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EP3020835B1 - Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy - Google Patents

Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy Download PDF

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Publication number
EP3020835B1
EP3020835B1 EP14193495.0A EP14193495A EP3020835B1 EP 3020835 B1 EP3020835 B1 EP 3020835B1 EP 14193495 A EP14193495 A EP 14193495A EP 3020835 B1 EP3020835 B1 EP 3020835B1
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EP
European Patent Office
Prior art keywords
palladium
alloy
alloys
rhodium
jewelry
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.)
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Application number
EP14193495.0A
Other languages
German (de)
French (fr)
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EP3020835A1 (en
Inventor
Gregory Kissling
Denis Vincent
Stéphane Lauper
Gaëtan Villard
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.)
Omega SA
Original Assignee
Omega 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 Omega SA filed Critical Omega SA
Priority to EP14193495.0A priority Critical patent/EP3020835B1/en
Priority to US14/922,264 priority patent/US20160138134A1/en
Priority to JP2015215461A priority patent/JP2016098437A/en
Priority to CN201510783813.7A priority patent/CN105603241B/en
Priority to CN201810787163.7A priority patent/CN108728684B/en
Publication of EP3020835A1 publication Critical patent/EP3020835A1/en
Priority to JP2017234867A priority patent/JP2018090909A/en
Priority to JP2020218662A priority patent/JP7529563B2/en
Application granted granted Critical
Publication of EP3020835B1 publication Critical patent/EP3020835B1/en
Priority to US18/750,903 priority patent/US20240344179A1/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
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • 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

Definitions

  • the invention relates to a timepiece, piece of jewelry or jewelry comprising at least one component made from a palladium alloy.
  • the 18k white gold and silver alloys are mostly rhodium plated, the 950 ⁇ platinum alloys are very white but very expensive, due to the high platinum content and the high cost of platinum.
  • Palladium alloys known to date have a color that is too gray, not white enough, and pure rhodium, in the solid state, is difficult to cold deform, its melting point being high.
  • the Platinum Metal Journal (2013, 57, (3), 202-213 ) describes the main colorimetric characteristics of the precious alloys presented in Table 1, according to the L * a * b chromatic model (CIE 1976). Table 1: Colorimetric values of precious metal alloys. Platinum Metal Journal (2013, 57, (3), 202-213) L a * green-red b * yellow-blue Platinum alloys and platinum group alloys 85 0 4.5 Pure silver 95 -0.5 4.2 18k white gold 84 0 9.5 14k white gold 84 -0.5 9
  • the patent application WO 2010/127458 discloses a nickel-free and copper-free, gold-based gray gold alloy comprising palladium as well as a number of addition elements used to improve various properties of alloys.
  • the alloys obtained advantageously exhibit colorimetric values whose chromaticity (a *; b *) is slightly lower than the 18-carat binary gold-palladium alloy, but while remaining gray (L> 81).
  • the patent application EP 2,546,371 discloses a white gold alloy based on gold and comprising chromium as well as a number of addition elements used to improve various properties of the alloys.
  • the alloys obtained exhibit colorimetric values which are exceptional as regards chromaticity, and interesting for the L value (> 83).
  • the addition elements used are relatively reactive to the processes used by traditional jewelry, in particular the torch, by producing oxides which obstruct the much sought-after shine, indicated by the high L value.
  • the document GB 1 128 136 discloses an anode produced either in an alloy of palladium and platinum with a percentage by weight of palladium of between 5 and 80% and of platinum of between 95 and 20%, or of an alloy of palladium and rhodium with, by weight, a percentage of palladium between 3 and 80% and rhodium between 97 and 20%.
  • the object of the invention is in particular to overcome the various drawbacks of known alloys.
  • an objective of the invention is to provide very white alloys, close to the color of rhodium, economical, which can be marked with a legal hallmark, with a lower melting ( ⁇ 1750 ° C), and a resistance. to oxidation allowing the use of classic jewelry techniques
  • Another objective of the invention is to provide nickel-free precious metal alloys which therefore respond favorably to the regulations on the release of nickel.
  • the present invention relates to a timepiece, piece of jewelry or jewelry comprising at least one component made of a palladium-based alloy comprising, expressed by weight: between 50 and 55% of palladium, between 45% and 50% rhodium; a quantity x of silver, where 0% ⁇ x ⁇ 5%, and a quantity R of a residue comprising at least one element chosen from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and their combinations, where 0% ⁇ R ⁇ 5%.
  • x is less than or equal to 2%.
  • the alloy may comprise, expressed by weight: between 50 and 53% palladium, between 47% and 50% rhodium; a quantity x of silver, where 0% ⁇ x ⁇ 2%, and a quantity R of a residue comprising at least one element chosen from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and their combinations, where 0% ⁇ R ⁇ 3%.
  • x is equal to 0.
  • R is less than or equal to 1%, preferably less than or equal to 0.5%, and more preferably less than or equal to 0.1%.
  • R is equal to 0.
  • x and R are equal to 0.
  • the alloys according to the invention are very white, can be marked with a legal hallmark, and have the appropriate properties allowing use in the field of watchmaking, jewelry or jewelry.
  • the present invention relates to a timepiece, piece of jewelry or jewelry comprising at least one component made of a palladium-based alloy comprising, expressed by weight: between 50 and 55% of palladium, between 45% and 50% of rhodium ; a quantity x of silver, where 0% ⁇ x ⁇ 5%, preferably 0% ⁇ x ⁇ 4%, and more preferably 0% ⁇ x ⁇ 2%, and a quantity R of a residue comprising at least one element chosen from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and their combinations, where 0% ⁇ R ⁇ 5%, preferably 0% ⁇ R ⁇ 3%, preferably 0% ⁇ R ⁇ 1%, and more preferably 0% ⁇ R ⁇ 0.1%.
  • the alloys obtained exhibit, after polishing, colorimetric values according to the chromatic model L * a * b (CIE 1976) such that L * is between 84 and 91, a * is less than or equal to 1 and b * is less than or equal to 4.5.
  • L * is between 88 and 90, a * is less than or equal to 0.8 and b * is less than or equal to 3.
  • the additional elements such as iridium, ruthenium, platinum, titanium, zirconium and rhenium can optionally be used to improve for example the metallurgical properties, such as casting, to avoid porosities, or to improve the properties of the alloy such as deformation. or its shine.
  • the alloys meeting the aforementioned definition are precious metal alloys meeting all the criteria required for alloys intended for use in the watchmaking, jeweler or jeweler field, in particular in terms of their color, their luster, the hallmark of title, reasonable price, better flowability, solid alloys with good corrosion resistance, nickel free, scratch resistant (minimum 160 HV in annealed condition) and easy to machine.
  • the alloy comprises a quantity of silver x less than or equal to 2%.
  • the palladium alloy comprises, expressed by weight: from 50 to 53% of palladium, from 47% to 50% of rhodium, from 0 to 2% of silver, the remainder comprising at least one of the elements Ir, Ru, Pt, Ti, Zr and Re.
  • the palladium alloy comprises, expressed by weight from 50 to 55% of palladium, from 45% to 50% of rhodium, and from 0 to 2% of silver, the quantity R of additional elements ( remainder) preferably being equal to 0.
  • x is equal to 0 so that the alloy of the invention does not contain silver.
  • the palladium alloy can then comprise, expressed by weight: from 50 to 55% of palladium, from 45% to 50% of rhodium, the remainder comprising at least one of the elements Ir, Ru, Pt, Ti, Zr and Re, for a total value of the remainder as defined above, and preferably less than 0.1.
  • x is different from 0 so that the alloy of the invention contains silver.
  • the palladium alloy can then comprise, expressed by weight: between 50 and 55% of palladium, between 45% and 50% of rhodium; an amount x of silver, where 0% ⁇ x ⁇ 5%, and an amount R of a residue comprising at least one element selected from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and combinations thereof, where 0% ⁇ R ⁇ 5%, preferably 0% ⁇ R ⁇ 3%, preferably 0% ⁇ R ⁇ 1%, and more preferably 0% ⁇ R ⁇ 0.1%.
  • the quantity x of silver can then be such that 0.1% ⁇ x ⁇ 5%, preferably such that 0.1% ⁇ x ⁇ 4%, and more preferably 0.1% ⁇ x ⁇ 2%.
  • x and R are equal to 0 so that the alloy of the invention contains neither silver nor additional element (remainder) as defined in the remainder above.
  • the palladium alloy comprises, expressed by weight from 50% to 55% of palladium, and from 45% to 50% of rhodium.
  • the palladium-based alloy is a Pd500 alloy and comprises, expressed by weight, 50% of palladium, at least 49% of rhodium, the remainder comprising at least one of the elements Ir, Ru, Pt, Ti, Zr.
  • the palladium alloy is a Pd500 alloy and comprises, expressed by weight, 50% of palladium, 45% of rhodium and at most 4% of silver, the remainder comprising at least one of the elements Ir, Ru, Pt, Ti, Zr.
  • the palladium alloy is a Pd500 alloy and comprises, expressed by weight, 50% of palladium, 45% of rhodium and 5% of silver.
  • the palladium alloy comprises, expressed by weight, 50% of palladium, and 50% of rhodium.
  • the main elements in the composition of the alloy have a purity of at least 999 ⁇ 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. After solidification, the ingot is quenched with water. The quenched ingot is then hot deformed at 1000 ° C and then annealed.
  • the rate of work hardening between each annealing is 60 to 80%.
  • Each annealing lasts between 20 to 30 minutes and is carried out at 1000 ° C under a reducing atmosphere composed of N 2 and H 2 .
  • the cooling between annealing is done by a water quench.
  • Comparative Example 1 is an alloy consisting of 95% platinum and 5% ruthenium. This alloy is the color standard for platinum alloys in the jewelry world. Comparative example 2 relates to the alloy consisting of 50% platinum and 50% rhodium described in the application. EP 2 420 583 . Comparative Example 3 is pure rhodium.
  • Example 4 Two examples according to the invention (Examples 4 and 5) were produced, namely an alloy consisting of 50% palladium and 50% rhodium and an alloy consisting of 50% palladium, 45% rhodium and 5% rhodium. 'silver.
  • Table 2 Example Material 1 (comp.) Pt95Ru 2 (comp.) Pt50Rh50 3 (comp.) Pure rh 4 (inv.) Pd50Rh50 5 (inv.) Pd50Rh45Ag5
  • Example 3 The results of Table 3 show that the alloys according to the invention (Examples 4 and 5) exhibit colorimetric values very close to pure rhodium (Example 3) while offering densities and melting temperatures much lower than the alloys of the Examples. comparative 1 and 2, and therefore suitable for jewelry applications.
  • the alloys according to the invention meet the criterion of hardness after annealing and exhibit sufficient scratch resistance.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Adornments (AREA)
  • Display Devices Of Pinball Game Machines (AREA)

Description

Domaine de l'inventionField of the invention

L'invention se rapporte à une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé avec un alliage de palladium.The invention relates to a timepiece, piece of jewelry or jewelry comprising at least one component made from a palladium alloy.

Arrière-plan de l'inventionBackground of the invention

Dans les domaines de l'horlogerie et de la bijouterie, trois types d'alliages précieux sont blancs : les alliages de platine, les alliages de palladium et des alliages d'or. A l'heure actuelle, la majorité des fabricants d'alliages de métaux précieux pour ces domaines ont un même objectif : trouver un alliage très blanc, proche de la couleur du rhodium qui est une référence en la matière, ayant les caractéristiques suivantes : massif, recevant le marquage d'un poinçon au titre légal, résistant à la corrosion et particulièrement au ternissement, facile à couler, à déformer, résistant à la rayure (minimum 160 HV à l'état recuit) et facile à usiner, économique et qui répond à la norme européenne EN1811 sur la libération de nickel. Cet objectif est difficilement atteignable par les techniques traditionnelles connues. Les alliages 18 carats d'or gris et d'argent sont la plupart rhodiés, les alliages de platine 950 ‰ sont très blancs mais très chers, en raison de la forte teneur en platine et du coût élevé de celui-ci. Les alliages de palladium connus jusqu'à ce jour présentent une couleur trop grise, pas assez blanche, et le rhodium pur, à l'état massif, est difficile à déformer à froid, son point de fusion étant élevé.In the fields of watchmaking and jewelry, three types of precious alloys are white: platinum alloys, palladium alloys and gold alloys. At present, the majority of manufacturers of precious metal alloys for these fields have the same objective: to find a very white alloy, close to the color of rhodium which is a reference in the matter, having the following characteristics: solid , legally marked with a punch, resistant to corrosion and particularly tarnishing, easy to pour, to deform, resistant to scratching (minimum 160 HV in the annealed condition) and easy to machine, economical and which meets the European standard EN1811 on the release of nickel. This objective is difficult to achieve by known traditional techniques. The 18k white gold and silver alloys are mostly rhodium plated, the 950 ‰ platinum alloys are very white but very expensive, due to the high platinum content and the high cost of platinum. Palladium alloys known to date have a color that is too gray, not white enough, and pure rhodium, in the solid state, is difficult to cold deform, its melting point being high.

Le Journal Platinum Metal (2013, 57, (3), 202-213 ) décrit les caractéristiques principales colorimétriques des alliages précieux présentés au Tableau 1, selon le modèle chromatique L*a*b (C.I.E. 1976). Tableau 1 : Valeurs colorimétriques des alliages de métaux précieux. Journal Platinum Metal (2013, 57, (3), 202-213) L a* vert-rouge b* jaune-bleu Alliages de platine et alliages du groupe du platine 85 0 4.5 Argent pur 95 -0.5 4.2 Or gris 18 carats 84 0 9.5 Or gris 14 carats 84 -0.5 9 The Platinum Metal Journal (2013, 57, (3), 202-213 ) describes the main colorimetric characteristics of the precious alloys presented in Table 1, according to the L * a * b chromatic model (CIE 1976). Table 1: Colorimetric values of precious metal alloys. Platinum Metal Journal (2013, 57, (3), 202-213) L a * green-red b * yellow-blue Platinum alloys and platinum group alloys 85 0 4.5 Pure silver 95 -0.5 4.2 18k white gold 84 0 9.5 14k white gold 84 -0.5 9

Différentes recherches ont été menées pour proposer des alliages très blancs. Ainsi, la demande de brevet WO 2010/127458 décrit un alliage d'or gris sans nickel et sans cuivre, à base d'or, et comprenant du palladium ainsi qu'un certain nombre d'éléments d'addition utilisés pour améliorer diverses propriétés des alliages. Les alliages obtenus présentent avantageusement des valeurs colorimétriques dont la chromaticité (a* ; b*) est légèrement inférieure à l'alliage 18 carats binaire or-palladium, mais tout en restant gris (L > 81).Various researches have been carried out to propose very white alloys. Thus, the patent application WO 2010/127458 discloses a nickel-free and copper-free, gold-based gray gold alloy comprising palladium as well as a number of addition elements used to improve various properties of alloys. The alloys obtained advantageously exhibit colorimetric values whose chromaticity (a *; b *) is slightly lower than the 18-carat binary gold-palladium alloy, but while remaining gray (L> 81).

La demande de brevet EP 2 546 371 décrit un alliage d'or gris à base d'or et comprenant du chrome ainsi qu'un certain nombre d'éléments d'addition utilisés pour améliorer diverses propriétés des alliages. Les alliages obtenus présentent des valeurs colorimétriques, exceptionnelles en ce qui concerne la chromaticité, et intéressantes pour la valeur L (> 83). Mais dans ces deux cas, les éléments d'addition employés sont relativement réactifs aux procédés employés par la joaillerie traditionnelle, notamment le chalumeau, en produisant des oxydes qui obèrent l'éclat tant recherché, indiqué par la valeur L élevée.The patent application EP 2,546,371 discloses a white gold alloy based on gold and comprising chromium as well as a number of addition elements used to improve various properties of the alloys. The alloys obtained exhibit colorimetric values which are exceptional as regards chromaticity, and interesting for the L value (> 83). But in these two cases, the addition elements used are relatively reactive to the processes used by traditional jewelry, in particular the torch, by producing oxides which obstruct the much sought-after shine, indicated by the high L value.

La demande de brevet EP 2 420 583 a ouvert une nouvelle voie dans le monde des métaux précieux très blancs. Elle décrit notamment un alliage constitué en poids de 50% de platine et de 50% de Rhodium, massif, très blanc, très résistant à la corrosion, proche de la couleur du rhodium utilisant des techniques de déformation à haute température pour éviter la décomposition spinodale au-dessus de 800°C existant entre les deux éléments, induisant une mauvaise déformabilité de l'alliage à froid dû à l'hétérogénéité de l'alliage. Cette technique rend donc cet alliage particulièrement attractif pour le domaine horloger/bijoutier à l'exception de deux inconvénients majeurs non négligeables pour le consommateur final : son prix reste élevé en raison de la présence de platine ; et les titres platine 500 ou rhodium 500 ne sont pas reconnus légalement par les organisations internationales et nationales. Un produit sans poinçon de garantie est difficilement acceptable pour les consommateurs en laissant le doute sur la composition réelle des métaux précieux contenus dans l'alliage. Outre ces deux inconvénients, la fusion de l'alliage est relativement élevée (∼ 1900°C) le rendant particulièrement difficile à couler pour des applications bijoutières.The patent application EP 2 420 583 a opened a new way in the world of very white precious metals. It describes in particular an alloy consisting by weight of 50% platinum and 50% rhodium, massive, very white, very resistant to corrosion, close to the color of rhodium using high temperature deformation techniques to avoid spinodal decomposition. above 800 ° C existing between the two elements, inducing poor deformability of the cold alloy due to the heterogeneity of the alloy. This technique therefore makes this alloy particularly attractive for the watchmaking / jeweler field, with the exception of two major drawbacks which are not negligible for the end consumer: its price remains high due to the presence of platinum; and platinum 500 or rhodium 500 titles are not legally recognized by international and national organizations. A product without a guarantee mark is difficult to accept for consumers, leaving in doubt the real composition of the precious metals contained in the alloy. In addition to these two drawbacks, the melting of the alloy is relatively high (∼ 1900 ° C) making it particularly difficult to cast for jewelry applications.

Le document GB 1 128 136 divulgue une anode réalisée, soit dans un alliage de palladium et de platine avec en poids un pourcentage de palladium compris entre 5 et 80% et de platine compris entre 95 et 20%, soit dans un alliage de palladium et de rhodium avec en poids un pourcentage de palladium compris entre 3 et 80% et de rhodium compris entre 97 et 20%.The document GB 1 128 136 discloses an anode produced either in an alloy of palladium and platinum with a percentage by weight of palladium of between 5 and 80% and of platinum of between 95 and 20%, or of an alloy of palladium and rhodium with, by weight, a percentage of palladium between 3 and 80% and rhodium between 97 and 20%.

Résumé de l'inventionSummary of the invention

L'invention a notamment pour objectif de pallier les différents inconvénients des alliages connus.The object of the invention is in particular to overcome the various drawbacks of known alloys.

Plus précisément, un objectif de l'invention est de fournir des alliages très blancs, proches de la couleur du rhodium, économiques, pouvant être marqués d'un poinçon légal, avec une fusion plus faible (∼ 1750°C), et une résistance à l'oxydation permettant l'utilisation des techniques classiques de la joaillerieMore precisely, an objective of the invention is to provide very white alloys, close to the color of rhodium, economical, which can be marked with a legal hallmark, with a lower melting (∼ 1750 ° C), and a resistance. to oxidation allowing the use of classic jewelry techniques

L'invention a également pour objectif de fournir des alliages de métaux précieux sans nickel qui répondent donc favorablement à la réglementation sur la libération de nickel.Another objective of the invention is to provide nickel-free precious metal alloys which therefore respond favorably to the regulations on the release of nickel.

A cet effet, la présente invention concerne une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé dans un alliage à base de palladium comprenant, exprimé en poids: entre 50 et 55% de palladium, entre 45% et 50% de rhodium; une quantité x d'argent, où 0%≤x≤5%, et une quantité R d'un reste comprenant au moins un élément choisi parmi iridium, ruthénium, platine, titane, zirconium et rhénium, et leurs combinaisons, où 0%≤R≤5%.To this end, the present invention relates to a timepiece, piece of jewelry or jewelry comprising at least one component made of a palladium-based alloy comprising, expressed by weight: between 50 and 55% of palladium, between 45% and 50% rhodium; a quantity x of silver, where 0% ≤x≤5%, and a quantity R of a residue comprising at least one element chosen from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and their combinations, where 0% ≤R≤5%.

Selon une variante de réalisation, x est inférieur ou égal à 2%.According to an alternative embodiment, x is less than or equal to 2%.

Selon une variante de réalisation préférée, l'alliage peut comprendre, exprimé en poids: entre 50 et 53% de palladium, entre 47% et 50% de rhodium; une quantité x d'argent, où 0%≤x≤2%, et une quantité R d'un reste comprenant au moins un élément choisi parmi iridium, ruthénium, platine, titane, zirconium et rhénium, et leurs combinaisons, où 0%≤R≤3%.According to a preferred embodiment variant, the alloy may comprise, expressed by weight: between 50 and 53% palladium, between 47% and 50% rhodium; a quantity x of silver, where 0% ≤x≤2%, and a quantity R of a residue comprising at least one element chosen from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and their combinations, where 0% ≤R≤3%.

Selon une autre variante de réalisation préférée, x est égal à 0.According to another preferred variant embodiment, x is equal to 0.

Selon une variante de réalisation, R est inférieur ou égal à 1%, de préférence inférieur ou égal à 0.5%, et plus préférentiellement inférieur ou égal à 0,1%.According to an alternative embodiment, R is less than or equal to 1%, preferably less than or equal to 0.5%, and more preferably less than or equal to 0.1%.

Selon une variante de réalisation préférée, R est égal à 0.According to a preferred variant embodiment, R is equal to 0.

Selon une variante de réalisation préférée, x et R sont égaux à 0.According to a preferred variant embodiment, x and R are equal to 0.

Les alliages selon l'invention sont très blancs, peuvent être marqués d'un poinçon légal, et présentent les propriétés appropriées autorisant une utilisation dans le domaine de l'horlogerie, de la bijouterie ou de la joaillerie.The alloys according to the invention are very white, can be marked with a legal hallmark, and have the appropriate properties allowing use in the field of watchmaking, jewelry or jewelry.

Description détaillée de modes de réalisation préférésDetailed description of preferred embodiments

La présente invention concerne une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé dans un alliage à base de palladium comprenant, exprimé en poids: entre 50 et 55% de palladium, entre 45% et 50% de rhodium; une quantité x d'argent, où 0%≤x≤5%, de préférence 0%≤x≤4%, et plus préférentiellement 0%≤x≤2%, et une quantité R d'un reste comprenant au moins un élément choisi parmi iridium, ruthénium, platine, titane, zirconium et rhénium, et leurs combinaisons, où 0%≤R≤5%, de préférence 0%≤R≤3%, de préférence 0%≤R≤1%, et plus préférentiellement 0%≤R≤0.1%.The present invention relates to a timepiece, piece of jewelry or jewelry comprising at least one component made of a palladium-based alloy comprising, expressed by weight: between 50 and 55% of palladium, between 45% and 50% of rhodium ; a quantity x of silver, where 0% ≤x≤5%, preferably 0% ≤x≤4%, and more preferably 0% ≤x≤2%, and a quantity R of a residue comprising at least one element chosen from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and their combinations, where 0% ≤R≤5%, preferably 0% ≤R≤3%, preferably 0% ≤R≤1%, and more preferably 0% ≤R≤0.1%.

Les alliages obtenus présentent, après polissage, des valeurs colorimétriques selon le modèle chromatique L*a*b (C.I.E. 1976) telles que L* est compris entre 84 et 91, a* est inférieur ou égal à 1 et b* est inférieur ou égal à 4.5. De préférence, L* est compris entre 88 et 90, a* est inférieur ou égal à 0.8 et b* est inférieur ou égal à 3.The alloys obtained exhibit, after polishing, colorimetric values according to the chromatic model L * a * b (CIE 1976) such that L * is between 84 and 91, a * is less than or equal to 1 and b * is less than or equal to 4.5. Preferably, L * is between 88 and 90, a * is less than or equal to 0.8 and b * is less than or equal to 3.

Les éléments additionnels tels que iridium, ruthénium, platine, titane, zirconium et rhénium peuvent éventuellement être utilisés pour améliorer par exemple les propriétés métallurgiques, telle que la coulée, éviter les porosités, ou pour améliorer les propriétés de l'alliage telles que la déformation ou son éclat.The additional elements such as iridium, ruthenium, platinum, titanium, zirconium and rhenium can optionally be used to improve for example the metallurgical properties, such as casting, to avoid porosities, or to improve the properties of the alloy such as deformation. or its shine.

Les alliages répondant à la définition susmentionnée sont des alliages en métaux précieux répondant à l'ensemble des critères requis pour des alliages destinés à être utilisés dans le domaine horloger, bijoutier ou joaillier, notamment au niveau de leur couleur, leur éclat, le poinçon de titre, leur prix raisonnable, leur meilleure coulabilité, des alliages massifs avec une bonne résistance à la corrosion, sans nickel, résistants à la rayure (minimum 160 HV à l'état recuit) et faciles à usiner.The alloys meeting the aforementioned definition are precious metal alloys meeting all the criteria required for alloys intended for use in the watchmaking, jeweler or jeweler field, in particular in terms of their color, their luster, the hallmark of title, reasonable price, better flowability, solid alloys with good corrosion resistance, nickel free, scratch resistant (minimum 160 HV in annealed condition) and easy to machine.

Selon un premier mode de réalisation, l'alliage comprend une quantité d'argent x inférieure ou égale à 2%.According to a first embodiment, the alloy comprises a quantity of silver x less than or equal to 2%.

Selon une première variante, l'alliage de palladium comprend, exprimé en poids : de 50 à 53% de palladium, de 47 % à 50 % de rhodium, de 0 à 2 % d'argent, le reste comprenant au moins un des éléments Ir, Ru, Pt, Ti, Zr et Re.According to a first variant, the palladium alloy comprises, expressed by weight: from 50 to 53% of palladium, from 47% to 50% of rhodium, from 0 to 2% of silver, the remainder comprising at least one of the elements Ir, Ru, Pt, Ti, Zr and Re.

Selon une autre variante, l'alliage de palladium comprend, exprimé en poids de 50 à 55% de palladium, de 45 % à 50 % de rhodium, et de 0 à 2 % d'argent, la quantité R d'éléments additionnels (reste) étant de préférence égale à 0.According to another variant, the palladium alloy comprises, expressed by weight from 50 to 55% of palladium, from 45% to 50% of rhodium, and from 0 to 2% of silver, the quantity R of additional elements ( remainder) preferably being equal to 0.

Selon un deuxième mode de réalisation, x est égal à 0 de sorte que l'alliage de l'invention ne contient pas d'argent. L'alliage de palladium peut alors comprendre, exprimé en poids : de 50 à 55% de palladium, de 45 % à 50 % de rhodium, le reste comprenant au moins un des éléments Ir, Ru, Pt, Ti, Zr et Re, pour une valeur totale du reste telle que définie ci-dessus, et de préférence inférieure à 0.1.According to a second embodiment, x is equal to 0 so that the alloy of the invention does not contain silver. The palladium alloy can then comprise, expressed by weight: from 50 to 55% of palladium, from 45% to 50% of rhodium, the remainder comprising at least one of the elements Ir, Ru, Pt, Ti, Zr and Re, for a total value of the remainder as defined above, and preferably less than 0.1.

Selon un autre mode de réalisation, x est différent de 0 de sorte que l'alliage de l'invention contient de l'argent. L'alliage de palladium peut alors comprendre, exprimé en poids: entre 50 et 55% de palladium, entre 45% et 50% de rhodium; une quantité x d'argent, où 0%<x≤5%, et une quantité R d'un reste comprenant au moins un élément choisi parmi iridium, ruthénium, platine, titane, zirconium et rhénium, et leurs combinaisons, où 0%≤R≤5%, de préférence 0%≤R≤3%, de préférence 0%≤R≤1%, et plus préférentiellement 0%≤R≤0.1%. La quantité x d'argent peut alors être telle que 0.1%≤x≤5%, de préférence telle que 0.1%≤x≤4%, et plus préférentiellement 0.1%≤x≤2%.According to another embodiment, x is different from 0 so that the alloy of the invention contains silver. The palladium alloy can then comprise, expressed by weight: between 50 and 55% of palladium, between 45% and 50% of rhodium; an amount x of silver, where 0% <x≤5%, and an amount R of a residue comprising at least one element selected from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and combinations thereof, where 0% ≤R≤5%, preferably 0% ≤R≤3%, preferably 0% ≤R≤1%, and more preferably 0% ≤R≤0.1%. The quantity x of silver can then be such that 0.1% ≤x≤5%, preferably such that 0.1% ≤x≤4%, and more preferably 0.1% ≤x≤2%.

Selon un autre mode de réalisation, x et R sont égaux à 0 de sorte que l'alliage de l'invention ne contient ni argent ni élément additionnel (reste) tel que défini dans le reste ci-dessus. Dans ce cas, l'alliage de palladium comprend, exprimé en poids de 50% à 55% de palladium, et de 45% à 50 % de rhodium.According to another embodiment, x and R are equal to 0 so that the alloy of the invention contains neither silver nor additional element (remainder) as defined in the remainder above. In this case, the palladium alloy comprises, expressed by weight from 50% to 55% of palladium, and from 45% to 50% of rhodium.

Selon un mode de réalisation préféré, l'alliage à base de palladium est un alliage Pd500 et comporte, exprimé en poids, 50% de palladium, minimum 49 % de rhodium, le reste comprenant au moins un des éléments Ir, Ru, Pt, Ti, Zr.According to a preferred embodiment, the palladium-based alloy is a Pd500 alloy and comprises, expressed by weight, 50% of palladium, at least 49% of rhodium, the remainder comprising at least one of the elements Ir, Ru, Pt, Ti, Zr.

Selon un autre mode de réalisation préféré, l'alliage de palladium est un alliage Pd500 et comporte, exprimé en poids, 50% de palladium, 45% de rhodium et au maximum 4% d'argent, le reste comprenant au moins un des éléments Ir, Ru, Pt, Ti, Zr.According to another preferred embodiment, the palladium alloy is a Pd500 alloy and comprises, expressed by weight, 50% of palladium, 45% of rhodium and at most 4% of silver, the remainder comprising at least one of the elements Ir, Ru, Pt, Ti, Zr.

Selon un autre mode de réalisation préféré, l'alliage de palladium est un alliage Pd500 et comporte, exprimé en poids, 50% de palladium, 45% de rhodium et 5% d'argent.According to another preferred embodiment, the palladium alloy is a Pd500 alloy and comprises, expressed by weight, 50% of palladium, 45% of rhodium and 5% of silver.

Selon un autre mode de réalisation préféré, l'alliage de palladium comporte, exprimé en poids, 50% de palladium, et 50% de rhodium.According to another preferred embodiment, the palladium alloy comprises, expressed by weight, 50% of palladium, and 50% of rhodium.

Pour préparer l'alliage de palladium selon l'invention, on procède de la manière suivante :
Les principaux éléments entrant dans la composition de l'alliage ont une pureté d'au moins 999 ‰ et sont désoxydés. On place les éléments de la composition de l'alliage dans un creuset que l'on chauffe jusqu'à fusion des éléments. Le chauffage est réalisé dans un four à induction étanche sous pression partielle d'azote. L'alliage fondu est coulé dans une lingotière. Après solidification, on fait subir au lingot une trempe à l'eau. Le lingot trempé est ensuite déformé à chaud à 1000°C puis recuit. Le taux d'écrouissage entre chaque recuit est de 60 à 80 %. Chaque recuit dure entre 20 à 30 minutes et se fait à 1000 °C sous une atmosphère réductrice composée de N2 et H2. Le refroidissement entre les recuits se fait par une trempe à l'eau.To prepare the palladium alloy according to the invention, the procedure is as follows:
The main elements in the composition of the alloy have a purity of at least 999 ‰ 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. After solidification, the ingot is quenched with water. The quenched ingot is then hot deformed at 1000 ° C and then annealed. The rate of work hardening between each annealing is 60 to 80%. Each annealing lasts between 20 to 30 minutes and is carried out at 1000 ° C under a reducing atmosphere composed of N 2 and H 2 . The cooling between annealing is done by a water quench.

Les exemples suivants illustrent la présente invention sans toutefois en limiter la portée.The following examples illustrate the present invention without, however, limiting its scope.

Le tableau 2 ci-dessous indique la composition de différents matériaux « très blancs » testés. Les proportions indiquées sont exprimées en pourcentage en poids. L'exemple comparatif 1 est un alliage constitué de 95% de platine et de 5% de ruthénium. Cet alliage est la référence au niveau couleur des alliages de platine dans le monde de la joaillerie. L'exemple comparatif 2 est relatif à l'alliage constitué de 50% de platine et de 50% de rhodium décrit dans la demande EP 2 420 583 . L'exemple comparatif 3 est le rhodium pur.Table 2 below indicates the composition of various “very white” materials tested. The proportions indicated are expressed as a percentage by weight. Comparative Example 1 is an alloy consisting of 95% platinum and 5% ruthenium. This alloy is the color standard for platinum alloys in the jewelry world. Comparative example 2 relates to the alloy consisting of 50% platinum and 50% rhodium described in the application. EP 2 420 583 . Comparative Example 3 is pure rhodium.

Deux exemples selon l'invention (exemples 4 et 5) ont été réalisés, à savoir un alliage constitué de 50% de palladium et de 50% de rhodium et un alliage constitué de 50% de palladium, 45% de rhodium et 5% d'argent. Tableau 2 Exemple Matériau 1 (comp.) Pt95Ru 2 (comp.) Pt50Rh50 3 (comp.) Rh pur 4 (inv.) Pd50Rh50 5 (inv.) Pd50Rh45Ag5 Two examples according to the invention (Examples 4 and 5) were produced, namely an alloy consisting of 50% palladium and 50% rhodium and an alloy consisting of 50% palladium, 45% rhodium and 5% rhodium. 'silver. Table 2 Example Material 1 (comp.) Pt95Ru 2 (comp.) Pt50Rh50 3 (comp.) Pure rh 4 (inv.) Pd50Rh50 5 (inv.) Pd50Rh45Ag5

On mesure pour ces matériaux les valeurs colorimétriques, selon le modèle chromatique L*a*b (C.I.E. 1976) (mesurées après polissage, les échantillons ayant été polis jusqu'à 1 micron), la densité, la dureté Vickers à l'état recuit et la température de fusion.We measure for these materials the colorimetric values, according to the chromatic model L * a * b (CIE 1976) (measured after polishing, the samples having been polished to 1 micron), the density, the Vickers hardness in the annealed state and the melting temperature.

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
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

Les valeurs mesurées sont indiquées dans le tableau 3 ci-dessous : Tableau 3 Exemple ° L* a* vert-rouge b* jaune-bleu Densité [g/cm3] HV recuit Fusion [°C] 1 (comp.) 88.5 0.2 4.1 20.7 140 1850 2 (comp.) 89.5 0.60 2.8 15.7 150 1900 3 (comp.) 90.4 0.93 2.0 12.4 100 1963 4 (inv.) 89.2 0.75 2.6 12.2 160 1750 5 (inv.) 88.7 0.79 2.9 12.1 180 1735 The measured values are shown in Table 3 below: Table 3 Example ° L * a * green-red b * yellow-blue Density [g / cm 3 ] HV annealed Fusion [° C] 1 (comp.) 88.5 0.2 4.1 20.7 140 1850 2 (comp.) 89.5 0.60 2.8 15.7 150 1900 3 (comp.) 90.4 0.93 2.0 12.4 100 1963 4 (inv.) 89.2 0.75 2.6 12.2 160 1750 5 (inv.) 88.7 0.79 2.9 12.1 180 1735

Les résultats du tableau 3 montrent que les alliages selon l'invention (exemples 4 et 5) présentent des valeurs colorimétriques très proches de rhodium pur (exemple 3) tout en offrant des densités et des températures de fusion beaucoup plus faibles que les alliages des exemples comparatifs 1 et 2, et donc appropriées aux applications bijoutières. Les alliages selon l'invention répondent au critère de dureté après recuit et présentent une résistance à la rayure suffisante.The results of Table 3 show that the alloys according to the invention (Examples 4 and 5) exhibit colorimetric values very close to pure rhodium (Example 3) while offering densities and melting temperatures much lower than the alloys of the Examples. comparative 1 and 2, and therefore suitable for jewelry applications. The alloys according to the invention meet the criterion of hardness after annealing and exhibit sufficient scratch resistance.

Claims (4)

  1. Timepiece or piece of jewellery comprising at least one component made of a Palladium-based alloy comprising, expressed in weight, between 50 and 55% of palladium, between 45% and 50% of rhodium; a quantity x of silver where 0%>x≥5%, and a quantity R of a balance comprising at least one element selected from among iridium, ruthenium, platinum, titanium, zirconium and rhenium and combinations thereof, where 0%≥R≥5%.
  2. Timepiece or piece of jewellery according to claim 1, characterized in that the quantity x of silver is such as 0,1%≥x≥5%.
  3. Timepiece or piece of jewellery according to claim 2, characterized in that the quantity x of silver is such as 0,1%≥x≥4%.
  4. Timepiece or piece of jewellery according to claim 3, characterized in that the quantity x of silver is such as 0,1%≥x≥2%.
EP14193495.0A 2014-11-17 2014-11-17 Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy Active EP3020835B1 (en)

Priority Applications (8)

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EP14193495.0A EP3020835B1 (en) 2014-11-17 2014-11-17 Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy
US14/922,264 US20160138134A1 (en) 2014-11-17 2015-10-26 Palladium-based alloy
JP2015215461A JP2016098437A (en) 2014-11-17 2015-11-02 Palladium alloy
CN201810787163.7A CN108728684B (en) 2014-11-17 2015-11-16 Palladium-based alloys
CN201510783813.7A CN105603241B (en) 2014-11-17 2015-11-16 Palladium-Based Alloys
JP2017234867A JP2018090909A (en) 2014-11-17 2017-12-07 Palladium-based alloy
JP2020218662A JP7529563B2 (en) 2014-11-17 2020-12-28 Palladium-based alloys
US18/750,903 US20240344179A1 (en) 2014-11-17 2024-06-21 Palladium-based alloy

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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
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CN117448716A (en) * 2022-07-18 2024-01-26 中国石油化工股份有限公司 Palladium alloy and preparation method thereof

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CN105603241B (en) 2018-08-10
US20240344179A1 (en) 2024-10-17
JP7529563B2 (en) 2024-08-06
CN108728684B (en) 2020-08-04
US20160138134A1 (en) 2016-05-19
CN105603241A (en) 2016-05-25
EP3020835A1 (en) 2016-05-18
CN108728684A (en) 2018-11-02
JP2018090909A (en) 2018-06-14
JP2016098437A (en) 2016-05-30

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