EP3502286B1 - Platinum alloy - Google Patents

Platinum alloy Download PDF

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Publication number
EP3502286B1
EP3502286B1 EP17208872.6A EP17208872A EP3502286B1 EP 3502286 B1 EP3502286 B1 EP 3502286B1 EP 17208872 A EP17208872 A EP 17208872A EP 3502286 B1 EP3502286 B1 EP 3502286B1
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EP
European Patent Office
Prior art keywords
alloy
elements
platinum
alloys
platinum alloy
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EP17208872.6A
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German (de)
French (fr)
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EP3502286A1 (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
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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
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—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 platinum alloy without nickel, without cobalt.
  • the invention also relates to a timepiece, piece of jewelry or jewelry comprising at least one component made from such an alloy.
  • the addition elements will therefore meet a technical constraint specific to the element.
  • the first classical 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.
  • Platinum ruthenium alloys have universal use for jewelry and watchmaking, especially for machined products. Platinum cobalt alloys respond to the technique of lost wax casting. Copper alloys meet an economic demand in the market. Iridium alloys are used in jewelry for their shine. As a result, each alloy only responds to a very limited number of constraints.
  • platinum iridium alloy The disadvantage of a platinum iridium alloy is that, at 95%, the alloy is very soft and does not meet watchmaking constraints. To meet these constraints, some use platinum / iridium alloys with lower platinum titers such as 90%, 85%, or even 80%. The downside of this is that they are no longer punchable under 95%.
  • the patent FR 2381832 A1 refers to alloys of at least 95% platinum, comprising iridium as well as 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 be cast more easily.
  • the patent JP1515724C relates to alloys comprising 80-85% platinum, 0.05% to 5% mischmetal and 1 to 15% in total of elements comprising inter alia iridium, the introduction of mischmetal improving the hardness and the flowability of the alloy.
  • the patent JP1509078C relates to alloys comprising 90-95% of platinum, 0.01% to 3% of Ca or calcium boride and 1 to 15% in total of elements comprising 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 Pd-Co combination increasing the hardness of the alloys.
  • alloys described in these four patents can have chromatically high values of a * and b * and a platinum level sometimes less than 95%, these two characteristics not allowing claim to use said alloys in the field of watchmaking and jewelry.
  • the object of the present invention is therefore to substantially improve the platinum alloys with respect to 95% iridium by providing a platinum alloy without nickel, without cobalt, having mechanical characteristics that meet watchmaking criteria while retaining the color and brightness specific to platinum iridium alloys.
  • Another object of the present invention is to provide a platinum alloy containing 95% iridium without nickel, without cobalt, exhibiting an interesting compromise between good machinability, casting, crimping and polishing. .
  • the present invention relates to a platinum alloy without nickel, without cobalt, 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 alloy complementing each other up to 100%.
  • a platinum alloy is obtained which meets all the criteria required for alloys intended for use in the watchmaking and jewelry field, in particular with regard to its color and its brilliance as well. as its ability to be machined, cast, polished and crimped.
  • the present invention also relates to a timepiece, piece of jewelry or jewelry 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, an applique, a needle, a piece of jewelry, or an accessory.
  • the present invention also relates to the use of an alloy such as defined above in a timepiece, jewelry or fine jewelry.
  • 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 addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.
  • 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 addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.
  • 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 addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.
  • 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 addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.
  • the 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 platinous elements.
  • the platinum alloys according to the invention find a particular application for the production of jewelry or watches timepieces. jewelry.
  • this alloy makes it possible in particular to have a brilliant color as well as sufficient hardness to be machined, cast, crimped and polished.
  • the main elements entering into the composition of the alloy have a purity between 999 and 999.9 per thousand and are deoxidized.
  • the elements of the alloy composition are placed in a crucible which is heated until the elements melt.
  • Heating is carried out in a sealed induction furnace under partial nitrogen pressure.
  • the molten alloy is poured into an ingot mold.
  • the ingot is quenched with water.
  • the hardened ingot is then cold rolled and then annealed.
  • the rate of hardening between each annealing is 66 to 80%.
  • Each annealing lasts 20 to 30 minutes and is carried out between 900 ° C and 1100 ° C under a reducing atmosphere composed of N 2 and H 2 .
  • the cooling after annealing is done by quenching in water.
  • Table 3 gives in particular the indications relating to the Vickers hardness of the alloy in the annealed condition, as well as those of the color measured in a three-axis coordinate system.
  • Alloys N ° 1 to 3 are binary Ptlr alloys on the market which have the drawback of not having an internationally recognized legal title.
  • Alloy N ° 4 is the Pt950lr50 alloy which has the disadvantage of having too low a hardness to be used in the watchmaking field,
  • Alloys Nos. 5 to 9 of the invention have been developed and tested in strain to meet the double constraint of brightness / whiteness and strain capacity required for alloys intended for use in the watchmaking and jewelry industry. , or to have chromatic values such as L ⁇ 87, a * ⁇ 0.7 and b * ⁇ 4.3, as well as 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 meet 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)

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 platinum alloy without nickel, without cobalt. The invention also relates to a timepiece, piece of jewelry or jewelry comprising at least one component made from 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 jewelry. These alloys have the particularity of being mainly used with an internationally recognized title of 95%, which greatly limits the content of the addition elements. The addition elements will therefore meet a technical constraint specific to the element. The first classical 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. Platinum ruthenium alloys have universal use for jewelry and watchmaking, especially for machined products. Platinum cobalt alloys respond to the technique of lost wax casting. Copper alloys meet an economic demand in the market. Iridium alloys are used in jewelry for their shine. 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 iridium alloy is that, at 95%, the alloy is very soft and does not meet watchmaking constraints. To meet these constraints, some use platinum / iridium alloys with lower platinum titers such as 90%, 85%, or even 80%. The downside of this is that they are no longer punchable 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 hardnesses of the platinum alloys as a function of the iridium content in the annealed state. <b> Table 1 </b>: Hardness in the annealed state 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 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, comprising iridium as well as 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 be cast 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% platinum, 0.05% to 5% mischmetal and 1 to 15% in total of elements comprising inter alia iridium, the introduction of mischmetal improving the hardness and the 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 relates to alloys comprising 90-95% of platinum, 0.01% to 3% of Ca or calcium boride and 1 to 15% in total of elements comprising 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 Pd-Co combination 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 can have chromatically high values of a * and b * and a platinum level sometimes less than 95%, these two characteristics not allowing claim to use said alloys in the field of watchmaking and jewelry.

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.The object of the present invention is therefore to substantially improve the platinum alloys with respect to 95% iridium by providing a platinum alloy without nickel, without cobalt, having mechanical characteristics that meet watchmaking criteria while retaining the color and brightness specific to platinum iridium alloys.

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 platinum alloy containing 95% iridium without nickel, without cobalt, exhibiting an interesting compromise between good machinability, casting, crimping and polishing. .

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%.To this end, the present invention relates to a platinum alloy without nickel, without cobalt, 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 alloy complementing each other 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 meeting the aforementioned definition, a platinum alloy is obtained which meets all the criteria required for alloys intended for use in the watchmaking and jewelry field, in particular with regard to its color and its brilliance as well. 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, piece of jewelry or jewelry 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, an applique, a needle, 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 such as defined above in a timepiece, jewelry or fine jewelry.

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 addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.

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 addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.

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 addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.

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 addition elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all the elements of the alloy being completed up to 100%.

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.The 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 platinous 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 a particular application for the production of jewelry or watches timepieces. jewelry. In this application, this alloy makes it possible in particular to have a brilliant color as well as sufficient hardness 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 entering into 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 alloy composition are placed in a crucible which is heated until the elements melt.

Le chauffage est réalisé dans un four à induction étanche sous pression partielle d'azote.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 quenched 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 then annealed. The rate of hardening 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 annealing lasts 20 to 30 minutes and is carried out 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.The cooling after annealing is done by quenching in 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 examples which follow were carried out in accordance with the conditions set out in Table 2 below and all relate to 95% platinum alloys or to market references of platinum alloys. The proportions indicated are expressed as a percentage by weight. <b> Table 2 </b>: Table of the compositions of the alloys tested. Pt Ir At 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.Various properties of the alloys obtained according to Examples No. 1 to No. 9 of Table 2 will be found 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 condition, as well as 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 on Illumination and Lab the three coordinate axes, the L axis measuring the white-black component (black = 0; white = 100), the axis a measuring the red-green component (red = positive values + a; green = negative values -a) and the axis b measuring the yellow-blue component (yellow = positive values + b; blue = negative values -b ). (cf. ISO7724 standard established by the International Commission on Illumination).

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

  • Illuminant : D65
  • Tilt : 10°
  • Mesure : SCI + SCE (spéculaire inclus + exclus)
  • UV : 100%
  • Focale de mesure : 4 mm
  • Etalonnage : corps noir et corps blanc
Tableau 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 colorimetric values are measured with a MINOLTA CM 3610 d device under the following conditions:
  • Illuminant: D65
  • Tilt: 10 °
  • Measurement: SCI + SCE (specular included + excluded)
  • UV: 100%
  • Measuring focal length: 4 mm
  • Calibration: black body and white body
<b> Table 3 </b>: Table of colors and hardness of the alloys tested. L 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 N ° 1 to 3 are binary Ptlr alloys on the market which have the drawback of not having an 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 N ° 4 is the Pt950lr50 alloy which has the disadvantage of having too low a hardness 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.Alloys Nos. 5 to 9 of the invention have been developed and tested in strain to meet the double constraint of brightness / whiteness and strain capacity required for alloys intended for use in the watchmaking and jewelry industry. , or to have chromatic values such as L ≥ 87, a * ≤ 0.7 and b * ≤ 4.3, as well as 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 meet this double constraint.

Claims (7)

  1. Nickel-free and cobalt-free platinum alloy, comprising, expressed by weight, the following elements:
    95.0% to 96.0% of Pt,
    0.5% to 4.5% of Ir
    0.01% to 2% of Au
    0 to 2% of Ge
    0 to 1% of at least one of the alloying elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all of the elements of the alloy adding up to 100%.
  2. Platinum alloy according to claim 1, comprising, 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 alloying elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all of the elements of the alloy adding up to 100%.
  3. Platinum alloy according to claim 2, comprising, 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 alloying elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all of the elements of the alloy adding up to 100%.
  4. Platinum alloy according to claim 3, comprising, 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 alloying elements Ru, Rh, Pd, Sn, Ga, Re, the respective percentages of all of the elements of the alloy adding up to 100%.
  5. Timepiece or piece of jewellery comprising at least one component made from Nickel-free and cobalt-free platinum alloy according to one of claims 1 to 4.
  6. Timepiece or piece of jewellery according to claim 5, characterized in that the component is chosen from the group comprising a watch case, a dial, a bracelet or watch strap, a bracelet or watch strap clasp or buckle, a crown, an index, an applique, a hand, a jewel and an accessory.
  7. Use of an alloy according to one of claims 1 to 4 in a timepiece or piece of jewellery.
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JP2018228754A JP6778732B2 (en) 2017-12-20 2018-12-06 Platinum alloy
CN201811492444.6A CN109943744B (en) 2017-12-20 2018-12-07 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
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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GB144119A (en) 1919-07-04 1920-06-10 Adolph Cohn Improvements in alloys
DE2807587A1 (en) * 1977-02-23 1978-08-24 Johnson Matthey Co Ltd PLATINUM ALLOY
JPS5629641A (en) 1979-08-14 1981-03-25 Tanaka Kikinzoku Kogyo Kk Decorative platinum alloy
JPS5681646A (en) 1979-12-08 1981-07-03 Tanaka Kikinzoku Kogyo Kk Platinum alloy for accessory
JPH061912B2 (en) 1984-12-05 1994-01-05 日本電気株式会社 Frequency shift keying optical transmitter
JP2005029879A (en) * 2003-07-14 2005-02-03 Kuwayama Corp Indium-containing hardened platinum alloy for jewel, and products
JP4426406B2 (en) * 2004-09-03 2010-03-03 株式会社徳力本店 Pt alloy for decoration

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JP6778732B2 (en) 2020-11-04
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CN109943744B (en) 2021-09-24
CN109943744A (en) 2019-06-28
JP2019112715A (en) 2019-07-11

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