EP3020835A1 - Palladium-based alloy - Google Patents

Palladium-based alloy Download PDF

Info

Publication number
EP3020835A1
EP3020835A1 EP14193495.0A EP14193495A EP3020835A1 EP 3020835 A1 EP3020835 A1 EP 3020835A1 EP 14193495 A EP14193495 A EP 14193495A EP 3020835 A1 EP3020835 A1 EP 3020835A1
Authority
EP
European Patent Office
Prior art keywords
alloy
palladium
rhodium
alloys
equal
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
EP14193495.0A
Other languages
German (de)
French (fr)
Other versions
EP3020835B1 (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/JP2021050420A/en
Application granted granted Critical
Publication of EP3020835B1 publication Critical patent/EP3020835B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—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 palladium alloy.
  • the invention also relates to a timepiece, jewelery or jewelery comprising at least one component made with such an alloy.
  • the 18-carat white gold and silver alloys are mostly rhodium-plated, the 950 platine platinum alloys are very white but very expensive, because of the high platinum content and the high cost of it.
  • the palladium alloys known to date have a color too gray, not white enough, and the pure rhodium, in the massive state, is difficult to deform cold, 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) The a * green-red b * yellow-blue Platinum group 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 gold-free, nickel-free and copper-free gray gold alloy comprising palladium and a number of additive elements used to improve various properties of the alloys.
  • the alloys obtained advantageously have colorimetric values whose chromaticity (a *; b *) is slightly lower than the 18-karat gold-palladium alloy, but while remaining gray (L> 81).
  • the patent application EP 2 546 371 discloses a gold-based gray gold alloy comprising chromium and a number of addition elements used to improve various properties of the alloys.
  • the alloys obtained have colorimetric values, which are exceptional in terms of 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 jewelery, especially the torch, producing oxides that obey the desired luster, indicated by the high L value.
  • the patent application EP 2 420 583 has opened a new path in the world of very white precious metals. It describes in particular an alloy consisting 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 bad 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 disadvantages that are not negligible for the end consumer: its price remains high because of the presence of platinum; and platinum 500 or rhodium 500 titles are not legally recognized by international and national organizations.
  • a product without warranty mark is hardly acceptable to consumers leaving doubt about the actual composition of the precious metals contained in the alloy.
  • the melting of the alloy is relatively high ( ⁇ 1900 ° C) making it particularly difficult to sink for jeweler applications.
  • the invention particularly aims to overcome the various disadvantages of known alloys.
  • an object of the invention is to provide very white alloys, close to the rhodium color, economic, which can be marked with a legal punch, with a lower melting ( ⁇ 1750 ° C), and a resistance to oxidation allowing the use of the classical techniques of jewelery.
  • the invention also aims to provide nickel-free precious metal alloys which therefore respond favorably to the regulation on the release of nickel.
  • the present invention relates to a palladium-based alloy comprising, 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%.
  • x is less than or equal to 2%.
  • the alloy may comprise, expressed by weight: between 50 and 53% of palladium, between 47% and 50% of rhodium; an amount x of silver, where 0% ⁇ x ⁇ 2%, 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 ⁇ 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 punch, and have the appropriate properties allowing use in the field of watchmaking, jewelery or jewelery.
  • the present invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of an alloy as defined above.
  • the present invention also relates to the use of an alloy as defined above in a timepiece, jewelery or jewelery.
  • the present invention relates to a palladium-based alloy comprising, expressed by weight: between 50 and 55% of palladium, between 45% and 50% of rhodium; an amount x of silver, where 0% ⁇ x ⁇ 5%, preferably 0% ⁇ x ⁇ 4%, and more preferably 0% ⁇ x ⁇ 2%, and an amount R of a remainder comprising at least one element selected from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and combinations thereof, wherein 0% ⁇ R ⁇ 5%, preferably 0% ⁇ R ⁇ 3%, preferably 0% ⁇ R ⁇ 1%, and more preferably 0% ⁇ R ⁇ 0.1%.
  • the alloys obtained have, 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 at 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.
  • Additional elements such as iridium, ruthenium, platinum, titanium, zirconium and rhenium may optionally be used to improve, for example, the metallurgical properties, such as casting, avoid porosities, or to improve the properties of the alloy such as deformation or its brilliance.
  • Alloys meeting the above definition are alloys of precious metals meeting all the criteria required for alloys intended to be used in the watchmaking, jeweler or jeweler's field, especially in terms of their color, their brilliance, the punch of As a matter of fact, their reasonable price, their better flowability, massive alloys with good corrosion resistance, nickel free, scratch resistant (minimum 160 HV in annealed state) 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 of 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) being preferably equal to 0.
  • x is equal to 0 so that the alloy of the invention does not contain silver.
  • the palladium alloy may 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 rest 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 may 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 rest above.
  • the palladium alloy comprises, expressed by weight of 50% to 55% of palladium, and 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.
  • Comparative Example 1 is an alloy consisting of 95% platinum and 5% ruthenium. This alloy is the reference at the color level of platinum alloys in the world of jewelery. 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 made, namely an alloy consisting of 50% of palladium and 50% of rhodium and an alloy consisting of 50% palladium, 45% rhodium and 5% aluminum. 'money.
  • Table 2 Example Material 1 (comp.) Pt95Ru 2 (comp.) Pt50Rh50 3 (comp.) Pure Rh 4 (inv.) Pd50Rh50 5 (inv.) Pd50Rh45Ag5
  • the colorimetric values are measured for these materials, according to the L * a * b (CIE 1976) color model (measured after polishing, the samples having been polished to 1 micron), the density, the Vickers hardness in the annealed state. and the melting temperature.
  • Table 3 example ° L * a * green-red b * yellow-blue Density [g / cm3] HV annealing 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
  • Example 3 show that the alloys according to the invention (Examples 4 and 5) have colorimetric values very close to pure rhodium (Example 3) while offering much lower densities and melting temperatures than the alloys of the examples. Comparatives 1 and 2, and therefore suitable for jewelery applications.
  • the alloys according to the invention meet the criterion of hardness after annealing and have a sufficient scratch resistance.

Abstract

L'invention se rapporte à 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%. L'invention concerne également une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé dans un tel alliage.The invention relates to a palladium-based alloy comprising, 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, wherein 0 %‰ ¤R ‰ ¤5%. The invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of such an alloy.

Description

Domaine de l'inventionField of the invention

L'invention se rapporte à un alliage de palladium. 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 invention relates to a palladium 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

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 jewelery, 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 areas have the same goal: to find a very white alloy, close to the color of rhodium which is a reference in the field, having the following characteristics: massive , receiving the marking of a punch under the legal title, resistant to corrosion and particularly to tarnishing, easy to cast, to deform, resistant to scratching (minimum 160 HV in the annealed state) and easy to machine, economical and which meets the European standard EN1811 on the release of nickel. This objective is difficult to attain by known traditional techniques. The 18-carat white gold and silver alloys are mostly rhodium-plated, the 950 platine platinum alloys are very white but very expensive, because of the high platinum content and the high cost of it. The palladium alloys known to date have a color too gray, not white enough, and the pure rhodium, in the massive state, is difficult to deform cold, 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) The a * green-red b * yellow-blue Platinum group 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 conducted to propose very white alloys. Thus, the patent application WO 2010/127458 discloses a gold-free, nickel-free and copper-free gray gold alloy comprising palladium and a number of additive elements used to improve various properties of the alloys. The alloys obtained advantageously have colorimetric values whose chromaticity (a *; b *) is slightly lower than the 18-karat 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 gold-based gray gold alloy comprising chromium and a number of addition elements used to improve various properties of the alloys. The alloys obtained have colorimetric values, which are exceptional in terms of 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 jewelery, especially the torch, producing oxides that obey the desired luster, 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 has opened a new path in the world of very white precious metals. It describes in particular an alloy consisting 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 bad 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 disadvantages that are not negligible for the end consumer: its price remains high because of the presence of platinum; and platinum 500 or rhodium 500 titles are not legally recognized by international and national organizations. A product without warranty mark is hardly acceptable to consumers leaving doubt about the actual composition of the precious metals contained in the alloy. In addition to these two disadvantages, the melting of the alloy is relatively high (~ 1900 ° C) making it particularly difficult to sink for jeweler applications.

Résumé de l'inventionSummary of the invention

L'invention a notamment pour objectif de pallier les différents inconvénients des alliages connus.The invention particularly aims to overcome the various disadvantages 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 joaillerie.More specifically, an object of the invention is to provide very white alloys, close to the rhodium color, economic, which can be marked with a legal punch, with a lower melting (~ 1750 ° C), and a resistance to oxidation allowing the use of the classical techniques of jewelery.

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.The invention also aims to provide nickel-free precious metal alloys which therefore respond favorably to the regulation on the release of nickel.

A cet effet, la présente invention concerne 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%.For this purpose, the present invention relates to a palladium-based alloy comprising, 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%.

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, the alloy may comprise, expressed by weight: between 50 and 53% of palladium, between 47% and 50% of rhodium; an amount x of silver, where 0% ≤ x ≤ 2%, 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≤3%.

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

Selon une variante de réalisation préférée, x et R sont égaux à 0.According to a preferred 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 punch, and have the appropriate properties allowing use in the field of watchmaking, jewelery or jewelery.

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.The present invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of an alloy as defined above.

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

Description détaillée de modes de réalisation préférésDetailed Description of Preferred Embodiments

La présente invention concerne 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 palladium-based alloy comprising, expressed by weight: between 50 and 55% of palladium, between 45% and 50% of rhodium; an amount x of silver, where 0% ≤x≤5%, preferably 0% ≤x≤4%, and more preferably 0% ≤x≤2%, and an amount R of a remainder comprising at least one element selected from iridium, ruthenium, platinum, titanium, zirconium and rhenium, and combinations thereof, wherein 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 have, 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 at 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.Additional elements such as iridium, ruthenium, platinum, titanium, zirconium and rhenium may optionally be used to improve, for example, the metallurgical properties, such as casting, avoid porosities, or to improve the properties of the alloy such as deformation or its brilliance.

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.Alloys meeting the above definition are alloys of precious metals meeting all the criteria required for alloys intended to be used in the watchmaking, jeweler or jeweler's field, especially in terms of their color, their brilliance, the punch of As a matter of fact, their reasonable price, their better flowability, massive alloys with good corrosion resistance, nickel free, scratch resistant (minimum 160 HV in annealed state) 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 of 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) being preferably 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 may 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 rest 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 may 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 rest above. In this case, the palladium alloy comprises, expressed by weight of 50% to 55% of palladium, and 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.
In order to prepare the palladium alloy according to the invention, the procedure is as follows:
  • The main components of the alloy have a purity of at least 999 ‰ and are deoxidized. The elements of the composition of the alloy are placed in a crucible which is heated until the elements are melted. The heating is carried out in a sealed induction furnace under partial pressure of nitrogen. The molten alloy is cast in an ingot mold. After solidification, the ingot is subjected to quenching with water. The hardened ingot is then deformed hot at 1000 ° C and then annealed. The hardening rate between each annealing is 60 to 80%. Each anneal lasts between 20 to 30 minutes and is at 1000 ° C under a reducing atmosphere composed of N 2 and H 2 . The cooling between the anneals is done by a quenched with water.

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 shows the composition of different "very white" materials tested. The proportions indicated are expressed as percentage by weight. Comparative Example 1 is an alloy consisting of 95% platinum and 5% ruthenium. This alloy is the reference at the color level of platinum alloys in the world of jewelery. 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 made, namely an alloy consisting of 50% of palladium and 50% of rhodium and an alloy consisting of 50% palladium, 45% rhodium and 5% aluminum. 'money. 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.The colorimetric values are measured for these materials, according to the L * a * b (CIE 1976) color model (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 color values are measured with a MINOLTA CM 3610 d device under the following conditions:
  • Illuminant: D65
  • Tilt: 10 °
  • Measure: SCI + SCE (specular included + excluded)
  • UV: 100%
  • Focal length: 4 mm
  • Calibration: black body and white body

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 / cm3] HV annealing 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 in Table 3 show that the alloys according to the invention (Examples 4 and 5) have colorimetric values very close to pure rhodium (Example 3) while offering much lower densities and melting temperatures than the alloys of the examples. Comparatives 1 and 2, and therefore suitable for jewelery applications. The alloys according to the invention meet the criterion of hardness after annealing and have a sufficient scratch resistance.

Claims (9)

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%.Palladium-based alloy comprising, 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%. Alliage selon la revendication 1, caractérisé en ce que x est inférieur ou égal à 2%.An alloy according to claim 1, characterized in that x is less than or equal to 2%. Alliage selon l'une des revendications précédentes, comprenant, 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%.Alloy according to one of the preceding claims, comprising, expressed by weight: between 50 and 53% of palladium, between 47% and 50% of rhodium; an amount x of silver, where 0% ≤ x ≤ 2%, 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≤3%. Alliage selon l'une des revendications précédentes, caractérisé en ce que x est égal à 0.Alloy according to one of the preceding claims, characterized in that x is equal to 0. Alliage selon l'une des revendications précédentes, caractérisé en ce que R est inférieur ou égal à 1%, de préférence inférieur ou égal à 0.5%, et plus préférentiellement inférieur ou égal à 0,1%.Alloy according to one of the preceding claims, characterized in that 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%. Alliage selon l'une des revendications précédentes, caractérisé en ce que R est égal à 0.Alloy according to one of the preceding claims, characterized in that R is equal to 0. Alliage selon l'une des revendications précédentes, caractérisé en ce que x et R sont égaux à 0.Alloy according to one of the preceding claims, characterized in that R and x are equal to 0. 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 7.Timepiece, jewelery or jewels comprising at least one component made of an alloy according to one of claims 1 to 7. Utilisation d'un alliage selon l'une des revendications 1 à 7 dans une pièce d'horlogerie, de bijouterie ou de joaillerie.Use of an alloy according to one of claims 1 to 7 in a timepiece, jewelery or jewelery.
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 (7)

Application Number Priority Date Filing Date Title
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 Alloy based on palladium
JP2017234867A JP2018090909A (en) 2014-11-17 2017-12-07 Palladium-based alloy
JP2020218662A JP2021050420A (en) 2014-11-17 2020-12-28 Palladium-based alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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

Publications (2)

Publication Number Publication Date
EP3020835A1 true EP3020835A1 (en) 2016-05-18
EP3020835B1 EP3020835B1 (en) 2021-04-21

Family

ID=51900319

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14193495.0A Active EP3020835B1 (en) 2014-11-17 2014-11-17 Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy

Country Status (4)

Country Link
US (1) US20160138134A1 (en)
EP (1) EP3020835B1 (en)
JP (3) JP2016098437A (en)
CN (2) CN108728684B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP3339455B1 (en) * 2016-12-20 2020-02-05 Montres Breguet S.A. Grey-gold alloy

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2303402A (en) * 1941-07-09 1942-12-01 Baker & Co Inc Alloy
GB556431A (en) * 1941-02-11 1943-10-05 Baker & Co Improvements in or relating to electrical resistance wire
GB1128136A (en) * 1966-05-04 1968-09-25 Tsurumi Soda Kk Improvements in or relating to anodes for electrolytic cells
FR2528285A1 (en) * 1982-06-09 1983-12-16 Chugai Electric Ind Co Ltd Precious metal composite for personal ornaments - comprising palladium (alloy) base clad with gold (alloy)
EP1548135A1 (en) * 2003-12-23 2005-06-29 General Electric Company High temperature alloys, and articles made and repaired therewith
WO2010127458A1 (en) 2009-05-06 2010-11-11 Rolex S.A. White gold alloy free of nickel and copper
EP2420583A2 (en) 2010-07-12 2012-02-22 C. Hafner GmbH + Co. KG Perfectly white, tarnish-proof noble metal jewellery alloy
EP2546371A1 (en) 2011-07-12 2013-01-16 Cendres + Métaux SA 18-carat grey gold

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2129721A (en) * 1934-12-15 1938-09-13 Int Nickel Co Palladium-silver-platinum alloys
DE1080785B (en) * 1956-03-01 1960-04-28 Heraeus Gmbh W C Use of a palladium-rhodium alloy as a material for electrical contacts and potentiometers
DE1086442B (en) * 1957-03-29 1960-08-04 Heraeus Gmbh W C Use of a palladium alloy as a material for spinnerets
SE8206158L (en) * 1982-10-29 1984-04-30 Hans G Wahlbeck PROCEDURE AND DEVICE FOR THE PREPARATION OF ALLERGY FREE Precious Metal Forms
JP2004059362A (en) * 2002-07-26 2004-02-26 Tanaka Kikinzoku Kogyo Kk Crucible
JP4073848B2 (en) * 2003-09-01 2008-04-09 シチズンホールディングス株式会社 Decorative product and manufacturing method thereof
WO2006024928A1 (en) * 2004-09-02 2006-03-09 University Of Cape Town Hardening of metal alloys
US7740720B2 (en) * 2005-09-07 2010-06-22 Fogel Kenneth D Platinum-palladium alloy
EP1875827A4 (en) * 2006-03-01 2014-04-09 Nakakura Sekikazu Precious metal jewelry and process for producing the same
JP4848912B2 (en) * 2006-09-28 2011-12-28 富士ゼロックス株式会社 Authenticity determination apparatus, authenticity determination method, authenticity determination program, and method for producing amorphous alloy member
EP2400354A1 (en) * 2010-06-22 2011-12-28 The Swatch Group Research and Development Ltd. Dial feet for a timepiece
SE536911C2 (en) * 2011-02-09 2014-10-28 Impact Coatings Ab Material for providing an electrically conductive contact layer, a contact element with such layer, method for providing the contact element, and use of the material
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB556431A (en) * 1941-02-11 1943-10-05 Baker & Co Improvements in or relating to electrical resistance wire
US2303402A (en) * 1941-07-09 1942-12-01 Baker & Co Inc Alloy
GB1128136A (en) * 1966-05-04 1968-09-25 Tsurumi Soda Kk Improvements in or relating to anodes for electrolytic cells
FR2528285A1 (en) * 1982-06-09 1983-12-16 Chugai Electric Ind Co Ltd Precious metal composite for personal ornaments - comprising palladium (alloy) base clad with gold (alloy)
EP1548135A1 (en) * 2003-12-23 2005-06-29 General Electric Company High temperature alloys, and articles made and repaired therewith
WO2010127458A1 (en) 2009-05-06 2010-11-11 Rolex S.A. White gold alloy free of nickel and copper
EP2420583A2 (en) 2010-07-12 2012-02-22 C. Hafner GmbH + Co. KG Perfectly white, tarnish-proof noble metal jewellery alloy
EP2546371A1 (en) 2011-07-12 2013-01-16 Cendres + Métaux SA 18-carat grey gold

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LE JOURNAL PLATINUM METAL, vol. 57, no. 3, 2013, pages 202 - 213

Also Published As

Publication number Publication date
CN108728684A (en) 2018-11-02
EP3020835B1 (en) 2021-04-21
JP2021050420A (en) 2021-04-01
CN105603241B (en) 2018-08-10
US20160138134A1 (en) 2016-05-19
JP2018090909A (en) 2018-06-14
CN105603241A (en) 2016-05-25
CN108728684B (en) 2020-08-04
JP2016098437A (en) 2016-05-30

Similar Documents

Publication Publication Date Title
EP2450460B1 (en) Grey gold alloy with no nickel and no copper
EP3165622B1 (en) Method for manufacturing a gold alloy wire
BE1006333A3 (en) New ternary alloy based money.
EP3070182B1 (en) White-gold alloy
EP3502286B1 (en) Platinum alloy
EP3020835B1 (en) Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy
EP2546371B1 (en) 18-carat grey gold
EP1227166B1 (en) Grey gold alloy
EP3339455B1 (en) Grey-gold alloy
CH714477A2 (en) Platinum alloy.
CH710389A2 (en) Palladium-based alloy.
CH709923B1 (en) Golden alloy.
EP3808865B1 (en) White gold alloy and method for manufacturing same
FR2764906A1 (en) New eighteen and fourteen carat grey gold@ alloys
JP2007107040A (en) Green gold alloy for jewel
JP2007107040A5 (en)
JP2009228088A (en) Gold alloy for dental use, for ornament and for industrial product age-hardened as cast
CH713263A2 (en) White gold alloy.
EP3527678B1 (en) Alloy of gold and copper, method for preparing same and use thereof
CH710877B1 (en) Gray gold alloy.
CH703143B1 (en) Palladium-based alloy, useful in jewelry article, comprises palladium, aluminum, and at least one additional metal or germanium
EP4177366A1 (en) Platinum alloy
EP4198157A1 (en) Platinum alloy
CH719248A2 (en) Platinum alloy.
CH719112A2 (en) Platinum alloy.

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20161118

RBV Designated contracting states (corrected)

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

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180301

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20201215

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: CH

Ref legal event code: NV

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

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014076739

Country of ref document: DE

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1384716

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210515

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1384716

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210421

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210421

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

Ref country code: HR

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

Effective date: 20210421

Ref country code: LT

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

Effective date: 20210421

Ref country code: NL

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

Effective date: 20210421

Ref country code: FI

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

Effective date: 20210421

Ref country code: AT

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

Effective date: 20210421

Ref country code: BG

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

Effective date: 20210721

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

Ref country code: PT

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

Effective date: 20210823

Ref country code: NO

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

Effective date: 20210721

Ref country code: PL

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

Effective date: 20210421

Ref country code: ES

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

Effective date: 20210421

Ref country code: SE

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

Effective date: 20210421

Ref country code: RS

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

Effective date: 20210421

Ref country code: IS

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

Effective date: 20210821

Ref country code: LV

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

Effective date: 20210421

Ref country code: GR

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

Effective date: 20210722

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014076739

Country of ref document: DE

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

Ref country code: SM

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

Effective date: 20210421

Ref country code: SK

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

Effective date: 20210421

Ref country code: DK

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

Effective date: 20210421

Ref country code: EE

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

Effective date: 20210421

Ref country code: CZ

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

Effective date: 20210421

Ref country code: RO

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

Effective date: 20210421

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

26N No opposition filed

Effective date: 20220124

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

Ref country code: IS

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

Effective date: 20210821

Ref country code: AL

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

Effective date: 20210421

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

Ref country code: MC

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

Effective date: 20210421

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

Ref country code: LU

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

Effective date: 20211117

Ref country code: IT

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

Effective date: 20210421

Ref country code: BE

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

Effective date: 20211130

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20211130

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

Ref country code: IE

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

Effective date: 20211117

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

Ref country code: HU

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

Effective date: 20141117

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

Ref country code: CY

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

Effective date: 20210421

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

Effective date: 20230701

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

Ref country code: GB

Payment date: 20231019

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20231020

Year of fee payment: 10

Ref country code: DE

Payment date: 20231019

Year of fee payment: 10

Ref country code: CH

Payment date: 20231201

Year of fee payment: 10