EP2450460B1 - Grey gold alloy with no nickel and no copper - Google Patents

Grey gold alloy with no nickel and no copper Download PDF

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Publication number
EP2450460B1
EP2450460B1 EP11009183.2A EP11009183A EP2450460B1 EP 2450460 B1 EP2450460 B1 EP 2450460B1 EP 11009183 A EP11009183 A EP 11009183A EP 2450460 B1 EP2450460 B1 EP 2450460B1
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Prior art keywords
gold alloy
alloy
optionally
gray gold
alloys
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German (de)
French (fr)
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EP2450460A1 (en
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Michèle Reigner
Jean-Francois Ricard
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Rolex SA
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Rolex SA
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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.
  • the Japanese patent application published under the number JP-A-8-003662 discloses white gold alloys of the Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi types. These alloys are intended for the preparation of metal clays, that is to say of clays of precious metals.
  • Metal clays are indeed generally defined as being a raw material for the manufacture of jewelery or works of art and comprising a very fine powder of precious metals, an organic binder and water. After forming, they are dried and burned to remove the organic binder, so that only the sintered metals remain.
  • This Japanese patent application therefore relates to a white gold alloy powder of Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi type to have excellent sinterability. Concretely, by mixing this powder with water, a binder (plasticizer: di-n-butyl phthalate) and a surfactant (ethyl-cellulose), one should obtain a metal clay with a high degree of sintering.
  • the patent DE 3132143 A discloses gold alloys containing Pd, Pt and Nb 2
  • a gold alloy In order not to require rhodium-plating, a gold alloy must guarantee, according to ASTM Method D1925, a YI value: D1925 ⁇ 19 (YI: "yellowness index”), regarded as "good white” or "premium” and included in 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.
  • 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 (*) Ternary 18-carat gold (% by 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 87 179 119 18 At
  • Each of the ternary alloys according to the invention thus has satisfactory values L, a, b and HV annealing.
  • Quaternary alloys Nos. 33 and 34 and Quaternary No. 36 all have satisfactory L, a, b and HV annealing values.
  • the grain index is established according to ASTM E 112. TABLE IV Grain refiner Concentration grain index (Ppm) (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.

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.

Arrière-plan de l'inventionBackground of the invention

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 EP 1 227 166 (alliage AuCuMn), EP 1 010 768 (alliage AuCuPd) et JP 3130334 (alliage AuPdAgCu), proposent des alliages contenant du cuivre.Thus, patent applications EP 1 227 166 (AuCuMn alloy), EP 1 010 768 (AuCuPd alloy) and JP 3130334 (AuPdAgCu alloy), offer alloys containing copper.

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.

La demande de brevet japonais publiée sous le numéro JP-A-8-003662 décrit des alliages d'or blanc appartenant aux types Au-Pd-In, Au-Pd-Sn ou Au-Pd-Bi. Ces alliages sont destinés à la préparation d'argiles métalliques, c'est-à-dire d'argiles de métaux précieux. Les argiles métalliques sont en effet généralement définies comme étant une matière première destinée à la fabrication de bijoux ou d'objet d'art et comprenant une poudre très fine de métaux précieux, un liant organique et de l'eau. Après leur mise en forme, elles sont séchées et brûlées de façon à éliminer le liant organique, afin qu'il ne reste que les métaux frittés. Cette demande de brevet japonais a donc pour objet une poudre d'alliage d'or blanc du type Au-Pd-In, Au-Pd-Sn ou Au-Pd-Bi devant présenter une excellente aptitude au frittage. Concrètement, en mélangeant cette poudre à de l'eau, un liant (plastifiant : phtalate de di-n-butyle) et un tensioactif (éthyl-cellulose), on devrait obtenir une argile métallique à degré de frittage élevé.The Japanese patent application published under the number JP-A-8-003662 discloses white gold alloys of the Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi types. These alloys are intended for the preparation of metal clays, that is to say of clays of precious metals. Metal clays are indeed generally defined as being a raw material for the manufacture of jewelery or works of art and comprising a very fine powder of precious metals, an organic binder and water. After forming, they are dried and burned to remove the organic binder, so that only the sintered metals remain. This Japanese patent application therefore relates to a white gold alloy powder of Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi type to have excellent sinterability. Concretely, by mixing this powder with water, a binder (plasticizer: di-n-butyl phthalate) and a surfactant (ethyl-cellulose), one should obtain a metal clay with a high degree of sintering.

Cependant, 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.However, with regard to palladium, its alloys without the addition of copper are too soft given the substantial proportion that must be introduced to bleach the gold.

Le brevet DE 3132143 A divulgue des alliages d'or contenant du Pd, Pt et Nb2 The patent DE 3132143 A discloses gold alloys containing Pd, Pt and Nb 2

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 Proceedings of Santa Fe Symposium 2005, pp. 103-120 ).In order not to require rhodium-plating, a gold alloy must guarantee, according to ASTM Method D1925, a YI value: D1925 <19 (YI: "yellowness index"), regarded as "good white" or "premium" and included in 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 ).

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].

Exposé sommaire de l'inventionSummary of the invention

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% Nb
  • éventuellement de plus de 1% à moins de 6% d'au moins un élément choisi parmi Mn, Hf, Pt, 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%.
This goal is achieved by an alloy consisting of (in percentages by mass):
  • more than 75% Au;
  • from more than 18% to less than 24% of Pd;
  • from more than 1% to less than 6% Nb
  • optionally from more than 1% to less than 6% of at least one element selected from Mn, Hf, Pt, 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 gray gold alloy according to the invention may be prepared according to a process in which:
  • 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.

Exposé détaillé de l'inventionDetailed exposition of the invention

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% de Nb
  • éventuellement de 1,4% à 5,9% d'au moins un élément choisi parmi Mn, Hf, Pt, 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.
The preferred composition of the gray gold alloy according to the invention is the following (expressed in mass percentages):
  • more than 75% Au;
  • from 19% to 23.5% of Pd;
  • from 1.4% to 5.9% of Nb
  • optionally from 1.4% to 5.9% of at least one element selected from Mn, Hf, Pt, 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 définie ci-dessus, 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.
Other characteristics of the gray gold alloy according to the invention defined above, which are advantageous individually or in combination, are as follows:
  • 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
  • HV recuit (indice de dureté Vickers après recuit) > 85.
Whatever its formulation, the alloy according to the invention always meets the following conditions:
  • -2 ≤ a ≤ 2
  • b ≤ 10 and
  • 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.

Préparation de l'alliage selon l'inventionPreparation of the alloy according to the invention

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 alloys according to the invention are prepared under the following conditions:
  • 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.

ExemplesExamples

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. TABLEAU I (Etat de la technique) Ors 18 carats gris Commerciaux (% en poids) L a b HV coulée HV 75% HV recuit 1 Au 75 Ni 14,5 Cu 5,5 Zn 5 84,3 -0,8 8, 6 - 320 225 2 Au 75 Pd 15 Cu 5 Ni 5 79,8 1,1 8, 7 - 250 165 3 Au 75 Pd 15 Cu 5 Mn 5 78, 1 1,5 8,3 - 290 155 4 Au 75 Ni 11 Cu 9,5 Zn 4,5 85,1 0,3 8, 4 223 307 - 5 Au 75 Pd 13 Cu 7, 5 Ni 5 Zn 2 82,2 1,43 7,75 - - - 6 Au 75 Pd 14,9 Cu 2,6 Ag 7,5 80 1,3 7,8 70 175 90 7 Au 75 Cu 19,9 Mn 4,9 (1) 86,17 5,03 12,15 135 274 155 8 Au 75 Pd 14 Cu 7,4 In 3,5 (2) 81 2,0 7,63 145 250 188 9 Au 75,1 Pd 24,9 79,37 1,34 4,87 72 150 83 (1) : d'après EP1277166 (2 ) : d'après EP1010768 In addition to the composition of the alloys given in% by mass, 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. TABLE I (State of the art) 18K Gold Gray Commercial (% by weight) The at b HV casting HV 75% HV annealing 1 At 75 Ni 14.5 Cu 5.5 Zn 5 84.3 -0.8 8, 6 - 320 225 2 At 75 Pd 15 Cu 5 Ni 5 79.8 1.1 8, 7 - 250 165 3 At 75 Pd 15 Cu 5 Mn 5 78, 1 1.5 8.3 - 290 155 4 At 75 Ni 11 Cu 9.5 Zn 4.5 85.1 0.3 8, 4 223 307 - 5 At 75 Pd 13 Cu 7, 5 Ni 5 Zn 2 82.2 1.43 7.75 - - - 6 At 75 Pd 14.9 Cu 2.6 Ag 7.5 80 1.3 7.8 70 175 90 7 At 75 Cu 19.9 Mn 4.9 (1) 86.17 5.03 12.15 135 274 155 8 At 75 Pd 14 Cu 7.4 In 3.5 (2) 81 2.0 7.63 145 250 188 9 At 75.1 Pd 24.9 79.37 1.34 4.87 72 150 83 (1): according to EP1277166 (2 ) : according to EP1010768

On constate que les conditions précitées :

  • -2 ≤ a ≤ 2
  • b ≤ 10 et
  • HV recuit > 85
ne sont pas toujours cumulativement remplies.It can be seen that the aforementioned conditions:
  • -2 ≤ a ≤ 2
  • b ≤ 10 and
  • HV annealing> 85
are not always cumulatively fulfilled.

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. TABLEAU II (*) Ors 18 carats ternaires (% en poids) L a B HV coulée HV 75% HV recuit 10 Au 75,1 Pd 21,0 In 3,9 78,79 1,49 5,68 80 175 115 11 Au 75,1 Pd 22,0 V 2,9 81,04 1,33 5,36 115 195 127 12 Au 75,1 Pd 20,0 V 4,9 82,15 1,10 5,03 125 230 157 13 Au 75,1 Pd 21,0 Ta 3,9 80,15 1,35 5, 14 135 213 164 14 Au 75,1 Pd 23,0 V 1,9 79,34 1,38 5,05 90 182 112 15 Au 75,1 Pd 22,0 Sn 2,9 79,54 1,37 5,14 128 202 118 16 Au 75,1 Pd 22,0 Zn 2,9 79,36 1,37 4,84 80 156 108 17 Au 75,1 Pd 23,5 Zr 1,4 80,06 1,30 4,73 87 179 119 18 Au 75,1 Pd 23,0 Zr 1,9 79,72 1,32 5,10 91 180 127 19 Au 75,1 Pd 22,5 Zr 2,4 79,76 1,22 4,83 105 202 136 20 Au 75,1 Pd 22,0 Zr 2,9 79,91 1,19 4, 67 135 220 157 21 Au 75,1 Pd 21,5 Zr 3,4 80,14 1,15 4,54 164 249 194 22 Au 75,1 Pd 21,0 Zr 3,9 - - - 179 - - 23 Au 75,1 Pd 23,0 Mn 1,9 79, 10 1,35 5, 12 72 150 100 24 Au 75,1 Pd 22,0 Mn 2,9 79,77 1,33 4,86 73 156 105 25 Au 75,1 Pd 21,0 Mn 3,9 79,03 1,32 4, 95 90 182 104 26 Au 75,1 Pd 20,0 Mn 4,9 78,73 1,28 5,02 135 217 150 27 Au 75,1 Pd 23,5 Nb 1,4 80,34 1,37 5, 15 97 173 124 28 Au 75,1 Pd 23,0 Nb 1,9 81,28 1,35 4,86 132 200 151 29 Au 75,1 Pd 22,5 Nb 2,4 80,76 1,32 4,76 120 192 144 30 Au 75,1 Pd 22,0 Nb 2,9 81,02 1,34 5,17 138 221 168 31 Au 75,1 Pd 21,5 Nb 3,4 80, 94 1,34 5,70 138 221 168 32 Au 75,1 Pd 21,0 Nb 3,9 81,00 1,29 5,15 135 230 208 (*) Les alliages 27 à 32 sont des alliages selon l'invention. Table II below includes gray gold alloys according to the invention which are ternary. TABLE II (*) Ternary 18-carat gold (% by 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 87 179 119 18 At 75.1 Pd 23.0 Zr 1.9 79.72 1.32 5.10 91 180 127 19 At 75.1 Pd 22.5 Zr 2.4 79.76 1.22 4.83 105 202 136 20 At 75.1 Pd 22.0 Zr 2.9 79.91 1.19 4, 67 135 220 157 21 At 75.1 Pd 21.5 Zr 3.4 80.14 1.15 4.54 164 249 194 22 At 75.1 Pd 21.0 Zr 3.9 - - - 179 - - 23 At 75.1 Pd 23.0 Mn 1.9 79, 10 1.35 5, 12 72 150 100 24 At 75.1 Pd 22.0 Mn 2.9 79.77 1.33 4.86 73 156 105 25 At 75.1 Pd 21.0 Mn 3.9 79,03 1.32 4, 95 90 182 104 26 At 75.1 Pd 20.0 Mn 4.9 78.73 1.28 5.02 135 217 150 27 At 75.1 Pd 23.5 Nb 1.4 80.34 1.37 5, 15 97 173 124 28 At 75.1 Pd 23.0 Nb 1.9 81,28 1.35 4.86 132 200 151 29 At 75.1 Pd 22.5 Nb 2.4 80.76 1.32 4.76 120 192 144 30 At 75.1 Pd 22.0 Number 2.9 81.02 1.34 5.17 138 221 168 31 At 75.1 Pd 21.5 Nb 3.4 80, 94 1.34 5.70 138 221 168 32 At 75.1 Pd 21.0 Number 3.9 81,00 1.29 5.15 135 230 208 (*) Alloys 27 to 32 are alloys according to the invention.

Chacun des alliages ternaires selon l'invention présente donc des valeurs L, a, b et HV recuit satisfaisantes.Each of the ternary alloys according to the invention thus has satisfactory values L, a, b and HV annealing.

Le Tableau III suivant est relatif à des alliages quaternaires et quinternaires selon l'invention. TABLEAU III (*) Ors 18 carats quaternaires et quinternaires (% poids) L a b HV coulée HV 75% HV recuit 33 Au 75,1 Pd 21,0 Nb 1,9 Zr 2,0 80,76 1,18 4,53 167 260 169 34 Au 75,1 Pd 21,0 Nb 1,9 Mn 2,0 80,41 1,33 4,79 133 213 147 35 Au 75,1 Pd 21,0 Zr 2,0 Mn 1,9 79,95 1,24 4,55 150 237 153 36 Au 75,1 Pd 19,0 Nb 2,0 Zr 2,0 Mn 1,9 80,77 1,13 4,16 170 285 255 37 Au 75,1 Pd 20,0 Zr 2,0 Pt 2,4 Ga 0,5 79,86 1,20 4,65 185 226 192 38 Au 75,1 Pd 20,0 Zr 2,5 Pt 2,4 79,96 1,14 4,31 153 209 188 Les alliages 33, 34 et 36 sont des alliages selon l'invention The following Table III relates to quaternary and quinternal alloys according to the invention. TABLE III (*) 18 carats quaternary and quinternary (% 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 Alloys 33, 34 and 36 are alloys according to the invention

On constate que les alliages selon l'invention quaternaires n° 33 et 34 et quinternaire n° 36 ont tous des valeurs L, a, b et HV recuit satisfaisantes.It is found that Quaternary alloys Nos. 33 and 34 and Quaternary No. 36 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 composé de 75,3 Au, 21,7 Pd et 3,0 Zr (en % en poids).In Table IV below are reported the effects of grain refiners commonly used in 18-carat white gold on an alloy 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. TABLEAU IV Affineur de grains Concentration indice de grains (ppm) (ASTM E 112) 39 Iridium 500 2 40 Iridium 1000 3 41 Ruthénium 500 4 42 Ruthénium 1000 7 43 Rhénium 20 5 44 Rhénium 50 6 The grain index is established according to ASTM E 112. TABLE IV Grain refiner Concentration grain index (Ppm) (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

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)

  1. A nickel-free and copper-free gray gold alloy, constituted of (in percentages by weight):
    - more than 75% of Au;
    - from more than 18% to less than 24% of Pd;
    - from more than 1% to less than 6% of Nb;
    - optionally, from more than 1% to less than 6% of at least one element chosen from Mn, Hf, Pt, Ta, V, Zn and Zr;
    - optionally, at most 0.5% of at least one element chosen from Si, Ga and Ti; and
    - optionally, at most 0.2% of at least one element chosen from Ru, Ir and Re.
  2. The gray gold alloy as claimed in claim 1, constituted of (in percentages by weight):
    - more than 75% of Au;
    - from 19% to 23.5% of Pd;
    - from 1.4% to 5.9% of Nb;
    - optionally, from 1.4% to 5.9% of at least one element chosen from Mn, Hf, Pt, Ta, V, Zn and Zr;
    - optionally, at most 0.5% of at least one element chosen from Si, Ga and Ti; and
    - optionally, at most 0.1% of at least one element chosen from Ru, Ir and Re.
  3. The gray gold alloy as claimed in claim 1 or 2, comprising at least 20% of Pd.
  4. The gray gold alloy as claimed in any one of claims 1 to 3, comprising at least 1.5% of Zr or of Nb.
  5. The gray gold alloy as claimed in one of claims 1 to 4, comprising from 0.002% to 0.006% (20 to 60 ppm) of Re.
  6. The gray gold alloy as claimed in one of claims 1 to 5, comprising around 75.1% of Au.
  7. A process for preparing a gray gold alloy as claimed in one of claims 1 to 6, in which:
    - the components of the gray gold alloy are placed in a crucible;
    - the crucible is heated until the components melt;
    - the molten alloy is cast;
    - it is left to solidify;
    - it is subjected to water hardening;
    - it is subjected to at least one cold-rolling operation; and
    - it is annealed in a reducing atmosphere.
  8. The process as claimed in claim 7, in which the heating is carried out via induction in a leaktight furnace under a partial pressure of inert gas.
  9. The process as claimed in claim 8, in which the inert gas is Ar.
  10. The process as claimed in one of claims 7 to 9, in which the annealing is carried out in a reducing atmosphere constituted of a mixture of N2 and H2.
  11. The process as claimed in claim 10, in which the mixture of N2 and H2 is constituted of around 80% of N2 and 20% of H2.
  12. The process as claimed in one of claims 7 to 11, in which the annealing is carried out over around 30 minutes.
  13. The process as claimed in one of claims 7 to 12, in which the annealing is carried out at around 850°C.
EP11009183.2A 2009-05-06 2010-04-15 Grey gold alloy with no nickel and no copper Active EP2450460B1 (en)

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CH707537B1 (en) * 2013-02-06 2017-01-13 Rolex Sa Pink gold alloy for timepiece.
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EP3070182B1 (en) * 2015-03-17 2017-08-30 The Swatch Group Research and Development Ltd. White-gold alloy
FR3034106B1 (en) 2015-03-23 2022-07-22 Centre Nat Rech Scient MONOPHASIC ALLOY OF GOLD AND TUNGSTEN
EP3315620B1 (en) * 2016-10-25 2020-06-24 Nivarox-FAR S.A. Non-magnetic precious alloy for clockmaking applications
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CH703415B1 (en) 2014-03-14
WO2010127458A1 (en) 2010-11-11
EP2450460A1 (en) 2012-05-09
EP2427582A1 (en) 2012-03-14
EP2427582B1 (en) 2014-03-12
JP5793136B2 (en) 2015-10-14
CN102549179A (en) 2012-07-04
EP2450461A1 (en) 2012-05-09
US9650697B2 (en) 2017-05-16
CN102549179B (en) 2016-03-30
EP2450461B1 (en) 2014-10-29

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