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EP2427582A1 - White gold alloy free of nickel and copper - Google Patents

White gold alloy free of nickel and copper

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Publication number
EP2427582A1
EP2427582A1 EP10716257A EP10716257A EP2427582A1 EP 2427582 A1 EP2427582 A1 EP 2427582A1 EP 10716257 A EP10716257 A EP 10716257A EP 10716257 A EP10716257 A EP 10716257A EP 2427582 A1 EP2427582 A1 EP 2427582A1
Authority
EP
European Patent Office
Prior art keywords
gold alloy
gray
element selected
alloy
copper
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
EP10716257A
Other languages
German (de)
French (fr)
Other versions
EP2427582B1 (en
Inventor
Michèle Reigner
Jean-François Ricard
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.)
Rolex SA
Original Assignee
Rolex 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 Rolex SA filed Critical Rolex SA
Priority to EP11009183.2A priority Critical patent/EP2450460B1/en
Priority to EP11009184.0A priority patent/EP2450461B1/en
Priority to EP10716257.0A priority patent/EP2427582B1/en
Publication of EP2427582A1 publication Critical patent/EP2427582A1/en
Application granted granted Critical
Publication of EP2427582B1 publication Critical patent/EP2427582B1/en
Active legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—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.
  • 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.
  • Japanese Patent Application Publication No. 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 so as 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.
  • a white gold alloy powder of Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi type to have excellent sinterability.
  • a binder plasticizer: di-n-butyl phthalate
  • a surfactant ethyl-cellulose
  • 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”), considered as "good white” or "premium” and included in the Grade 1 category (see also http://www.utilgold.com/goodery technology / colors / whit e guide and Proceedings of Santa Fe Symposium 2005, pp. 103- 120).
  • CIE being the acronym of the International Commission on Illumination and Lab the three coordinate axes
  • 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 [
  • 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.
  • the gray gold alloy according to the invention may be prepared by 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; the molten alloy is cast; 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.
  • the preferred composition of the gray gold alloy according to the invention is the following (expressed in mass percentages):
  • the alloy comprises at least 20% of Pd; it comprises at least 1.5% of Zr or Nb;
  • the alloy according to the invention always satisfies the following conditions: -2 ⁇ a ⁇ 2 b ⁇ 10 and
  • HV annealed (Vickers hardness after annealing)> 85. These properties are those that must have a gray gold alloy to meet the requirements of watchmakers, jewelers and jewelers. Preparation of the alloy according to the invention
  • the alloys according to the invention are prepared under the following conditions:
  • the main elements forming the alloy 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 ZrC> 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 annealing is carried out under a reducing atmosphere (preferably 80% N 2 -20% H 2 ) for 30 minutes at 850 ° C.
  • a reducing atmosphere preferably 80% N 2 -20% H 2
  • 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.
  • 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.
  • 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.
  • the grain index is established according to ASTM E 112.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adornments (AREA)

Abstract

The present invention relates to a white gold alloy free of nickel and copper having a hardness that is suitable in particular for watchmakers and jewellers. Said alloy consists of (in wt %): more than 75% of Au; more than 18% to less than 24% of Pd; more than 1% to less than 6% of at least one element selected from among Mn, Hf, Nb, Pt, Ta, V, Zn and Zr; optionally, no more than 0.5% of at least one element selected from among Si, Ga and Ti; and optionally, no more than 0.2% of at least one element selected from among Ru, Ir and Re. The invention also relates to a method for preparing said alloy.

Description

ALLIAGE D'OR GRIS SANS NICKEL ET SANS CUIVRE GRAY GOLD ALLOY WITHOUT NICKEL AND COPPER
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.The present invention relates to a nickel-free and copper-free gray gold alloy having a hardness particularly suitable for watchmakers, jewelers and jewelers.
L' invention a également trait à un procédé de préparation de cet alliage.The invention also relates to a process for preparing this alloy.
Arrière-plan de l'invention II 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.BACKGROUND OF THE INVENTION There are on the market two main types of gray gold alloys, nickel alloys and palladium alloys, in which these two elements act 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. 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 .So many proposals have been made to replace nickel. Thus, patent applications EP 1 227 166 (AuCuMn alloy), EP 1 010 768 (AuCuPd alloy) and JP 3130334 (AuPdAgCu alloy), propose 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. 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 frittes. 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 tensio- actif (éthyl-cellulose) , on devrait obtenir une argile métallique à degré de frittage élevé.In addition, copper carries a risk of oxidation. Japanese Patent Application Publication No. 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 so as 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.
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"), considered as "good white" or "premium" and included in the Grade 1 category (see also http://www.utilgold.com/goodery 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). 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 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). 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) :This goal is achieved by an alloy consisting of (in percentages by mass):
- plus de 75% d'Au ;- more than 75% of 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 Mn, Hf, Nb, 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%. 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 .- from more than 18% to less than 24% of Pd; from more than 1% to less than 6% of at least one element chosen from Mn, Hf, Nb, 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%. 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 by 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; the molten alloy is cast; 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) :The preferred composition of the gray gold alloy according to the invention is the following (expressed in mass percentages):
- 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 Mn, Hf, Nb, 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.- more than 75% of Au; from 19% to 23.5% of Pd; from 1.4% to 5.9% of at least one member selected from Mn, Hf, Nb, 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, 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 ;Other characteristics of the gray gold alloy according to the invention, which are advantageous individually or in combination, are as follows: the alloy comprises at least 20% of Pd; it comprises at least 1.5% of Zr or Nb;
- il comprend de 0,002% à 0,006% (20 à 60 ppm) de Re ; il comprend environ 75,1% d'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. 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.it comprises from 0.002% to 0.006% (20 to 60 ppm) of Re; it comprises about 75.1% of Au. 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.
Quelle que soit sa formulation, l'alliage selon l'invention répond toujours aux conditions suivantes : -2 < a < 2 b < 10 etWhatever its formulation, the alloy according to the invention always satisfies the following conditions: -2 <a <2 b <10 and
HV recuit (indice de dureté Vickers après recuit) > 85. Ces propriétés sont celles que doit posséder un alliage d'or gris pour satisfaire aux exigences des horlogers, bijoutiers et joailliers. Préparation de l'alliage selon l'inventionHV annealed (Vickers hardness after annealing)> 85. These properties are those that must have a gray gold alloy to meet the requirements of watchmakers, jewelers and jewelers. Preparation of the alloy according to the invention
Les alliages selon l'invention sont préparés dans les conditions suivantes :The alloys according to the invention are prepared under the following conditions:
• 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% ;The main elements forming the alloy preferably have a purity of 99.95% with the exception of gold with 99.99% and Zr with 99.8%;
• l'alliage est obtenu par fusion des éléments dans un creuset (par exemple en ZrC>2) . 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 ;The alloy is obtained by melting the elements in a crucible (for example ZrC> 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;
• le lingot est ensuite laminé une ou plusieurs fois à froid, jusqu'à obtention d'un taux d' écrouissage de 75 à 80% ;• the ingot is then rolled one or more times cold, until a hardening rate of 75 to 80%;
• le recuit est réalisé sous atmosphère réductrice (de préférence 80% N2-20% H2) durant 30 minutes à 8500C.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 couléIn 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 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)(HV cast), hardened to 75% (HV 75%) and annealed (HV annealed), as well as to the color measured in the CIELab system. TABLE I (State of the art)
Ors 18 carats gris HV HV HV Commerciaux (% en poids) L a b coulée 75% recuit18K gold gray HV HV HV Commercial (% by weight) 75% annealed cast iron
1 Au 75 Ni 14, 5 Cu 5, 5 Zn 5 84,3 -0,8 8 ,6 - 320 2251 at 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 1652 At 75 Pd 15 Cu 5 Ni 5 79.8 1.18, 7 - 250 165
3 Au 75 Pd 15 Cu 5 Mn 5 78,1 1,5 8 ,3 - 290 1553 At 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 -4 at 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 - - -At 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 I1 5 80 1,3 7 ,8 70 175 906 At 75 Pd 14, 9 Cu 2.6 Ag I 1 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 1557 At 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 1888 At 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 72 150 839 At 75, 1 Pd 24.9 79.37 1.34 4, 87 72 150 83
(1) : d'après EP1277166(1): according to EP1277166
(2) : d'après EP1010768 On constate que les conditions précitées : -2 < a < 2 b < 10 et HV recuit > 85 ne sont pas toujours cumulativement remplies. De plus, l'alliage n° 6 présente une valeur HV à peine satisfaisante, bien qu'il contienne du cuivre.(2): from EP1010768 It can be seen that the above-mentioned conditions: -2 <a <2 b <10 and HV annealed> 85 are not always cumulatively fulfilled. 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. Le Tableau II suivant regroupe des alliages d'or gris selon l'invention qui sont ternaires. 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.
TABLEAU II (invention)TABLE II (invention)
Ors 18 carats ternaires HV (% en poids) L a b HV coulée HV 75% recuitTernary 18-carat gold HV (% by weight) L a b HV HV cast 75% annealed
10 Au 75, 1 Pd 21,0 In 3, 9 78,79 1,49 5,68 80 175 11510 At 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 12711 At 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 15712 At 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 16413 At 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 11214 At 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 11815 At 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 10816 At 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 11917 At 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 12718 At 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 13619 At 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 15720 At 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 19421 At 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 - -22 At 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 10023 At 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 10524 At 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 10425 At 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 15026 At 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 12427 At 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 15128 At 75.1 Pd 23.0 Number 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 14429 At 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 16830 At 75.1 Pd 22.0 Nb 2.9 81.02 2.14 5.17 138 221 168
31 Au 75,1 Pd 21,5 Nb 3,4 80, 94 1,34 5,70 138 221 16831 At 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 20832 At 75.1 Pd 21.0 Number 3.9 81.00 1.29 5.15 135 230 208
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.The following Table III relates to quaternary and quinternal alloys according to the invention.
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.The grain index is established according to 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

Revendications claims
1.- Alliage d'or gris sans nickel et sans cuivre, constitué de (en pourcentages massiques) : - plus de 75% d'Au ;1.- Nickel-free and copper-free gray gold alloy, consisting of (in percentages by mass): - more than 75% of 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 Mn, Hf, Nb, 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.- 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 Mn, Hf, Nb, 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.
2.- Alliage d'or gris selon la revendication 1, constitué de (en pourcentages massiques) :2. A gray gold alloy according to claim 1, consisting of (in percentages by weight):
- plus de 75% d'Au ;- more than 75% of Au;
- de 19% à 23,5% de Pd ; de 1,4% à 5,9% d'au moins un élément choisi parmi Mn, Hf, Nb, 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.from 19% to 23.5% of Pd; from 1.4% to 5.9% of at least one member selected from Mn, Hf, Nb, 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.
3.- Alliage d'or gris selon la revendication 1 ou 2, comprenant au moins 20% de Pd.3. A gray gold alloy according to claim 1 or 2, comprising at least 20% of Pd.
4.- Alliage d'or gris selon l'une quelconque des revendications 1 à 3, comprenant au moins 1,5% de Zr ou de Nb. 4. A gray gold alloy according to any one of claims 1 to 3, comprising at least 1.5% Zr or Nb.
5.- Alliage d'or gris selon l'une des revendications 1 à 4, comprenant de 0,002% à 0,006% (20 à 60 ppm) de Re.5. A gray gold alloy according to one of claims 1 to 4, comprising from 0.002% to 0.006% (20 to 60 ppm) of Re.
6.- Alliage d'or gris selon l'une des revendications 1 à 5, comprenant environ 75,1% d'Au.6. Gray gold alloy according to one of claims 1 to 5, comprising about 75.1% of Au.
7.- Procédé de préparation d'un alliage d'or gris selon l'une des revendications 1 à 6, 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.7. A process for preparing a gray-gold alloy according to one of claims 1 to 6, wherein: placing the components of the gray gold alloy 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.
8.- Procédé selon la revendication 7, dans lequel le chauffage est réalisé par induction dans un four étanche sous pression partielle de gaz rare.8. A process according to claim 7, wherein the heating is performed by induction in a sealed oven under partial pressure of rare gas.
9.- Procédé selon la revendication 8, dans lequel le gaz rare est Ar.9. The process of claim 8, wherein the rare gas is Ar.
10.- Procédé selon l'une des revendications 7 à 9, dans lequel le recuit est effectué sous une atmosphère réductrice constituée d'un mélange de N2 et H2.10.- Method according to one of claims 7 to 9, wherein the annealing is performed under a reducing atmosphere consisting of a mixture of N 2 and H 2 .
11.- Procédé selon la revendication 10, dans lequel le mélange de N2 et H2 est constitué d'environ 80% de N2 et 20% de H2. 11. The process of claim 10 wherein the mixture of N 2 and H 2 is about 80% N 2 and 20% H 2 .
12.- Procédé selon l'une des revendications 7 à 11, dans lequel le recuit est effectué durant environ 30 minutes.12. A process according to one of claims 7 to 11, wherein the annealing is carried out for about 30 minutes.
13.- Procédé selon l'une des revendications 7 à 12, dans lequel le recuit est réalisé à environ 8500C. 13.- Method according to one of claims 7 to 12, wherein the annealing is carried out at about 850 0 C.
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JP2012526192A (en) 2012-10-25
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US20120114522A1 (en) 2012-05-10
US9650697B2 (en) 2017-05-16
CN102549179B (en) 2016-03-30
EP2450461A1 (en) 2012-05-09
CN102549179A (en) 2012-07-04
WO2010127458A1 (en) 2010-11-11
EP2450460B1 (en) 2013-09-25
EP2251444A1 (en) 2010-11-17
EP2450460A1 (en) 2012-05-09
WO2010127458A8 (en) 2011-04-14
EP2450461B1 (en) 2014-10-29

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