, jewelery or jewelery comprising at least one component made of an alloy according to one of claims 1 to 4. Pièce d'horlogerie, de bijouterie ou de joaillerie selon la revendication 5, caractérisé en ce que le composant est choisi parmi le groupe comprenant une boite de montre, un cadran, un bracelet, un fermoir de bracelet, une couronne, un index, une applique, une aiguille, un bijou, et un accessoire.Timepiece, jewelery or jewelery according to claim 5, characterized in that the component is selected from the group consisting of a watch case, a dial, a bracelet, a bracelet clasp, a crown, an index, a applique, a needle, a jewel, and an accessory. Utilisation d'un alliage selon l'une des revendications 1 à 4 dans une pièce d'horlogerie, de bijouterie ou de joaillerie.Use of an alloy according to one of claims 1 to 4 in a timepiece, jewelery or jewelery.
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EP4177366A1 (en) * 2021-11-03 2023-05-10 Omega SA Platinum alloy
EP4198157A1 (en) * 2021-12-14 2023-06-21 Nivarox-FAR S.A. Platinum alloy

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CN110527862A (en) * 2019-09-18 2019-12-03 深圳市甘露珠宝首饰有限公司 Platinum alloy and preparation method thereof
CN113322394B (en) * 2021-05-13 2022-03-01 北京有色金属与稀土应用研究所 High-performance bonded platinum alloy fine material for packaging and preparation method thereof

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EP4177366A1 (en) * 2021-11-03 2023-05-10 Omega SA Platinum alloy
EP4198157A1 (en) * 2021-12-14 2023-06-21 Nivarox-FAR S.A. Platinum alloy
US11702722B2 (en) 2021-12-14 2023-07-18 Nivarox-Far S.A. Platinum alloy

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EP3502286B1 (en) 2021-01-27
CN109943744B (en) 2021-09-24

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