EP2954079B1 - Pink-gold alloy for timepiece - Google Patents

Pink-gold alloy for timepiece Download PDF

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Publication number
EP2954079B1
EP2954079B1 EP14704109.9A EP14704109A EP2954079B1 EP 2954079 B1 EP2954079 B1 EP 2954079B1 EP 14704109 A EP14704109 A EP 14704109A EP 2954079 B1 EP2954079 B1 EP 2954079B1
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Prior art keywords
alloy
palladium
indium
equal
timepiece
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EP14704109.9A
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German (de)
French (fr)
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EP2954079A1 (en
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Pascal Dubos
Jean-François 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
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases

Definitions

  • the invention relates to a rose gold alloy, particularly suitable for a timepiece, and a timepiece, jewelry or jewelry as such comprising such an alloy, such as a watch.
  • the color of gold alloys depends on their content of alloying elements.
  • AuCuAg 18ct alloys for example, a copper content greater than 180 ⁇ and a silver content of the order of 40 une gives them a red color.
  • the color evolves towards pink then towards yellow if the copper content decreases from 180 ⁇ to 150 ⁇ then from 150 ⁇ to 60 ⁇ and if the silver content increases from 40 ⁇ to 150 ⁇ .
  • watch cases or bracelets made from these usual gold alloys tended to undergo a gradual change in their color under the action of tap water, sea water, water. swimming pool water, salt water or soapy water.
  • One of the aims of the invention is to improve the resistance to a change in color of a timepiece, piece of jewelry or jewelry made from a rose gold alloy and subjected, in use, to to weakly aggressive aqueous media.
  • Another object of the invention is to define a rose-colored gold alloy, the pink of which has the most attractive aesthetic appearance possible.
  • the document JP11-335755 describes a rose gold alloy with a weight composition of 75% Au, 22% Cu, 1.5% Ag, 1% Pd, 0.5% In.
  • ingots are prepared by static casting under vacuum (melting in a graphite crucible and cooling under nitrogen). Samples are cut from the ingot in the as-cast state. The surface is prepared by polishing. A typical sample has a 20mm x 20mm x 5mm square section. All the tests are carried out on as-cast alloys, without deformation or subsequent heat treatment, and without the addition of the usual grain refiners.
  • the crystallographic analysis of the samples is carried out with an X-ray diffractometer with Cu anode.
  • a metallographic check and an analysis of the stoichiometries of the phases are carried out by SEM - EDX scanning electron microscopy.
  • the color variations are measured with a spectrocolorimeter with integrating sphere.
  • the color is defined in a conventional manner by a point in CIELAB space formed by a green-red axis on the abscissa, a blue-yellow axis on the ordinate and an axis representative of the contrast (cf. report CIE15: 2004 established by the International Commission on Illumination).
  • the measurements were all performed using the following convention: illuminant D65 and standard observer 10 ° (CIE1964).
  • the color differences ⁇ E are defined by DE2000 (equation 8.36, paragraph 8.3, report CIE15: 2004).
  • a measurement of the color difference is made between new samples (cast and polished) and samples which have undergone accelerated aging in salt spray, with exposure according to NIHS 96-50 at a temperature of 45 ° C. with a saline solution at 50g / l of pure NaCl.
  • the 750Au250Cu alloy is used as a reference base.
  • the table in figure 2 and the graph of the figure 1 synthesize the results obtained after aging in a salt spray for various massive gold alloy ingots.
  • the table in figure 3 presents other results obtained on alloys after aging for 40 days in a salt spray.
  • the 13Pd alloy is very interesting from the point of view of the color obtained and of the discoloration. This discoloration as a function of time is represented by curve 1 of the figure 1 . More generally, an alloy composed of at least 750 ⁇ of gold, copper, and with a level of Palladium (Pd) defined by: Pd ⁇ 20 ⁇ or Pd ⁇ 15 ⁇ , or 5 ⁇ ⁇ Pd ⁇ 15 ⁇ , or 8 ⁇ ⁇ Pd ⁇ 15 ⁇ , or 11 ⁇ ⁇ Pd ⁇ 15 ⁇ , is advantageous.
  • AuCuIn alloys are interesting because the results show that In makes it possible to form a single-phase alloy with Au and Cu.
  • the 5In alloy drifts little, as appears on curve 2 of the figure 1 , and already shows an improvement over the reference of a 250Cu alloy.
  • the tests carried out show that there is an optimum at the level of the color drift between 5 and 20 ⁇ In, in particular around 10 ⁇ , with a preferred interval between 7 ⁇ ⁇ In ⁇ 15 ⁇ .
  • an alloy composed of at least 750 ⁇ of gold, copper, and with an Indium (In) rate defined by: In ⁇ 20 ⁇ or In ⁇ 15 ⁇ , or 5% 0 ⁇ In ⁇ 20 % 0, or 7 ⁇ ⁇ In ⁇ 15 ⁇ , is advantageous.
  • Quaternary or quinternary alloys comprising palladium are also very interesting.
  • the alloys 20Pd 10In, 10Pd 5In 5Ca, 15Pd 10ln 5Ca, 5Pd 10ln 5Ca, 10Pd 5In, 20Pd 10In 0.1 Si, etc. exhibit weak drifts and are interesting. Alloys comprising a small amount of calcium or silicon are particularly advantageous.
  • an alloy composed of at least 750 ⁇ of gold, copper, palladium and indium is interesting, particularly when the sum of the levels of Pd and In is less than or equal to 45 ⁇ , or even 40 ⁇ , or even 35 ⁇ , or even 30 ⁇ , and / or when the sum of the Pd and In levels is between 15 ⁇ and 40 ⁇ , or even between 20 ⁇ and 35 ⁇ , and / or when the alloy comprises at least 1 ⁇ of Pd and 1 ⁇ of In, or even at least 5 ⁇ of Pd and 5 ⁇ of In.
  • an alloy composed of at least 750 ⁇ of gold, copper, palladium and at least one element Y, Y being chosen from Ca, Zr, or In is advantageous, particularly when the sum of the levels of Palladium and element (s) Y is less than or equal to 40 ⁇ , or even 35 ⁇ , or even 30 ⁇ , or even 25 ⁇ , or even 20 ⁇ , or even 17 ⁇ , or even 15 ⁇ , or even 13 ⁇ , and / or when the sum of the levels of Pd and of the element (s) Y is included in the 'interval between 15 ⁇ and 40 ⁇ , or even between 20 ⁇ and 35 ⁇ , and / or when the alloy comprises at least 1 ⁇ of Pd and 1 ⁇ of the element (s) Y, or even at least 5 ⁇ of Pd and 5 ⁇ of the Y element (s).
  • an alloy composed of at least 750 ⁇ of gold, copper, palladium and at least one element Y, Y being chosen from In, Ca, Sr, Si, Ti, Zr, or Mg is interesting , particularly when the sum of the levels of Palladium and of the element (s) Y is less than or equal to 40 ⁇ , or even 35 ⁇ , or even 30 ⁇ , or even 25 ⁇ , or even 20 ⁇ , or even 17 ⁇ , or even 15 ⁇ , or even 13 ⁇ , and / or when the sum of the levels of Pd and of the element (s) Y is between 15 ⁇ and 40 ⁇ , or even between 20 ⁇ and 35 ⁇ , and / or when the
  • the alloy comprises at least 1 ⁇ of Pd and 1 ⁇ of the Y element (s), or even at least 5 ⁇ of Pd and 5 ⁇ of the Y element (s).
  • Quaternary or quinternary alloys with In are also interesting. More generally, an alloy composed of at least 750 ⁇ of gold, copper, indium and at least one element Y, Y being chosen from Ca, Sr, Si, Ti, Zr, Mg or Pd is interesting , particularly when the sum of the levels of Indium and of the element Y is less than or equal to 40 ⁇ , or even 35 ⁇ , or even 30 ⁇ , or even 25 ⁇ , or even 20 ⁇ , or even 17 ⁇ , or even 15 ⁇ , or even 13 ⁇ , and / or when the sum of the rates of In and of the element (s) Y is in the range between 15 ⁇ and 40 ⁇ , or even between 20 ⁇ and 35 ⁇ , and / or when the alloy comprises at least 1 ⁇ of In and 1 ⁇ of element (s) Y, or even at least 5 ⁇ of In and 5 ⁇ of element (s) Y.
  • alloys comprising more than four elements can be also interesting, for example five or six, obtained by replacing the element Y of the quaternary compounds.
  • the elements Y i being preferably chosen from Ca, Sr, Si, Ti, Zr, Mg, Pd or In, and so that the sum of rate of all elements except Au and Cu is less than or equal to 40 ⁇ .
  • Such alloys include in particular the alloys comprising the components Au, Cu, Pd, In, and X, where X is at least one element chosen from Ca, Sr, Si, Ti, Zr, Mg.
  • the alloys combining both Palladium and Indium are particularly advantageous compared to the alloys comprising only one or the other of these components, as illustrated by curve 3 of the diagram. figure 1 and the results of the tables of figures 2 and 3 . It is also noted above all that the addition of a small amount of calcium and / or silicon in these alloys makes it possible to obtain an improvement in the resistance to discoloration.
  • an alloy comprising by weight at least 750 ⁇ of gold, also comprising copper, palladium and indium, the sum of the levels of palladium and indium being less than or equal to 35 ⁇ , or even less than or equal to 30 ⁇ , and / or the sum of the levels of palladium and indium being between 20 ⁇ and 35 ⁇ , is advantageous.
  • Such an alloy can include an indium rate defined by: 7 ⁇ ⁇ rate of In ⁇ 15 ⁇ .
  • the figures 4 and 5 further illustrate the advantage of combining palladium and indium and make it possible to visualize the optimum quantities.
  • the figure 4 illustrates the discoloration obtained after 40 days for different alloys, as a function of the sum of the levels of palladium and indium they include. It appears that the best results are obtained for a sum greater than or equal to 15 ⁇ , are further improved for a sum greater than or equal to 20 ⁇ .
  • the 20 ⁇ -35 ⁇ intervals group together several high performance alloys, and the reduced 25 ⁇ -33 ⁇ interval brings together further optimized results.
  • the figure 5 gives additional information on the division of these rates between the two components palladium and indium. It appears that the best results are obtained for a palladium level of between 15 ⁇ and 30 ⁇ , or even between 19 ⁇ and 29 ⁇ , and an indium level of between 1 ⁇ and 15 ⁇ inclusive. As a note, we note that, as soon as a small amount of indium is used, for example between 1 ⁇ and 10 ⁇ , or between 1 ⁇ and 6 ⁇ , and even between 1 ⁇ and 4 ⁇ , there is a significant advantageous effect due to its combination with palladium.
  • the addition of the various components mentioned above has an effect not only on the maintenance over time of the color, but also on the color of the alloy itself.
  • the addition of palladium in a rose gold alloy has the effect of desaturating the pink color, even of making the color of the alloy tend towards gray, and the addition of indium has the effect of a drift. towards the yellow of a pink alloy.
  • the figure 6 schematically illustrates these remarks.
  • the first reference alloy is a conventional 18-karat yellow gold alloy, positioned on the upper left-hand side of the diagram, near the y-axis, corresponding to a strong yellow cast.
  • the second reference alloy is a very red 18-karat gold alloy, comprising 250 cuivre of copper, positioned on the right and lower part of the diagram, near the abscissa axis.
  • the sum of the levels of palladium and indium is advantageously included in the intervals between 15 ⁇ -35 ⁇ , even between 20 ⁇ and 35 ⁇ , or even between 25 ⁇ and 33 ⁇ , which represent choices interesting for obtaining a satisfactory pink color of a gold alloy, these limits can be included or excluded.
  • rose gold alloys combining palladium and indium are interesting because they allow both to achieve a color of satisfactory aesthetics and which fades little over time.
  • the precise amounts for each of these two components and their sum represent tradeoffs between the reduction of discoloration and the aesthetics of the desired pink color.
  • the intervals for this sum of the levels of palladium and indium which make it possible both to achieve a satisfactory pink color and a weak discoloration are between 15 ⁇ and 35 ⁇ , or even between 20 ⁇ and 35 ⁇ , or even between 25 ⁇ and 33 ⁇ , as shown in previous analyzes.
  • a high level of palladium greater than or equal to 15 ⁇ , or even greater than or equal to 19 ⁇ , is favorable to the reduction of discoloration.
  • a low level of palladium less than or equal to 20% 0, or even less than or equal to 19 ⁇ or 18 ⁇ , is favorable to the aesthetics of the color pink.
  • a level of palladium between 19 ⁇ and 25 ⁇ inclusive forms a good solution.
  • the preceding considerations can be adapted to any quantity of copper greater than or equal to 180 ⁇ , in particular also for a relatively small quantity of copper, for example between 180 ⁇ and 200 ⁇ .
  • a large quantity of copper is imposed, in particular greater than or equal to 200 ⁇ .
  • a pink color can be more easily obtained, even by using larger quantities of the components tending to degrade it, as explained previously.
  • the amount of copper Cu is greater than or equal to 200 ⁇ , it is possible to obtain suitable alloys with a palladium level between 4 ⁇ and 35 ⁇ and an indium level between 1 ⁇ and 16 ⁇ .
  • compositions only mention the majority elements of the alloy, to which can be added at least one grain refiner element according to the knowledge of those skilled in the art, which gives other variant embodiments of the invention.
  • This grain refiner element can be present, for example, at most at the rate of 2 ⁇ , or even 1 ⁇ , of at least one element chosen by way of example from Ru, Ir, Re, Co, V and Mo.
  • elements such as Ir, Re or Ru make it possible to guarantee the fineness of the grain and to avoid porosities, without appreciably modify the hardness, nor affect the color, which is advantageous compared to the sought object.
  • the various figures illustrate a particular technical effect obtained with the addition of calcium Ca and / or silicon Si, in very small quantities, on the reduction of the discoloration of the alloys mentioned by way of example.
  • a very small amount in particular less than or equal to 10 ⁇ , or even 7 ⁇ , or even 5 ⁇ , for calcium, and / or less than or equal to 2 ⁇ , or even 0.5 ⁇ for silicon, is sufficient to significantly reduce discoloration over time of the illustrated alloys, without having a noticeable effect on the color itself, in particular when a sufficient copper content, preferably greater than or equal to 200 ⁇ , is used.
  • the 10Pd 5In 5Ca alloy is more resistant to discoloration than a 10Pd 5In alloy.
  • a 20Pd 10ln 1Ca or 20Pd 10ln 0.5Ca or 20Pd 10ln 0.1Si or 20Pd 10In 0.02Si alloy is better than a 20Pd 10In alloy.
  • Previous studies have underlined the interest of combining calcium or silicon with a rose gold alloy combining palladium and indium. However, this favorable effect of the Ca and Si components is also verified on any other rose gold alloy, which does not necessarily include palladium and indium. For example, we can see on the figure 2 that a 10Pd 5Ca alloy is much better than a 13Pd or 10Pd 5In alloy.
  • the addition of the Ca and Si components in rose gold alloys comprising platinum also makes it possible to obtain alloys which are better resistant to discoloration.
  • the invention relates to a timepiece, jewelry or jewelry comprising an alloy comprising by weight at least 750 ⁇ of gold, characterized in that the alloy also comprises at least 180 ⁇ of copper, or even at least 200 ⁇ of copper, and comprises calcium, with a calcium level less than or equal to 10 ⁇ or even 7 ⁇ , or even 5 ⁇ , and / or silicon, with a silicon content less than or equal to 2 ⁇ , or even 0.5 ⁇ .
  • the upper limits of preferential concentration are different for Ca and Si, because it appeared that their behavior as a function of the concentration in the alloy is not identical. It is in fact preferable to avoid the formation of precipitates in order to be able to deform and / or polish the solid alloy.
  • concentration of Ca and Si should be adjusted by a person skilled in the art depending on the composition chosen for the rose gold alloy.
  • such a rose gold alloy according to the embodiments of the invention may not include silver, which induces the negative effect of yellowing the color of the alloy and even of making tender this color towards an unsightly greenish color, moving it away from the sought-after pink.
  • silver does not have a very effective effect on the durability of the color over time, compared to the other alloys studied. There are therefore two good reasons to exclude money from all the achievements proposed above. However, alloys comprising silver are not totally excluded since they could still take the advantages mentioned above.
  • the alloys described will therefore be particularly effective for producing all or part of a timepiece, such as a watch case, a bracelet, a watch, etc., or a piece of jewelry. or jewelry.
  • this production of a timepiece, piece of jewelry or jewelry means the manufacture of all or a significant part of the thickness of a timepiece, and not a simple surface coating.
  • the tests studied and described above also relate to massive volumes of certain alloys.
  • the parts considered comprise a large amount of alloy are advantageously in the form of a solid alloy capable of being deformed and of being polished, comprising in particular at least a part of thickness greater than or equal to 0.1 mm. .

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Description

IntroductionIntroduction

L'invention concerne un alliage d'or rose, particulièrement adapté pour une pièce d'horlogerie, et une pièce d'horlogerie, de bijouterie ou de joaillerie en tant que telle comprenant un tel alliage, comme une montre.The invention relates to a rose gold alloy, particularly suitable for a timepiece, and a timepiece, jewelry or jewelry as such comprising such an alloy, such as a watch.

Etat de l'ArtState of the art

La couleur d'alliages d'or dépend de leurs teneurs en éléments d'alliage. Pour des alliages AuCuAg 18ct par exemple, une teneur en cuivre supérieure à 180‰ et une teneur en argent de l'ordre de 40‰ leur confère une couleur rouge. La couleur évolue vers le rose puis vers le jaune si la teneur en cuivre décroît de 180‰ à 150‰ puis de 150‰ à 60‰ et si la teneur en argent augmente de 40‰ à 150‰. Nous avons constaté que des boîtiers ou des bracelets de montres fabriqués dans ces alliages d'or usuels avaient tendance à subir une modification progressive de leur couleur sous l'action de l'eau du robinet, de l'eau de mer, de l'eau des piscines, de l'eau salée ou encore de l'eau savonneuse.The color of gold alloys depends on their content of alloying elements. For AuCuAg 18ct alloys, for example, a copper content greater than 180 ‰ and a silver content of the order of 40 une gives them a red color. The color evolves towards pink then towards yellow if the copper content decreases from 180 ‰ to 150 ‰ then from 150 ‰ to 60 ‰ and if the silver content increases from 40 ‰ to 150 ‰. We have observed that watch cases or bracelets made from these usual gold alloys tended to undergo a gradual change in their color under the action of tap water, sea water, water. swimming pool water, salt water or soapy water.

L'un des buts de l'invention est d'améliorer la résistance à une modification de couleur d'une pièce d'horlogerie, de bijouterie ou de joaillerie fabriquée dans un alliage d'or rose et soumise, en cours d'utilisation, à des milieux aqueux faiblement agressifs.One of the aims of the invention is to improve the resistance to a change in color of a timepiece, piece of jewelry or jewelry made from a rose gold alloy and subjected, in use, to to weakly aggressive aqueous media.

Un autre but de l'invention est de définir un alliage d'or de couleur rose dont le rose présente un aspect esthétique le plus attractif possible.Another object of the invention is to define a rose-colored gold alloy, the pink of which has the most attractive aesthetic appearance possible.

Le document JP11-335755 décrit un alliage d'or rose avec une composition pondérale de 75%Au, 22%Cu, 1.5%Ag, 1%Pd, 0.5%In.The document JP11-335755 describes a rose gold alloy with a weight composition of 75% Au, 22% Cu, 1.5% Ag, 1% Pd, 0.5% In.

Brève description de l'inventionBrief description of the invention

L'invention est précisément définie par les revendications.The invention is precisely defined by the claims.

Brève description des figuresBrief description of the figures

Ces objets, caractéristiques et avantages de la présente invention seront exposés en détail dans la description suivante de modes de réalisation particuliers faits à titre non-limitatif en relation avec les figures jointes parmi lesquelles :

  • La figure 1 montre trois courbes expérimentales de décoloration obtenues respectivement sur un alliage 13Pd, (courbe 1), 5In (courbe 2) et 20Pd10ln (courbe 3).
  • La figure 2 représente un tableau de résultats de test de décoloration obtenus après 20 jours sur différents alliages.
  • La figure 3 représente un tableau de résultats de test de décoloration obtenus après 40 jours sur différents alliages.
  • La figure 4 représente la décoloration obtenue après 40 jours en fonction de la somme des composants palladium et indium de différents alliages.
  • La figure 5 illustre la décoloration obtenue après 40 jours pour différents alliages en fonction de leurs taux de palladium et d'indium.
  • La figure 6 positionne schématiquement plusieurs alliages sur un graphe pour illustrer la couleur obtenue pour ces différents alliages.
These objects, characteristics and advantages of the present invention will be explained in detail in the following description of particular embodiments made without limitation in relation to the accompanying figures, among which:
  • The figure 1 shows three experimental discoloration curves obtained respectively on a 13Pd alloy (curve 1), 5In (curve 2) and 20Pd10ln (curve 3).
  • The figure 2 shows a table of discoloration test results obtained after 20 days on different alloys.
  • The figure 3 shows a table of discoloration test results obtained after 40 days on different alloys.
  • The figure 4 represents the discoloration obtained after 40 days as a function of the sum of the palladium and indium components of different alloys.
  • The figure 5 illustrates the discoloration obtained after 40 days for different alloys as a function of their levels of palladium and indium.
  • The figure 6 schematically positions several alloys on a graph to illustrate the color obtained for these different alloys.

Des modes de réalisation de l'invention vont maintenant être présentés, à partir d'exemples précis et de résultats d'expériences empiriques. Les exemples qui ne tombent pas dans l'étendue des revendications ne font pas partie de l'invention. Pour cela, des lingots sont préparés par coulée statique sous vide (fusion dans un creuset en graphite et refroidissement sous azote). Des échantillons sont tronçonnés depuis le lingot à l'état brut de coulée. La surface est préparée par polissage. Un échantillon typique présente une section carrée 20mm x 20mm x 5mm. Tous les tests sont réalisés sur des alliages bruts de coulée, sans déformation ou traitement thermique ultérieurs, et sans adjonction des affineurs de grains habituels.Embodiments of the invention will now be presented, based on specific examples and results of empirical experiments. Examples which do not fall within the scope of the claims do not form part of the invention. For this, ingots are prepared by static casting under vacuum (melting in a graphite crucible and cooling under nitrogen). Samples are cut from the ingot in the as-cast state. The surface is prepared by polishing. A typical sample has a 20mm x 20mm x 5mm square section. All the tests are carried out on as-cast alloys, without deformation or subsequent heat treatment, and without the addition of the usual grain refiners.

L'analyse cristallographique des échantillons est réalisée avec un diffractomètre à rayons X avec anode Cu. Un contrôle métallographique et une analyse des stoechiométries des phases sont réalisés par microscopie électronique à balayage MEB - EDX.The crystallographic analysis of the samples is carried out with an X-ray diffractometer with Cu anode. A metallographic check and an analysis of the stoichiometries of the phases are carried out by SEM - EDX scanning electron microscopy.

Les variations de couleur sont mesurées avec un spectrocolorimètre avec sphère d'intégration. La couleur est définie de façon conventionnelle par un point de l'espace CIELAB formé d'un axe vert-rouge en abscisses, d'un axe bleu-jaune en ordonnées et d'un axe représentatif du contraste (cf. rapport CIE15:2004 établi par la Commission internationale de l'Eclairage). Les mesures ont toutes été réalisées en utilisant la convention suivante : illuminant D65 et observateur standard 10° (CIE1964). Les écarts de couleur ΔE sont définis par le DE2000 (équation 8.36, paragraphe 8.3, rapport CIE15:2004). Une mesure de l'écart de couleur est effectuée entre des échantillons à neuf (coulés et polis) et des échantillons ayant subi un vieillissement accéléré au brouillard salin, avec une exposition selon la norme NIHS 96-50 à une température de 45°C avec une solution saline à 50g/l de NaCl pur. L'alliage 750Au250Cu sert de base de référence.The color variations are measured with a spectrocolorimeter with integrating sphere. The color is defined in a conventional manner by a point in CIELAB space formed by a green-red axis on the abscissa, a blue-yellow axis on the ordinate and an axis representative of the contrast (cf. report CIE15: 2004 established by the International Commission on Illumination). The measurements were all performed using the following convention: illuminant D65 and standard observer 10 ° (CIE1964). The color differences ΔE are defined by DE2000 (equation 8.36, paragraph 8.3, report CIE15: 2004). A measurement of the color difference is made between new samples (cast and polished) and samples which have undergone accelerated aging in salt spray, with exposure according to NIHS 96-50 at a temperature of 45 ° C. with a saline solution at 50g / l of pure NaCl. The 750Au250Cu alloy is used as a reference base.

La convention suivante est utilisée pour les désignations des alliages :

  • Pour les alliages 18ct (750Au), indication de la teneur des éléments d'addition en pourmille poids avant le symbole de l'élément. La teneur en cuivre n'est pas indiquée car elle correspond au solde. Toutefois, cette teneur en cuivre sera avantageusement supérieure ou égale à 180‰, voire supérieure ou égale à 200‰. Exemple : 10In correspond à un alliage 750Au240Cu10In ;
  • Pour les alliages non 18ct, indication de la teneur en Au en pourmille poids avant l'élément puis indication des éléments d'addition selon le point précédent ;
  • Les plages de valeur qui seront mentionnées par la suite peuvent inclure ou exclure leurs bornes, dans les cas où cela n'est pas précisé..
The following convention is used for the designations of alloys:
  • For 18ct (750Au) alloys, indication of the content of the additive elements in per thousand weight before the element symbol. The copper content is not indicated because it corresponds to the balance. However, this copper content will advantageously be greater than or equal to 180 ‰, or even greater than or equal to 200 ‰. Example: 10In corresponds to a 750Au240Cu10In alloy;
  • For non 18ct alloys, indication of the Au content in per thousand weight before the element then indication of the addition elements according to the previous point;
  • The ranges of values that will be mentioned later can include or exclude their limits, in cases where this is not specified.

Le tableau en figure 2 et le graphique de la figure 1 synthétisent les résultats obtenus après vieillissement au brouillard salin pour différents lingots massifs en alliage d'or. Le tableau en figure 3 présente d'autres résultats obtenus sur des alliages après un vieillissement de 40 jours au brouillard salin.The table in figure 2 and the graph of the figure 1 synthesize the results obtained after aging in a salt spray for various massive gold alloy ingots. The table in figure 3 presents other results obtained on alloys after aging for 40 days in a salt spray.

L'alliage 13Pd est très intéressant, du point de vue de la couleur obtenue et de la décoloration. Cette décoloration en fonction du temps est représentée par la courbe 1 de la figure 1.
Plus généralement, un alliage composé d'au moins 750‰ d'or, de cuivre, et avec un taux de Palladium (Pd) défini par: Pd ≤ 20‰ ou Pd ≤ 15‰, ou 5‰ ≤ Pd ≤ 15‰, ou 8‰ ≤ Pd ≤ 15‰, ou 11‰ ≤ Pd ≤ 15‰, est avantageux.The 13Pd alloy is very interesting from the point of view of the color obtained and of the discoloration. This discoloration as a function of time is represented by curve 1 of the figure 1 .
More generally, an alloy composed of at least 750 ‰ of gold, copper, and with a level of Palladium (Pd) defined by: Pd ≤ 20 ‰ or Pd ≤ 15 ‰, or 5 ‰ ≤ Pd ≤ 15 ‰, or 8 ‰ ≤ Pd ≤ 15 ‰, or 11 ‰ ≤ Pd ≤ 15 ‰, is advantageous.

Les alliages AuCuIn sont intéressants, car les résultats mettent en évidence que In permet de former un alliage monophasé avec Au et Cu. En particulier, l'alliage 5In dérive peu, comme cela apparait sur la courbe 2 de la figure 1, et montre déjà une amélioration par rapport à la référence d'un alliage 250Cu. En effet, les essais réalisés montrent qu'il y a un optimum au niveau de la dérive de couleur entre 5 et 20‰ d'In, en particulier autour de 10‰, avec un intervalle préféré entre 7‰ ≤ In ≤ 15‰. Plus généralement, un alliage composé d'au moins 750‰ d'or, de cuivre, et avec un taux d'Indium (In) défini par: In ≤ 20‰ ou In ≤ 15‰, ou 5%0 ≤ In < 20%0, ou 7‰ ≤ In ≤ 15‰, est avantageux.AuCuIn alloys are interesting because the results show that In makes it possible to form a single-phase alloy with Au and Cu. In particular, the 5In alloy drifts little, as appears on curve 2 of the figure 1 , and already shows an improvement over the reference of a 250Cu alloy. Indeed, the tests carried out show that there is an optimum at the level of the color drift between 5 and 20 ‰ In, in particular around 10 ‰, with a preferred interval between 7 ‰ ≤ In ≤ 15 ‰. More generally, an alloy composed of at least 750 ‰ of gold, copper, and with an Indium (In) rate defined by: In ≤ 20 ‰ or In ≤ 15 ‰, or 5% 0 ≤ In <20 % 0, or 7 ‰ ≤ In ≤ 15 ‰, is advantageous.

Les alliages quaternaires ou quinternaires comprenant du palladium sont aussi très intéressants. Notamment, comme cela ressort des résultats des figures 2 et 3 portant sur la résistance dans le temps à la décoloration, les alliages 20Pd 10In, 10Pd 5In 5Ca, 15Pd 10ln 5Ca, 5Pd 10ln 5Ca, 10Pd 5In, 20Pd 10In 0,1 Si, etc., présentent des dérives faibles et sont intéressants. Les alliages comprenant une faible quantité de calcium ou de silicium sont particulièrement intéressants.Quaternary or quinternary alloys comprising palladium are also very interesting. In particular, as emerges from the results of figures 2 and 3 bearing on the resistance over time to discoloration, the alloys 20Pd 10In, 10Pd 5In 5Ca, 15Pd 10ln 5Ca, 5Pd 10ln 5Ca, 10Pd 5In, 20Pd 10In 0.1 Si, etc., exhibit weak drifts and are interesting. Alloys comprising a small amount of calcium or silicon are particularly advantageous.

Plus généralement, on note aussi qu'un alliage composé d'au moins 750‰ d'or, de cuivre, de Palladium et d'Indium est intéressant, particulièrement lorsque la somme des taux de Pd et d'In est inférieure ou égale à 45‰, voire 40‰, voire 35‰, voire 30‰, et/ou lorsque la somme des taux de Pd et d'In est comprise dans l'intervalle entre 15‰ et 40‰, voire entre 20‰ et 35‰, et/ou lorsque l'alliage comprend au moins 1‰ de Pd et 1‰ de In, voire au moins 5‰ de Pd et 5‰ de In.More generally, we also note that an alloy composed of at least 750 ‰ of gold, copper, palladium and indium is interesting, particularly when the sum of the levels of Pd and In is less than or equal to 45 ‰, or even 40 ‰, or even 35 ‰, or even 30 ‰, and / or when the sum of the Pd and In levels is between 15 ‰ and 40 ‰, or even between 20 ‰ and 35 ‰, and / or when the alloy comprises at least 1 ‰ of Pd and 1 ‰ of In, or even at least 5 ‰ of Pd and 5 ‰ of In.

Plus généralement, un alliage composé d'au moins 750‰ d'or, de cuivre, de Palladium et d'au moins un élément Y, Y étant choisi parmi Ca, Zr, ou In est intéressant, particulièrement lorsque la somme des taux de Palladium et du ou des élément(s) Y est inférieure ou égale à 40‰, voire 35‰, voire 30‰, voire 25‰, voire 20‰, voire 17‰, voire 15‰, voire 13‰, et/ou lorsque la somme des taux de Pd et du ou des élément(s) Y est comprise dans l'intervalle entre 15‰ et 40‰, voire entre 20‰ et 35‰, et/ou lorsque l'alliage comprend au moins 1‰ de Pd et 1‰ du ou des éléments Y, voire au moins 5‰ de Pd et 5‰ du ou des éléments Y.More generally, an alloy composed of at least 750 ‰ of gold, copper, palladium and at least one element Y, Y being chosen from Ca, Zr, or In is advantageous, particularly when the sum of the levels of Palladium and element (s) Y is less than or equal to 40 ‰, or even 35 ‰, or even 30 ‰, or even 25 ‰, or even 20 ‰, or even 17 ‰, or even 15 ‰, or even 13 ‰, and / or when the sum of the levels of Pd and of the element (s) Y is included in the 'interval between 15 ‰ and 40 ‰, or even between 20 ‰ and 35 ‰, and / or when the alloy comprises at least 1 ‰ of Pd and 1 ‰ of the element (s) Y, or even at least 5 ‰ of Pd and 5 ‰ of the Y element (s).

Plus généralement, un alliage composé d'au moins 750‰ d'or, de cuivre, de Palladium et d'au moins un élément Y, Y étant choisi parmi In, Ca, Sr, Si, Ti, Zr, ou Mg est intéressant, particulièrement lorsque la somme des taux de Palladium et du ou des élément(s) Y est inférieure ou égale à 40‰, voire 35‰, voire 30‰, voire 25‰, voire 20‰, voire 17‰, voire 15‰, voire 13‰, et/ou lorsque la somme des taux de Pd et du ou des élément(s) Y est comprise dans l'intervalle entre 15‰ et 40‰, voire entre 20‰ et 35‰, et/ou lorsque l'alliage comprend au moins 1‰ de Pd et 1‰ du ou des éléments Y, voire au moins 5‰ de Pd et 5‰ du ou des éléments Y.More generally, an alloy composed of at least 750 ‰ of gold, copper, palladium and at least one element Y, Y being chosen from In, Ca, Sr, Si, Ti, Zr, or Mg is interesting , particularly when the sum of the levels of Palladium and of the element (s) Y is less than or equal to 40 ‰, or even 35 ‰, or even 30 ‰, or even 25 ‰, or even 20 ‰, or even 17 ‰, or even 15 ‰, or even 13 ‰, and / or when the sum of the levels of Pd and of the element (s) Y is between 15 ‰ and 40 ‰, or even between 20 ‰ and 35 ‰, and / or when the The alloy comprises at least 1 ‰ of Pd and 1 ‰ of the Y element (s), or even at least 5 ‰ of Pd and 5 ‰ of the Y element (s).

Les alliages quaternaires ou quinternaires avec In sont aussi intéressants. Plus généralement, un alliage composé d'au moins 750‰ d'or, de cuivre, d'Indium et d'au moins un élément Y, Y étant choisi parmi Ca, Sr, Si, Ti, Zr, Mg ou Pd est intéressant, particulièrement lorsque la somme des taux d'Indium et du élément Y est inférieure ou égale à 40‰, voire 35‰, voire 30‰, voire 25‰, voire 20‰, voire 17‰, voire 15‰, voire 13‰, et/ou lorsque la somme des taux de In et du ou des élément(s) Y est comprise dans l'intervalle entre 15‰ et 40‰, voire entre 20‰ et 35‰, et/ou lorsque l'alliage comprend au moins 1‰ de In et 1‰ du ou des éléments Y, voire au moins 5‰ de In et 5‰ du ou des éléments Y.Quaternary or quinternary alloys with In are also interesting. More generally, an alloy composed of at least 750 ‰ of gold, copper, indium and at least one element Y, Y being chosen from Ca, Sr, Si, Ti, Zr, Mg or Pd is interesting , particularly when the sum of the levels of Indium and of the element Y is less than or equal to 40 ‰, or even 35 ‰, or even 30 ‰, or even 25 ‰, or even 20 ‰, or even 17 ‰, or even 15 ‰, or even 13 ‰, and / or when the sum of the rates of In and of the element (s) Y is in the range between 15 ‰ and 40 ‰, or even between 20 ‰ and 35 ‰, and / or when the alloy comprises at least 1 ‰ of In and 1 ‰ of element (s) Y, or even at least 5 ‰ of In and 5 ‰ of element (s) Y.

Les alliages ternaires suivants titrant 18ct ou plus sont particulièrement intéressants :

  • AuCuPd avec Pd<20‰, plus particulièrement avec 5‰≤Pd<20‰, plus particulièrement avec 5‰≤Pd≤15‰
  • AuCuIn avec In<20‰, plus particulièrement avec 5‰≤In<20‰, plus particulièrement avec 7‰≤In≤15‰
Of particular interest are the following ternary alloys grading 18ct or more:
  • AuCuPd with Pd <20 ‰, more particularly with 5 ‰ ≤Pd <20 ‰, more particularly with 5 ‰ ≤Pd≤15 ‰
  • AuCuIn with In <20 ‰, more particularly with 5 ‰ ≤In <20 ‰, more particularly with 7 ‰ ≤In≤15 ‰

Les alliages quaternaires AuCuPdln titrant 18ct ou plus sont particulièrement intéressants :

  • en particulier avec la somme des taux de Pd et d'In inférieure ou égale à 45‰, voire 40‰, voire 35‰, voire 30‰ ;
  • et/ou avec la somme des taux de Pd et d'In comprise dans l'intervalle entre 15‰ et 40‰, voire entre 20‰ et 35‰;
  • et/ou avec au moins 1‰ de Pd et 1‰ de In, voire au moins 5‰ de Pd et 5‰ de In ;
  • en particulier l'alliage 20Pd10In ou l'alliage 10Pd5In.
Of particular interest are AuCuPdln quaternary alloys grading 18ct or more:
  • in particular with the sum of the rates of Pd and In less than or equal to 45 ‰, or even 40 ‰, or even 35 ‰, or even 30 ‰;
  • and / or with the sum of the Pd and In rates in the range between 15 ‰ and 40 ‰, or even between 20 ‰ and 35 ‰;
  • and / or with at least 1 ‰ of Pd and 1 ‰ of In, or even at least 5 ‰ of Pd and 5 ‰ of In;
  • in particular the 20Pd10In alloy or the 10Pd5In alloy.

Les alliages quaternaires ou quinternaires titrant 18 ct ou plus suivants sont aussi particulièrement intéressants :

  • AuCuXY, où X est Pd ou In, et Y est au moins un élément parmi Pd (si X≠Pd), In (si X≠In), Ca, Sr, Si, Ti, Zr, ou Mg,
  • en particulier avec la somme des taux X+Y≤40‰
  • et/ou avec les concentrations pour Pd, In et élément(s) Y : Pd, In ≤ 40‰ et Y (Y≠In,Pd) ≤ 10‰;
  • et/ou avec au moins 1‰ de Pd et 1‰ du ou des éléments Y, voire au moins 5‰ de Pd et 5‰ du ou des éléments Y.
The following quaternary or quinternary alloys grading 18 ct or more are also particularly interesting:
  • AuCuXY, where X is Pd or In, and Y is at least one of Pd (if X ≠ Pd), In (if X ≠ In), Ca, Sr, Si, Ti, Zr, or Mg,
  • in particular with the sum of the rates X + Y≤40 ‰
  • and / or with the concentrations for Pd, In and element (s) Y: Pd, In ≤ 40 ‰ and Y (Y ≠ In, Pd) ≤ 10 ‰;
  • and / or with at least 1 ‰ of Pd and 1 ‰ of the Y element (s), or even at least 5 ‰ of Pd and 5 ‰ of the Y element (s).

Les alliages quinternaires AuCuPdInX où X est choisi parmi Ca, Sr, Si, Ti, Zr, Mg sont aussi intéressants.Quinternary AuCuPdInX alloys where X is chosen from Ca, Sr, Si, Ti, Zr, Mg are also interesting.

Enfin, il est à noter que d'autres alliages comprenant plus de quatre éléments peuvent être aussi intéressants, par exemple cinq ou six, obtenus en remplaçant l'élément Y des composés quaternaires mentionnés précédemment par n éléments Y1, Y2, ..., Yn, les éléments Yi étant de préférence choisis parmi Ca, Sr, Si, Ti, Zr, Mg, Pd ou In, et de sorte que la somme des taux de tous les éléments hors Au et Cu soit inférieure ou égale à 40‰. De tels alliages incluent notamment les alliages comprenant les composants Au, Cu, Pd, In, et X, où X est au moins un élément choisi parmi Ca, Sr, Si, Ti, Zr, Mg.Finally, it should be noted that other alloys comprising more than four elements can be also interesting, for example five or six, obtained by replacing the element Y of the quaternary compounds. previously mentioned by n elements Y 1 , Y 2 , ..., Y n , the elements Y i being preferably chosen from Ca, Sr, Si, Ti, Zr, Mg, Pd or In, and so that the sum of rate of all elements except Au and Cu is less than or equal to 40 ‰. Such alloys include in particular the alloys comprising the components Au, Cu, Pd, In, and X, where X is at least one element chosen from Ca, Sr, Si, Ti, Zr, Mg.

Finalement, on note que les alliages combinant à la fois du Palladium et de l'Indium sont particulièrement avantageux par rapport aux alliages ne comprenant que l'un ou l'autre de ces composants, comme l'illustrent la courbe 3 de la figure 1 et les résultats des tableaux des figures 2 et 3. On note aussi surtout que l'ajout d'une faible quantité de calcium et/ou de silicium dans ces alliages permet d'obtenir une amélioration de la résistance à la décoloration.Finally, it is noted that the alloys combining both Palladium and Indium are particularly advantageous compared to the alloys comprising only one or the other of these components, as illustrated by curve 3 of the diagram. figure 1 and the results of the tables of figures 2 and 3 . It is also noted above all that the addition of a small amount of calcium and / or silicon in these alloys makes it possible to obtain an improvement in the resistance to discoloration.

Notamment, il apparaît qu'un alliage comprenant en poids au moins 750‰ d'or, comprenant également du cuivre, du palladium et de l'indium, la somme des taux de palladium et d'indium étant inférieure ou égale à 35‰, voire inférieure ou égale à 30‰, et/ou la somme des taux de palladium et d'indium étant comprise entre 20‰ et 35‰, est avantageux. Un tel alliage peut comprendre un taux d'Indium défini par: 7‰ ≤ taux de In ≤ 15‰.In particular, it appears that an alloy comprising by weight at least 750 ‰ of gold, also comprising copper, palladium and indium, the sum of the levels of palladium and indium being less than or equal to 35 ‰, or even less than or equal to 30 ‰, and / or the sum of the levels of palladium and indium being between 20 ‰ and 35 ‰, is advantageous. Such an alloy can include an indium rate defined by: 7 ‰ ≤ rate of In ≤ 15 ‰.

Les figures 4 et 5 illustrent de manière complémentaire l'intérêt de combiner du palladium et de l'indium et permettent de visualiser les quantités optimales.The figures 4 and 5 further illustrate the advantage of combining palladium and indium and make it possible to visualize the optimum quantities.

La figure 4 illustre la décoloration obtenue après 40 jours pour différents alliages, en fonction de la somme des taux de palladium et d'indium qu'ils comprennent. Il apparaît que les meilleurs résultats sont obtenus pour une somme supérieure ou égale à 15‰, sont encore améliorés pour une somme supérieure ou égale à 20‰. Les intervalles 20‰-35‰ regroupent plusieurs alliages très performants, et l'intervalle réduit 25‰-33‰ regroupe des résultats encore optimisés.The figure 4 illustrates the discoloration obtained after 40 days for different alloys, as a function of the sum of the levels of palladium and indium they include. It appears that the best results are obtained for a sum greater than or equal to 15 ‰, are further improved for a sum greater than or equal to 20 ‰. The 20 ‰ -35 ‰ intervals group together several high performance alloys, and the reduced 25 ‰ -33 ‰ interval brings together further optimized results.

La figure 5 donne des indications complémentaires sur le partage de ces taux entre les deux composants palladium et indium. Il apparaît que les meilleurs résultats sont obtenus pour un taux de palladium compris entre 15‰ et 30‰, voire entre 19‰ et 29‰, et un taux d'indium compris entre 1‰ et 15‰ inclus. En remarque, on note que, dès l'utilisation d'une faible quantité d'indium, par exemple comprise entre 1‰ et 10‰, ou entre 1‰ et 6‰, et même entre 1‰ et 4‰, il existe un effet significatif avantageux du fait de sa combinaison avec le palladium.The figure 5 gives additional information on the division of these rates between the two components palladium and indium. It appears that the best results are obtained for a palladium level of between 15 ‰ and 30 ‰, or even between 19 ‰ and 29 ‰, and an indium level of between 1 ‰ and 15 ‰ inclusive. As a note, we note that, as soon as a small amount of indium is used, for example between 1 ‰ and 10 ‰, or between 1 ‰ and 6 ‰, and even between 1 ‰ and 4 ‰, there is a significant advantageous effect due to its combination with palladium.

Outre les considérations précédentes très importantes portant sur le maintien de la couleur d'un alliage dans le temps, il est aussi nécessaire de prendre en compte la qualité de la couleur elle-même obtenue pour un alliage considéré, et particulièrement l'esthétique de la couleur rose obtenue. En effet, l'ajout des différents composants mentionnés précédemment a un effet non seulement sur le maintien dans le temps de la couleur, mais aussi sur la couleur elle-même de l'alliage. Par exemple, l'ajout de palladium dans un alliage d'or rose a pour effet de désaturer la couleur rose, même de faire tendre la couleur de l'alliage vers le gris, et l'ajout d'indium a pour effet une dérive vers le jaune d'un alliage rose.In addition to the above very important considerations relating to the maintenance of the color of an alloy over time, it is also necessary to take into account the quality of the color itself obtained for a considered alloy, and particularly the aesthetics of the pink color obtained. Indeed, the addition of the various components mentioned above has an effect not only on the maintenance over time of the color, but also on the color of the alloy itself. For example, the addition of palladium in a rose gold alloy has the effect of desaturating the pink color, even of making the color of the alloy tend towards gray, and the addition of indium has the effect of a drift. towards the yellow of a pink alloy.

La figure 6 illustre schématiquement ces remarques. On note en abscisse la coordonnée a* et en ordonnée la coordonnée b*. En remarque, cette couleur peut se mesurer par rapport à des couleurs de référence, et peut aussi faire l'objet d'un examen visuel, l'effet esthétique obtenu étant particulièrement notable par une observation visuelle. Le premier alliage de référence est un alliage d'or jaune 18 carats conventionnel, positionné sur la partie gauche et haute du diagramme, à proximité de l'axe des ordonnées, correspondant à une forte dominante jaune. Le second alliage de référence est un alliage d'or 18 carats très rouge, comprenant 250‰ de cuivre, positionné sur la partie droite et basse du diagramme, à proximité de l'axe des abscisses. On note que l'ajout d'une quantité relativement importante de palladium, comme l'illustre l'exemple de l'alliage 40Pd, a pour effet de fortement atténuer la saturation de la couleur, pour finalement donner un alliage très pâle, d'apparence grisâtre. Après plusieurs essais, il apparaît utile d'utiliser une quantité de palladium inférieure ou égale à 29‰ pour conserver une couleur rose satisfaisante, ce qui se manifeste par un positionnement dans la zone 5 mise en évidence sur la figure 6. Ainsi, un alliage 20Pd se positionne par exemple au niveau d'une couleur rose satisfaisante. On note que l'ajout d'une faible quantité d'indium à cet alliage 20Pd a peu d'effet sur la couleur, comme l'illustre schématiquement le positionnement de l'alliage 20Pd10ln sur la figure 6, qui est très proche de l'alliage 20Pd. En remarque, si nous avions ajouté 10Pd à l'alliage 20Pd, pour obtenir un alliage 30Pd, en remplacement des 10ln ajoutés, la désaturation de la couleur rose aurait été très marquée. Cela permet aussi de conclure que du point de vue de la couleur, il est avantageux de combiner de l'indium et du palladium, plutôt que de considérer une seule quantité équivalente de palladium. Il apparaît de plus que, pour conserver une couleur rose satisfaisante, la somme des taux des deux composants ne doit pas être trop importante, sinon le rose sera dégradé par rapport au rose recherché. Il est ainsi préférable de rester inférieur ou égal à 35‰, voire 33‰, 30‰, 29%0 ou 25‰, ces valeurs représentant différents paliers, tous satisfaisants, mais permettant successivement d'améliorer le résultat. En complément, il est aussi intéressant de choisir une quantité minimale suffisante de la somme des taux des composants palladium et indium, pour éviter que la couleur rose ne tende vers le rouge. Pour cela, il apparaît qu'un minimum de 15‰ est fortement recommandé, et qu'il faut choisir de préférence une valeur supérieure ou égale à 20%0, voire 25‰. En synthèse de ces considérations, la somme des taux de palladium et d'indium est avantageusement comprise dans les intervalles entre 15‰-35‰, voire entre 20‰ et 35‰, ou même entre 25‰ et 33‰, qui représentent des choix intéressants pour l'obtention d'une couleur rose satisfaisante d'un alliage d'or, ces bornes pouvant être inclues ou exclues.The figure 6 schematically illustrates these remarks. We denote on the abscissa the coordinate a * and on the ordinate the coordinate b *. As a note, this color can be measured against reference colors, and may also be the subject of a visual examination, the aesthetic effect obtained being particularly noticeable by visual observation. The first reference alloy is a conventional 18-karat yellow gold alloy, positioned on the upper left-hand side of the diagram, near the y-axis, corresponding to a strong yellow cast. The second reference alloy is a very red 18-karat gold alloy, comprising 250 cuivre of copper, positioned on the right and lower part of the diagram, near the abscissa axis. It is noted that the addition of a relatively large quantity of palladium, as illustrated by the example of the 40Pd alloy, has the effect of greatly reducing the saturation of the color, to finally give a very pale alloy, of grayish appearance. After several tests, it appears useful to use a quantity of palladium less than or equal to 29 ‰ to keep a satisfactory pink color, which is manifested by positioning in zone 5 highlighted on the figure 6 . Thus, a 20Pd alloy is positioned for example at the level of a satisfactory pink color. It is noted that the addition of a small quantity of indium to this 20Pd alloy has little effect on the color, as schematically illustrated by the positioning of the 20Pd10ln alloy on the figure 6 , which is very close to the 20Pd alloy. As a note, if we had added 10Pd to the 20Pd alloy, to obtain a 30Pd alloy, replacing the added 10ln, the desaturation of the pink color would have been very marked. This also allows to conclude that from a color point of view it is advantageous to combine indium and palladium, rather than considering a single equivalent amount of palladium. It also appears that, in order to maintain a satisfactory pink color, the sum of the levels of the two components must not be too great, otherwise the pink will be degraded in relation to the desired pink. It is thus preferable to remain less than or equal to 35 ‰, or even 33 ‰, 30 ‰, 29% 0 or 25 ‰, these values representing different levels, all satisfactory, but successively making it possible to improve the result. In addition, it is also interesting to choose a sufficient minimum quantity of the sum the levels of the components palladium and indium, to prevent the pink color from tending towards red. For this, it appears that a minimum of 15 ‰ is strongly recommended, and that it is preferable to choose a value greater than or equal to 20% 0, or even 25 ‰. In summary of these considerations, the sum of the levels of palladium and indium is advantageously included in the intervals between 15 ‰ -35 ‰, even between 20 ‰ and 35 ‰, or even between 25 ‰ and 33 ‰, which represent choices interesting for obtaining a satisfactory pink color of a gold alloy, these limits can be included or excluded.

Finalement, les alliages d'or rose combinant du palladium et de l'indium sont intéressants car ils permettent à la fois d'atteindre une couleur d'esthétique satisfaisante et qui se décolore peu avec le temps. Les quantités précises pour chacun de ces deux composants et leur somme représentent des compromis entre la réduction de la décoloration et l'esthétique de la couleur rose recherchée. Nous notons toutefois que les intervalles pour cette somme des taux de palladium et d'indium qui permettent à la fois d'atteindre une couleur rose satisfaisante et une faible décoloration se trouvent entre 15‰ et 35‰, voire entre 20‰ et 35‰, voire entre 25‰ et 33‰, comme cela ressort des analyses précédentes. Dans ces intervalles, un taux de palladium élevé, supérieur ou égal à 15‰, voire supérieur ou égal à 19‰, est favorable à la réduction de la décoloration. Au contraire, un taux de palladium faible, inférieur ou égal à 20%0, voire inférieur ou égal à 19‰ ou 18‰, est favorable à l'esthétique de la couleur rose. En compromis, un taux de palladium compris entre 19‰ et 25‰ inclus forme une bonne solution.Finally, rose gold alloys combining palladium and indium are interesting because they allow both to achieve a color of satisfactory aesthetics and which fades little over time. The precise amounts for each of these two components and their sum represent tradeoffs between the reduction of discoloration and the aesthetics of the desired pink color. We note, however, that the intervals for this sum of the levels of palladium and indium which make it possible both to achieve a satisfactory pink color and a weak discoloration are between 15 ‰ and 35 ‰, or even between 20 ‰ and 35 ‰, or even between 25 ‰ and 33 ‰, as shown in previous analyzes. In these intervals, a high level of palladium, greater than or equal to 15 ‰, or even greater than or equal to 19 ‰, is favorable to the reduction of discoloration. On the contrary, a low level of palladium, less than or equal to 20% 0, or even less than or equal to 19 ‰ or 18 ‰, is favorable to the aesthetics of the color pink. In compromise, a level of palladium between 19 ‰ and 25 ‰ inclusive forms a good solution.

Les considérations précédentes peuvent être adaptées à toute quantité de cuivre supérieure ou égale à 180‰, notamment aussi pour une quantité de cuivre relativement faible, par exemple comprise entre 180‰ et 200‰. Toutefois, nous notons qu'il est possible d'assouplir certaines des plages précédentes dans l'hypothèse où une quantité de cuivre importante est imposée, notamment supérieure ou égale à 200‰. En effet, dans ce cas, une couleur rose peut être plus aisément obtenue, même en utilisant des quantités plus importantes des composants tendant à la dégrader, comme explicité précédemment. Il en résulte que si la quantité de cuivre Cu est supérieure ou égale à 200‰, il est possible d'obtenir des alliages convenables avec un taux de palladium compris entre 4‰ et 35‰ et un taux d'indium compris entre 1‰ et 16‰.The preceding considerations can be adapted to any quantity of copper greater than or equal to 180 ‰, in particular also for a relatively small quantity of copper, for example between 180 ‰ and 200 ‰. However, we note that it is possible to relax some of the ranges above in the hypothesis where a large quantity of copper is imposed, in particular greater than or equal to 200 ‰. Indeed, in this case, a pink color can be more easily obtained, even by using larger quantities of the components tending to degrade it, as explained previously. As a result, if the amount of copper Cu is greater than or equal to 200 ‰, it is possible to obtain suitable alloys with a palladium level between 4 ‰ and 35 ‰ and an indium level between 1 ‰ and 16 ‰.

Dans tous les cas, si on souhaite garantir l'effet anti-décoloration (antivieillissement avec le temps) optimal, il devient alors avantageux de choisir un taux de palladium relativement élevé, qui peut alors se trouver entre 19‰ et 35‰, voire entre 21‰ et 35‰. Si on veut aussi éviter une trop grande dégradation de l'esthétique de la couleur rose, on peut abaisser le seuil supérieur du taux de palladium, plus proche de 30‰ si possible et de préférence strictement sous 30‰. Les plages optimales tenant compte de ces contraintes sont alors un taux de palladium compris entre 23‰ et 31‰ inclus, voire entre 23‰ et 29‰ inclus, voire entre 23‰ et 27‰ inclus, pour converger autour d'une valeur de 25‰ qui apparaît un bon compromis.In all cases, if one wishes to guarantee the optimum anti-discoloration effect (anti-aging over time), it then becomes advantageous to choose a relatively high level of palladium, which can then be between 19 ‰ and 35 ‰, or even between 21 ‰ and 35 ‰. If we also want to avoid too great a degradation of the aesthetics of the pink color, we can lower the upper threshold of the palladium level, closer to 30 ‰ if possible and preferably strictly below 30 ‰. The optimal ranges taking these constraints into account are then a level of palladium between 23 ‰ and 31 ‰ inclusive, or even between 23 ‰ and 29 ‰ inclusive, or even between 23 ‰ and 27 ‰ inclusive, to converge around a value of 25 ‰ which appears to be a good compromise.

Les considérations précédentes ont été réalisées à partir d'exemple d'or rose de 18 carats, soit 750‰ d'or. En variante, les résultats restent pertinents pour une quantité d'or supérieure, notamment comprise entre 750‰ et 800‰, voire 750‰ et 770‰.The foregoing considerations have been made from an example of 18 karat rose gold, ie 750 ‰ gold. As a variant, the results remain relevant for a greater quantity of gold, in particular between 750 ‰ and 800 ‰, or even 750 ‰ and 770 ‰.

Les compositions ci-dessus ne mentionnent que les éléments majoritaires de l'alliage, auxquels on peut ajouter au moins un élément affineur de grains selon les connaissances de l'homme du métier, ce qui donne d'autres variantes de réalisation de l'invention. Cet élément affineur de grains peut être présent, par exemple, au plus au taux de 2‰, voire 1‰, d'au moins un élément choisi à titre d'exemple parmi Ru, Ir, Re, Co, V et Mo. Notamment, les éléments comme Ir, Re ou Ru permettent de garantir la finesse du grain et d'éviter les porosités, sans modifier sensiblement la dureté, ni affecter la couleur, ce qui est avantageux par rapport à l'objet recherché.The above compositions only mention the majority elements of the alloy, to which can be added at least one grain refiner element according to the knowledge of those skilled in the art, which gives other variant embodiments of the invention. . This grain refiner element can be present, for example, at most at the rate of 2 ‰, or even 1 ‰, of at least one element chosen by way of example from Ru, Ir, Re, Co, V and Mo. In particular, elements such as Ir, Re or Ru make it possible to guarantee the fineness of the grain and to avoid porosities, without appreciably modify the hardness, nor affect the color, which is advantageous compared to the sought object.

Comme mentionné précédemment, les différentes figures illustrent un effet technique particulier obtenu avec l'ajout de calcium Ca et/ou de silicium Si, en très faible quantité, sur la réduction de la décoloration des alliages cités à titre d'exemple. Une très faible quantité, notamment inférieure ou égale à 10‰, voire 7‰, voire 5‰, pour le calcium, et/ou inférieure ou égale à 2‰, voire 0,5‰ pour le silicium, suffit pour significativement réduire la décoloration avec le temps des alliages illustrés, sans avoir d'effet notable sur la couleur elle-même, en particulier dès lors qu'un taux de cuivre suffisant, de préférence supérieur ou égal à 200‰, est utilisé. Par exemple, il apparaît sur la figure 2 que l'alliage 10Pd 5In 5Ca résiste mieux à la décoloration qu'un alliage 10Pd 5In. De même, un alliage 20Pd 10ln 1Ca ou 20Pd 10ln 0,5Ca ou 20Pd 10ln 0,1Si ou 20Pd 10In 0,02Si est meilleur qu'un alliage 20Pd 10In. Les études précédentes ont souligné l'intérêt de la combinaison du calcium ou du silicium avec un alliage d'or rose combinant du palladium et de l'indium. Toutefois, cet effet favorable des composants Ca et Si se vérifient aussi sur tout autre alliage d'or rose, ne comprenant pas obligatoirement du palladium et de l'indium. A titre d'exemple, on s'aperçoit sur la figure 2 qu'un alliage 10Pd 5Ca est bien meilleur qu'un alliage 13Pd ou 10Pd 5In. Comme autre exemple, l'ajout des composants Ca et Si dans des alliages d'or rose comprenant du platine permet aussi d'obtenir des alliages résistants mieux à la décoloration.As mentioned above, the various figures illustrate a particular technical effect obtained with the addition of calcium Ca and / or silicon Si, in very small quantities, on the reduction of the discoloration of the alloys mentioned by way of example. A very small amount, in particular less than or equal to 10 ‰, or even 7 ‰, or even 5 ‰, for calcium, and / or less than or equal to 2 ‰, or even 0.5 ‰ for silicon, is sufficient to significantly reduce discoloration over time of the illustrated alloys, without having a noticeable effect on the color itself, in particular when a sufficient copper content, preferably greater than or equal to 200 ‰, is used. For example, it appears on the figure 2 that the 10Pd 5In 5Ca alloy is more resistant to discoloration than a 10Pd 5In alloy. Likewise, a 20Pd 10ln 1Ca or 20Pd 10ln 0.5Ca or 20Pd 10ln 0.1Si or 20Pd 10In 0.02Si alloy is better than a 20Pd 10In alloy. Previous studies have underlined the interest of combining calcium or silicon with a rose gold alloy combining palladium and indium. However, this favorable effect of the Ca and Si components is also verified on any other rose gold alloy, which does not necessarily include palladium and indium. For example, we can see on the figure 2 that a 10Pd 5Ca alloy is much better than a 13Pd or 10Pd 5In alloy. As another example, the addition of the Ca and Si components in rose gold alloys comprising platinum also makes it possible to obtain alloys which are better resistant to discoloration.

Ainsi, l'invention porte sur une pièce d'horlogerie, de bijouterie ou de joaillerie comprenant un alliage comprenant en poids au moins 750‰ d'or, caractérisée en ce que l'alliage comprend également au moins 180‰ de cuivre, voire au moins 200‰ de cuivre, et comprend du calcium, avec un taux de calcium inférieur ou égal à 10 ‰ voire 7‰, voire 5‰, et/ou du silicium, avec un taux de silicium inférieur ou égal à 2‰, voire 0,5 ‰.Thus, the invention relates to a timepiece, jewelry or jewelry comprising an alloy comprising by weight at least 750 ‰ of gold, characterized in that the alloy also comprises at least 180 ‰ of copper, or even at least 200 ‰ of copper, and comprises calcium, with a calcium level less than or equal to 10 ‰ or even 7 ‰, or even 5 ‰, and / or silicon, with a silicon content less than or equal to 2 ‰, or even 0.5 ‰.

En remarque, les bornes supérieures de concentration préférentielle sont différentes pour Ca et Si, car il est apparu que leur comportement en fonction de la concentration dans l'alliage n'est pas identique. Il est en effet préférable d'éviter la formation de précipités pour pouvoir déformer et/ou polir l'alliage massif. La concentration de Ca et Si devra être ajustée par l'homme du métier en fonction de la composition retenue pour l'alliage d'or rose.As a remark, the upper limits of preferential concentration are different for Ca and Si, because it appeared that their behavior as a function of the concentration in the alloy is not identical. It is in fact preferable to avoid the formation of precipitates in order to be able to deform and / or polish the solid alloy. The concentration of Ca and Si should be adjusted by a person skilled in the art depending on the composition chosen for the rose gold alloy.

En remarque supplémentaire, d'autres essais ont montré que d'autres éléments comme le gallium n'ont pas un effet comparable au calcium et/ou au silicium.As a further remark, other tests have shown that other elements such as gallium do not have an effect comparable to calcium and / or silicon.

En remarque supplémentaire, on note qu'un tel alliage d'or rose selon les modes de réalisation de l'invention peut ne pas comprendre d'argent, qui induit l'effet négatif de jaunir la couleur de l'alliage et même de faire tendre cette couleur vers une couleur verdâtre inesthétique, l'éloignant alors du rose recherché. De plus, comme cela apparaît en bas du tableau de la figure 3 à partir d'un essai effectué avec un exemple d'alliage 40Ag, il apparaît que l'argent n'a pas d'effet très efficace sur la tenue dans le temps de la couleur, en comparaison aux autres alliages étudiés. Il y a donc deux bonnes raisons d'exclure l'argent de toutes les réalisations proposées ci-dessus. Toutefois, des alliages comprenant de l'argent ne sont pas totalement exclus puisqu'ils pourraient quand même reprendre les avantages mentionnés précédemment.As a further remark, it is noted that such a rose gold alloy according to the embodiments of the invention may not include silver, which induces the negative effect of yellowing the color of the alloy and even of making tender this color towards an unsightly greenish color, moving it away from the sought-after pink. Moreover, as it appears at the bottom of the table of the figure 3 from a test carried out with an example of a 40Ag alloy, it appears that silver does not have a very effective effect on the durability of the color over time, compared to the other alloys studied. There are therefore two good reasons to exclude money from all the achievements proposed above. However, alloys comprising silver are not totally excluded since they could still take the advantages mentioned above.

Enfin, dans tous les modes de réalisation précédents, les alliages décrits seront donc particulièrement performants pour réaliser tout ou partie d'une pièce d'horlogerie, comme un boîtier de montre, un bracelet, une montre, etc., ou une pièce de bijouterie ou de joaillerie. Naturellement, cette réalisation d'une pièce d'horlogerie, de bijouterie ou de joaillerie, signifie la fabrication de tout ou une partie significative de l'épaisseur d'une pièce d'horlogerie, et non un simple revêtement de surface. Les essais étudiés et décrits précédemment portent d'ailleurs sur des volumes massifs de certains alliages. Ainsi, les pièces considérées comprennent une quantité importante d'alliage, se présentent avantageusement sous la forme d'un alliage massif apte à être déformé et à être poli, comprenant notamment au moins une partie d'épaisseur supérieure ou égale à 0,1 mm.Finally, in all the preceding embodiments, the alloys described will therefore be particularly effective for producing all or part of a timepiece, such as a watch case, a bracelet, a watch, etc., or a piece of jewelry. or jewelry. Naturally, this production of a timepiece, piece of jewelry or jewelry, means the manufacture of all or a significant part of the thickness of a timepiece, and not a simple surface coating. The tests studied and described above also relate to massive volumes of certain alloys. Thus, the parts considered comprise a large amount of alloy, are advantageously in the form of a solid alloy capable of being deformed and of being polished, comprising in particular at least a part of thickness greater than or equal to 0.1 mm. .

Claims (13)

  1. A timepiece or jewelry part comprising an alloy consisting of, by weight:
    - at least 750‰ gold, and
    - at least 180‰ copper, and
    - calcium, wherein a content of calcium is less than or equal to 10‰, or even 7‰, or even 5‰, and/or silicon, with a silicon content less than or equal to 2‰, or even less than or equal to 0.5‰,
    - palladium and/or indium,
    - optionally platinum and/or silver,
    - optionally at least one grain refining element, the content of which being less than or equal to 2‰, especially selected from Ru, Ir, Re, Co, V and Mo,
    - optionally at least one element Y, Y being selected from Sr, Ti, Zr, and/or Mg,
    And characterized in that the sum of the contents of palladium and indium and calcium and silicon is between 20‰ and 35‰ inclusive.
  2. The timepiece or jewelry part as claimed in the preceding claim, characterized in that the alloy comprises at least 200‰ copper.
  3. The timepiece or jewelry part as claimed in either of claims 1 and 2, characterized in that the alloy comprises between 1‰ and 40‰ palladium and/or between 1‰ and 40‰ indium and/or between 1‰ and 40‰ platinum and/or between 1‰ and 50‰ silver.
  4. The timepiece or jewelry part as claimed in either of claims 1 and 2, characterized in that the sum of the contents of palladium and/or indium and calcium and/or silicon is less than or equal to 35‰, or even less than or equal to 30‰, or even less than or equal to 25‰.
  5. The timepiece or jewelry part as claimed in one of the preceding claims, characterized in that the alloy does not comprise silver.
  6. The timepiece or jewelry part as claimed in claim 1, characterized in that the alloy comprises between 4‰ and 35‰ palladium and between 1‰ and 16‰ indium.
  7. The timepiece or jewelry part as claimed in one of the preceding claims, characterized in that the alloy comprises between 19‰ and 35‰, or even between 21‰ and 35‰, or even between 23‰ and 31‰, or even between 23‰ and 27‰ palladium and/or between 1‰ and 16‰ indium, or even between 1‰ and 10‰ indium, or even between 1‰ and 4‰ indium.
  8. The timepiece or jewelry part as claimed in claim 1, characterized in that, in the alloy, the sum of the contents of palladium and indium being less than or equal to 35‰, or even less than or equal to 30‰, or even less than or equal to 25‰, and/or the sum of the contents of palladium and indium is between 15‰ and 35‰, or even between 20‰ and 35‰, or even between 25‰ and 33‰.
  9. The timepiece or jewelry part as claimed in one of the preceding claims, characterized in that the piece or part has at least one solid portion composed of said alloy and comprising a thickness greater than or equal to 0.1 mm.
  10. The timepiece or jewelry part as claimed in the preceding claim, characterized in that the content of the grain refining elements is less than or equal to 1‰.
  11. The timepiece or jewelry part as claimed in one of the preceding claims, characterized in that the alloy consists of:
    - gold, copper, calcium and/or silicon, palladium and/or indium, or of
    - gold, copper, calcium and/or silicon, palladium and/or indium, and of at least one grain refining element.
  12. The timepiece or jewelry part as claimed in one of the preceding claims, characterized in that the sum of the contents of all the elements of the alloy apart from gold and copper is less than or equal to 40‰.
  13. The timepiece as claimed in one of the preceding claims, characterized in that it is a watch.
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PCT/EP2014/052373 WO2014122235A1 (en) 2013-02-06 2014-02-06 Timpepiece made from rose gold alloy
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WO2014122235A1 (en) 2014-08-14
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CH707539B1 (en) 2017-01-13
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CN104968813A (en) 2015-10-07
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US20150368756A1 (en) 2015-12-24
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US20150368757A1 (en) 2015-12-24
CN111809076A (en) 2020-10-23

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