EP2251444A1 - Grey gold alloy with no nickel and no copper - Google Patents
Grey gold alloy with no nickel and no copper Download PDFInfo
- Publication number
- EP2251444A1 EP2251444A1 EP09405077A EP09405077A EP2251444A1 EP 2251444 A1 EP2251444 A1 EP 2251444A1 EP 09405077 A EP09405077 A EP 09405077A EP 09405077 A EP09405077 A EP 09405077A EP 2251444 A1 EP2251444 A1 EP 2251444A1
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- European Patent Office
- Prior art keywords
- gold alloy
- alloy
- optionally
- gray gold
- copper
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/02—Alloys based on gold
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
Definitions
- the present invention relates to a nickel-free and copper-free gray gold alloy having a hardness particularly suitable for watchmakers, jewelers and jewelers.
- the invention also relates to a process for preparing this alloy.
- gray gold alloys There are two main types of gray gold alloys on the market, nickel alloys and palladium alloys, in which both are used as whiteners.
- Nickel with its allergenic potential tends to be abandoned.
- its alloys exhibit reduced hardness and deformability that lend themselves poorly to the fields of jewelery and watchmaking.
- the increase in the copper concentration is to the detriment of other elements having whitening effects.
- a gold alloy In order not to require rhodium-plating, a gold alloy must, according to ASTM Method D1925, guarantee a value YI: D1925 ⁇ 19 (YI: "yellowness index”), considered as "good white” or "premium” And integrated into the Grade 1 category (see also http://www.utilisegold.com/jewellery technology / colors / whit e guide and Proceedings of Santa Fe Symposium 2005, pp. 103-120 ).
- the colors of the gold alloys are defined in the tri-chromatic space according to the ISO 8654.
- a YI ⁇ 19 value corresponds in first approximation to [-2 ⁇ a ⁇ 2; b ⁇ 10].
- the object of the present invention is to provide a nickel-free and copper-free gray gold alloy having satisfactory mechanical properties as well as a high whiteness (Grade 1) while not requiring rhodium-plating.
- Elements such as Si and Ti are known to those skilled in the art to improve, when added in small amounts, the surface condition and brightness and reduce the risk of corrosion, without substantially modifying the hardness or affect the colour.
- Elements such as Ir, Re or Ru are known to improve the metallurgical properties, in particular to guarantee the fineness of the grain and to avoid the porosities, without appreciably modifying the hardness or affecting the color.
- HV annealed (Vickers hardness value after annealing)> 85.
- Table I groups together 18-carat white gold alloys of the state of the art that are commercially available.
- this table gives indications relating to the Vickers HV hardness index of the alloy in the cast state (HV cast), hardened to 75% (HV 75%) and annealed ( HV annealing), as well as to the color measured in the CIELab system.
- alloy No. 6 has a hardly satisfactory HV value, although it contains copper.
- Alloy No. 9 which is composed only of gold and palladium and is therefore free of copper, has a very low annealed HV value.
- Table II below includes gray gold alloys according to the invention which are ternary.
- TABLE II (invention) 18-carat ternary golds (% in weight) The at b HV casting HV 75% HV annealing 10 At 75.1 Pd 21.0 In 3.9 78.79 1.49 5.68 80 175 115 11 At 75.1 Pd 22.0 V 2.9 81.04 1.33 5.36 115 195 127 12 At 75.1 Pd 20.0 V 4.9 82.15 1.10 5.03 125 230 157 13 At 75.1 Pd 21.0 Ta 3.9 80.15 1.35 5.14 135 213 164 14 At 75.1 Pd 23.0 V 1.9 79.34 1.38 5.05 90 182 112 15 At 75.1 Pd 22.0 Sn 2.9 79.54 1.37 5.14 128 202 118 16 At 75.1 Pd 22.0 Zn 2.9 79.36 1.37 4.84 80 156 108 17 At 75.1 Pd 23.5 Zr 1.4 80.06 1.30 4.73 87
- Each of the ternary alloys 10 to 32 according to the invention therefore has satisfactory L, a, b and HV annealing values.
- Table III relates to quaternary and quinternal alloys according to the invention.
- TABLE III (invention) 18-carat gold quaternaries and quinternaries (% by weight) The at b HV casting HV 75% HV annealing 33 At 75.1 Pd 21.0 Nb 1.9 Zr 2.0 80.76 1.18 4.53 167 260 169 34 At 75.1 Pd 21.0 Nb 1.9 Mn 2.0 80.41 1.33 4.79 133 213 147 35 At 75.1 Pd 21.0 Zr 2.0 Mn 1.9 79.95 1.24 4.55 150 237 153 36 At 75.1 Pd 19.0 Nb 2.0 Zr 2.0 Mn 1.9 80.77 1.13 4.16 170 285 255 37 At 75.1 Pd 20.0 Zr 2.0 Pt 2.4 Ga 0.5 79.86 1.20 4.65 185 226 192 38 At 75.1 Pd 20.0 Zr 2.5 Pt 2.4 79.96 1.14 4.31 153 209 188
- the grain index is established according to ASTM E 112. TABLE IV (invention) Refiner grains Concentration (Ppm) grain index (ASTM E 112) 39 Iridium 500 2 40 Iridium 1000 3 41 Ruthenium 500 4 42 Ruthenium 1000 7 43 Rhenium 20 5 44 Rhenium 50 6
- the alloys 39 and 40 show a grain structure in columns oriented in the direction of solidification.
- the other alloys exhibit an equiaxed microstructure.
- Ruthenium has the most pronounced grain refining effect, however, there are many inclusions that can penalize polishing.
- Rhenium shows a capacity of refinement of the grain without formation of inclusions. The addition of rhenium at 20 to 60 ppm therefore gives excellent polishing ability.
Abstract
Description
La présente invention concerne un alliage d'or gris sans nickel et sans cuivre présentant une dureté convenant en particulier aux horlogers, bijoutiers et joailliers. L'invention a également trait à un procédé de préparation de cet alliage.The present invention relates to a nickel-free and copper-free gray gold alloy having a hardness particularly suitable for watchmakers, jewelers and jewelers. The invention also relates to a process for preparing this alloy.
Il existe sur le marché deux principaux types d'alliages d'or gris, les alliages au nickel et les alliages au palladium, dans lesquels ces deux éléments interviennent comme blanchissants.There are two main types of gray gold alloys on the market, nickel alloys and palladium alloys, in which both are used as whiteners.
Le nickel avec son potentiel allergène tend à être abandonné. De plus, ses alliages exhibent une dureté et une déformabilité réduites qui se prêtent mal aux domaines de la bijouterie et de l'horlogerie.Nickel with its allergenic potential tends to be abandoned. In addition, its alloys exhibit reduced hardness and deformability that lend themselves poorly to the fields of jewelery and watchmaking.
De très nombreuses propositions ont donc été avancées pour remplacer le nickel.So many proposals have been made to replace nickel.
Ainsi, les demandes de brevet
L'ajout de cuivre permet de durcir les alliages mais il présente des inconvénients, notamment, une vitesse de refroidissement trop faible (lors de coulées en lingotière), et lors du traitement thermique, un durcissement non contrôlable et un risque de fissuration.The addition of copper makes it possible to harden the alloys but it has drawbacks, in particular, a cooling rate that is too low (during castings in the mold), and during the heat treatment, uncontrollable hardening and a risk of cracking.
De plus, l'augmentation de la concentration en cuivre se fait au détriment d'autres éléments ayant des effets blanchissants.In addition, the increase in the copper concentration is to the detriment of other elements having whitening effects.
En outre, le cuivre comporte un risque d'oxydation.In addition, copper carries a risk of oxidation.
En ce qui concerne le palladium, ses alliages sans ajout de cuivre sont trop mous compte tenu de la proportion substantielle qu'il faut introduire pour blanchir l'or.In the case of palladium, its alloys without the addition of copper are too soft considering the substantial proportion that must be introduced to bleach the gold.
Par ailleurs, lors du choix d'un alliage, d'autres paramètres importants sont la couleur et l'éclat du métal. La plupart des alliages contenant du Pd et/ou du Cu requièrent un dépôt galvanique de rhodium afin de se rapprocher de la couleur visée. L'épaisseur de ce revêtement (quelques microns) reste sensible au frottement et la couleur du substrat réapparaît ponctuellement, ce qui ne permet pas de réaliser des objets en or destinés à durer.In addition, when choosing an alloy, other important parameters are the color and brightness of the metal. Most alloys containing Pd and / or Cu require galvanic deposition of rhodium to approximate the target color. The thickness of this coating (a few microns) remains sensitive to friction and the color of the substrate reappears punctually, which does not allow to make gold objects to last.
Afin de ne pas nécessiter de rhodiage, un alliage d'or doit garantir, d'après la norme ASTM Method D1925, une valeur YI : D1925 < 19 (YI : « yellowness index »), considérée comme « good white » ou « premium » et intégrée à la catégorie Grade 1 (voir également http://www.utilisegold.com/jewellery technology/colours/whit e guide et
La valeur YI peut être transposée dans le système CIELab, CIE étant le sigle de la Commission Internationale de l'Eclairage et Lab les trois axes de coordonnées, l'axe L mesurant la composante blanc-noir (noir = 0 et blanc = 100), l'axe a mesurant la composante rouge-vert (rouge = valeurs positives, vert = valeurs négatives) et l'axe b mesurant la composante jaune-bleu (jaune = valeurs positives, bleu = valeurs négatives). (Cf. norme ISO 7724 établie par la Commission Internationale de l'Eclairage).The value YI can be transposed into the CIELab system, CIE being the acronym of the International Commission on Illumination and Lab the three coordinate axes, the L axis measuring the white-black component (black = 0 and white = 100) , the axis measuring the red-green component (red = positive values, green = negative values) and the b axis measuring the yellow-blue component (yellow = positive values, blue = negative values). (See ISO 7724 standard issued by the International Commission on Illumination).
Les couleurs des alliages d'or sont définies dans l'espace tri-chromatique selon la norme ISO 8654. Une valeur YI < 19 correspond en première approximation à [-2 ≤ a ≤ 2 ; b ≤ 10].The colors of the gold alloys are defined in the tri-chromatic space according to the ISO 8654. A YI <19 value corresponds in first approximation to [-2 ≤ a ≤ 2; b ≤ 10].
Le but de la présente invention est de proposer un alliage d'or gris sans nickel et sans cuivre présentant des propriétés mécaniques satisfaisantes ainsi qu'une grande blancheur (de Grade 1) tout en ne nécessitant pas de rhodiage.The object of the present invention is to provide a nickel-free and copper-free gray gold alloy having satisfactory mechanical properties as well as a high whiteness (Grade 1) while not requiring rhodium-plating.
Ce but est atteint par un alliage constitué de (en pourcentages massiques) :
- plus de 75% d'Au ;
- de plus de 18% à moins de 24% de Pd ;
- de plus de 1% à moins de 6% d'au moins un élément choisi parmi In, Mn, Hf, Nb, Pt, Sn, Ta, V, Zn et Zr ;
- éventuellement, au plus 0,5% d'au moins un élément choisi parmi Si, Ga et Ti ; et
- éventuellement, au plus 0,2% d'au moins un élément choisi parmi Ru, Ir et Re ;
- la somme de tous ces pourcentages étant bien entendu égale à 100%.
- more than 75% Au;
- from more than 18% to less than 24% of Pd;
- from more than 1% to less than 6% of at least one element selected from In, Mn, Hf, Nb, Pt, Sn, Ta, V, Zn and Zr;
- optionally, at most 0.5% of at least one element selected from Si, Ga and Ti; and
- optionally, at most 0.2% of at least one element selected from Ru, Ir and Re;
- the sum of all these percentages being of course equal to 100%.
En effet, les longues et intenses recherches menées par les inventeurs leur ont permis de découvrir qu'un tel alliage répond à l'ensemble des critères requis pour des alliages destinés à la bijouterie et à l'horlogerie en particulier, aussi bien du point de vue de l'éclat et de la couleur que de celui de la résistance à la corrosion et de la capacité à être travaillé et poli, tout en offrant une dureté comparable ou supérieure aux ors gris contenant du cuivre.Indeed, the long and intense research carried out by the inventors allowed them to discover that such an alloy meets all the criteria required for alloys intended for jewelery and watchmaking in particular, both from the the brilliance and color of corrosion resistance and the ability to be worked and polished, while offering a hardness comparable or superior to gray gold containing copper.
L'alliage d'or gris selon l'invention peut être préparé suivant un procédé dans lequel :
- on place les composants de l'alliage d'or gris dans un creuset ;
- on chauffe le creuset jusqu'à fusion des composants ;
- on coule l'alliage fondu ;
- on le laisse se solidifier ;
- on lui fait subir une trempe à l'eau ;
- on lui fait subir au moins un laminage à froid ; et on le recuit sous atmosphère réductrice.
- the components of the gray gold alloy are placed in a crucible;
- the crucible is heated until the components have melted;
- casting the molten alloy;
- it is allowed to solidify;
- it is tempered with water;
- it is subjected to at least one cold rolling; and annealing under a reducing atmosphere.
La composition générale de l'alliage d'or gris selon l'invention est indiquée ci-dessus.The general composition of the gray gold alloy according to the invention is indicated above.
La composition préférée de l'alliage d'or gris selon l'invention est la suivante (exprimée en pourcentages massiques) :
- plus de 75% d'Au ;
- de 19% à 23,5% de Pd ;
- de 1,4% à 5,9% d'au moins un élément choisi parmi In, Mn, Hf, Nb, Pt, Sn, Ta, V, Zn et Zr ;
- éventuellement, au plus 0,5% d'au moins un élément choisi parmi Si, Ga et Ti ; et
- éventuellement, au plus 0,1% d'au moins un élément choisi parmi Ru, Ir et Re.
- more than 75% Au;
- from 19% to 23.5% of Pd;
- from 1.4% to 5.9% of at least one member selected from In, Mn, Hf, Nb, Pt, Sn, Ta, V, Zn and Zr;
- optionally, at most 0.5% of at least one element selected from Si, Ga and Ti; and
- optionally, at most 0.1% of at least one element selected from Ru, Ir and Re.
D'autres caractéristiques de l'alliage d'or gris selon l'invention, qui sont avantageuses individuellement ou en combinaison, s'énoncent comme suit :
- l'alliage comprend au moins 20% de Pd ;
- il comprend au moins 1,5% de Zr ou de Nb ;
- il comprend de 0,002% à 0,006% (20 à 60 ppm) de Re ;
- il comprend environ 75,1% d'Au.
- the alloy comprises at least 20% Pd;
- it comprises at least 1.5% of Zr or Nb;
- it comprises from 0.002% to 0.006% (20 to 60 ppm) of Re;
- it comprises about 75.1% of Au.
Les éléments tels que Si et Ti sont connus de l'homme du métier pour améliorer, lorsqu'ils sont ajoutés en petites quantités, l'état de surface et l'éclat et diminuer les risques de corrosion, sans modifier sensiblement la dureté ni affecter la couleur.Elements such as Si and Ti are known to those skilled in the art to improve, when added in small amounts, the surface condition and brightness and reduce the risk of corrosion, without substantially modifying the hardness or affect the colour.
Les éléments comme Ir, Re ou Ru sont connus pour améliorer les propriétés métallurgiques, en particulier garantir la finesse du grain et éviter les porosités, sans modifier sensiblement la dureté ni affecter la couleur.Elements such as Ir, Re or Ru are known to improve the metallurgical properties, in particular to guarantee the fineness of the grain and to avoid the porosities, without appreciably modifying the hardness or affecting the color.
Quelle que soit sa formulation, l'alliage selon l'invention répond toujours aux conditions suivantes :
- -2 ≤ a ≤ 2
- b ≤ 10 et
- -2 ≤ a ≤ 2
- b ≤ 10 and
HV recuit (indice de dureté Vickers après recuit) > 85.HV annealed (Vickers hardness value after annealing)> 85.
Ces propriétés sont celles que doit posséder un alliage d'or gris pour satisfaire aux exigences des horlogers, bijoutiers et joailliers.These properties are those that must have a gray gold alloy to meet the requirements of watchmakers, jewelers and jewelers.
Les alliages selon l'invention sont préparés dans les conditions suivante :
- les principaux éléments entrant dans la composition de l'alliage ont de préférence une pureté de 99,95% à l'exception de l'or avec 99,99% et du Zr avec 99,8% ;
- l'alliage est obtenu par fusion des éléments dans un creuset (par exemple en ZrO2). Le chauffage est obtenu par induction dans un four étanche sous pression partielle (par exemple d'argon à 800 mbar). L'alliage en fusion est ensuite coulé dans une lingotière en graphite. Après solidification, la lingotière est sortie du four étanche et le lingot est démoulé, refroidi par une trempe à l'eau et éventuellement écrouté ;
- le lingot est ensuite laminé une ou plusieurs fois à froid, jusqu'à obtention d'un taux d'écrouissage de 75 à 80% ;
- le recuit est réalisé sous atmosphère réductrice (de préférence 80% N2-20% H2) durant 30 minutes à 850°C.
- the main components in the alloy composition preferably have a purity of 99.95% with the exception of gold with 99.99% and Zr with 99.8%;
- the alloy is obtained by melting the elements in a crucible (for example in ZrO 2 ). The heating is obtained by induction in a sealed oven under partial pressure (for example argon at 800 mbar). The molten alloy is then cast in a graphite mold. After solidification, the mold is removed from the sealed oven and the ingot is demolded, cooled by quenching with water and optionally crushed;
- the ingot is then rolled one or more times cold, until a hardening rate of 75 to 80%;
- the annealing is carried out under a reducing atmosphere (preferably 80% N 2 -20% H 2 ) for 30 minutes at 850 ° C.
Dans les exemples qui vont suivre, le Tableau I regroupe des alliages en or gris 18 carats de l'état de la technique que l'on trouve dans le commerce.In the examples that follow, Table I groups together 18-carat white gold alloys of the state of the art that are commercially available.
Outre la composition des alliages donnée en % massiques, ce tableau donne des indications relatives à l'indice de dureté Vickers HV de l'alliage à l'état coulé (HV coulée), écroui à 75% (HV 75%) et recuit (HV recuit), ainsi qu'à la couleur mesurée dans le système CIELab.
Commerciaux (% en poids)
(2) : d'après
Commercial (% by weight)
(2): according to
On constate que les conditions précitées :
- -2 ≤ a ≤ 2
- b ≤ 10 et
- HV recuit > 85
- -2 ≤ a ≤ 2
- b ≤ 10 and
- HV annealing> 85
De plus, l'alliage n° 6 présente une valeur HV à peine satisfaisante, bien qu'il contienne du cuivre.In addition, alloy No. 6 has a hardly satisfactory HV value, although it contains copper.
L'alliage n°9, qui n'est composé que d'or et de palladium et est donc dépourvu de cuivre, présente une valeur HV recuit très basse.Alloy No. 9, which is composed only of gold and palladium and is therefore free of copper, has a very low annealed HV value.
Le Tableau II suivant regroupe des alliages d'or gris selon l'invention qui sont ternaires.
(% en poids)
(% in weight)
Chacun des alliages ternaires n° 10 à 32 selon l'invention présente donc des valeurs L, a, b et HV recuit satisfaisantes.Each of the ternary alloys 10 to 32 according to the invention therefore has satisfactory L, a, b and HV annealing values.
Le Tableau III suivant est relatif à des alliages quaternaires et quinternaires selon l'invention.
quaternaires et
quinternaires (% poids)
quaternaries and
quinternaries (% by weight)
On constate que les alliages selon l'invention quaternaires n° 33 à 35 et 38 et quinternaires n° 36 et 37 ont tous des valeurs L, a, b et HV recuit satisfaisantes.It is found that Quaternary alloys Nos. 33 to 35 and 38 and Quinternaries Nos. 36 and 37 all have satisfactory L, a, b and HV annealing values.
Dans le tableau IV suivant sont reportés les effets des affineurs de grains couramment employés dans les or gris 18 carats, sur un alliage selon l'invention composé de 75,3 Au, 21,7 Pd et 3,0 Zr (en % en poids).In the following Table IV are reported the effects of grain refiners commonly employed in 18-carat white gold, on an alloy according to the invention composed of 75.3 Au, 21.7 Pd and 3.0 Zr (in% by weight ).
On constate que les valeurs L, a et b d'un tel alliage ne sont pas affectées par l'ajout de l'affineur de grains.It can be seen that the values L, a and b of such an alloy are not affected by the addition of the grain refiner.
L'indice de grains est établi selon la norme ASTM E 112.
grains
(ppm)
(ASTM E 112)
grains
(Ppm)
(ASTM E 112)
De plus, tous les alliages du tableau IV présentent une dureté satisfaisante après recuit.In addition, all the alloys of Table IV have a satisfactory hardness after annealing.
Par ailleurs, les alliages 39 et 40 montrent une structure de grains en colonnes orientées dans le sens de la solidification. Les autres alliages exhibent une microstructure équiaxe. Le ruthénium a l'effet d'affineur de grain le plus prononcé, cependant, on relève de nombreuses inclusions pouvant pénaliser le polissage. Le rhénium montre une capacité d'affinement du grain sans formation d'inclusions. L'ajout de rhénium à hauteur de 20 à 60 ppm confère par conséquent une excellente aptitude au polissage.Moreover, the alloys 39 and 40 show a grain structure in columns oriented in the direction of solidification. The other alloys exhibit an equiaxed microstructure. Ruthenium has the most pronounced grain refining effect, however, there are many inclusions that can penalize polishing. Rhenium shows a capacity of refinement of the grain without formation of inclusions. The addition of rhenium at 20 to 60 ppm therefore gives excellent polishing ability.
Claims (13)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09405077A EP2251444A1 (en) | 2009-05-06 | 2009-05-06 | Grey gold alloy with no nickel and no copper |
EP11009183.2A EP2450460B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
CN201080019776.8A CN102549179B (en) | 2009-05-06 | 2010-04-15 | Without the White gold alloy of nickel and copper |
EP11009184.0A EP2450461B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
US13/265,655 US9650697B2 (en) | 2009-05-06 | 2010-04-15 | Gray gold alloy free of nickel and copper |
JP2012508867A JP5793136B2 (en) | 2009-05-06 | 2010-04-15 | Gray gold alloy without nickel and copper |
EP10716257.0A EP2427582B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
PCT/CH2010/000101 WO2010127458A1 (en) | 2009-05-06 | 2010-04-15 | White gold alloy free of nickel and copper |
CH01771/11A CH703415B1 (en) | 2009-05-06 | 2010-04-15 | White gold alloy without nickel and copper. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09405077A EP2251444A1 (en) | 2009-05-06 | 2009-05-06 | Grey gold alloy with no nickel and no copper |
Publications (1)
Publication Number | Publication Date |
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EP2251444A1 true EP2251444A1 (en) | 2010-11-17 |
Family
ID=41127638
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09405077A Withdrawn EP2251444A1 (en) | 2009-05-06 | 2009-05-06 | Grey gold alloy with no nickel and no copper |
EP11009183.2A Active EP2450460B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
EP11009184.0A Active EP2450461B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
EP10716257.0A Active EP2427582B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11009183.2A Active EP2450460B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
EP11009184.0A Active EP2450461B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
EP10716257.0A Active EP2427582B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
Country Status (6)
Country | Link |
---|---|
US (1) | US9650697B2 (en) |
EP (4) | EP2251444A1 (en) |
JP (1) | JP5793136B2 (en) |
CN (1) | CN102549179B (en) |
CH (1) | CH703415B1 (en) |
WO (1) | WO2010127458A1 (en) |
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EP3315620A1 (en) * | 2016-10-25 | 2018-05-02 | Nivarox-FAR S.A. | Non-magnetic precious alloy for clockmaking applications |
US10458002B2 (en) * | 2016-12-20 | 2019-10-29 | Montres Breguet S.A. | Grey gold alloy |
WO2020020528A1 (en) | 2018-07-26 | 2020-01-30 | Px Services Sa | Gold-based alloy which changes colour, and use thereof in the field of jewellery and watchmaking |
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CN104884650B (en) * | 2012-11-08 | 2017-09-05 | 贺利氏有限公司 | Nickeliferous billon with low nickel rate of release, the intermediate alloy for obtaining the nickeliferous billon and the wherein purposes of metallic element |
JP6595344B2 (en) * | 2013-02-06 | 2019-10-23 | ロレックス・ソシエテ・アノニム | Watch made from rose gold alloy |
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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WO2020020528A1 (en) | 2018-07-26 | 2020-01-30 | Px Services Sa | Gold-based alloy which changes colour, and use thereof in the field of jewellery and watchmaking |
Also Published As
Publication number | Publication date |
---|---|
JP5793136B2 (en) | 2015-10-14 |
CN102549179A (en) | 2012-07-04 |
EP2450460B1 (en) | 2013-09-25 |
EP2450460A1 (en) | 2012-05-09 |
EP2427582A1 (en) | 2012-03-14 |
WO2010127458A1 (en) | 2010-11-11 |
US9650697B2 (en) | 2017-05-16 |
WO2010127458A8 (en) | 2011-04-14 |
CN102549179B (en) | 2016-03-30 |
JP2012526192A (en) | 2012-10-25 |
US20120114522A1 (en) | 2012-05-10 |
EP2450461B1 (en) | 2014-10-29 |
EP2427582B1 (en) | 2014-03-12 |
EP2450461A1 (en) | 2012-05-09 |
CH703415B1 (en) | 2014-03-14 |
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