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EP1512765A1 - Watch or piece of jewellery resistant to decoloration - Google Patents

Watch or piece of jewellery resistant to decoloration Download PDF

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Publication number
EP1512765A1
EP1512765A1 EP03405645A EP03405645A EP1512765A1 EP 1512765 A1 EP1512765 A1 EP 1512765A1 EP 03405645 A EP03405645 A EP 03405645A EP 03405645 A EP03405645 A EP 03405645A EP 1512765 A1 EP1512765 A1 EP 1512765A1
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EP
European Patent Office
Prior art keywords
alloy
jewelery
copper
gold
color
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Granted
Application number
EP03405645A
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German (de)
French (fr)
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EP1512765B1 (en
Inventor
Jaques Baur
Frédéric Oulevey
Michèle Saudan
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Rolex SA
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Rolex SA
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Publication date
Application filed by Rolex SA filed Critical Rolex SA
Priority to EP03405645A priority Critical patent/EP1512765B1/en
Priority to DE60310555T priority patent/DE60310555T2/en
Priority to DE03405645T priority patent/DE03405645T1/en
Priority to US10/916,853 priority patent/US7311876B2/en
Priority to EP04104165A priority patent/EP1512766A1/en
Priority to JP2004252708A priority patent/JP4813028B2/en
Priority to CNB2004100751416A priority patent/CN100344780C/en
Publication of EP1512765A1 publication Critical patent/EP1512765A1/en
Application granted granted Critical
Publication of EP1512765B1 publication Critical patent/EP1512765B1/en
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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
    • 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 coin of timepieces, jewelery or manufactured jewelery in an alloy comprising by weight at least 75% of gold and at least 6% copper.
  • the color of such gold alloys depends on their copper and silver grades. A copper content greater than 18% and a silver content of around 4% gives them a red color. The color evolves towards the pink then to yellow if the copper content decreases 18% to 15% then 15% to 6% and if the silver content increases from 4% to 15%.
  • the color is defined so conventional by a point of CIELAB space formed of a green-red axis on the abscissa, a blue-yellow axis in ordered and an axis representative of the contrast (cf. ISO 7724 standard established by the International Commission Lighting).
  • the colors of the gold alloys are defined in the tri-chromatic space according to the ISO standard 8654.
  • enclosures or watch bracelets made in these gold alloys usually tended to change of their color under the action of the water of the faucet, sea water, water pools, water salty or soapy water.
  • the specialized literature reports an accelerated tarnishing study performed on an alloy intended for the manufacture of jewelery pieces and comprising 75% gold, 12% copper and 12% silver.
  • the tests take place in the gas phase or in the liquid phase. Tarnishing is quantitatively determined by the color difference of the alloy before and after the test.
  • the reactants in contact with which the alloy is exposed comprise essentially pure sulfur or sulfur compounds.
  • the tarnishing observed is attributed to the formation of silver sulphide Ag 2 S. (See “Tarnishing of AuAgCu alloys", 43, pp. 48-55, 1992, Werkstoffe und Korrosion ).
  • a timepiece, jewelery or of jewelery made of an alloy comprising minus 75% gold and between 15% and 23% copper is known of Japanese Patent Application JP 10245646 published in 1998.
  • the alloy also comprises between 0.3% and 5% of palladium to present greater resistance to the cracking during molding of the part.
  • One of the aims of the invention is to improve the resistance to a color change of a room of timepieces, jewelery or manufactured jewelery in a gold alloy and subjected, in use, to weakly aggressive aqueous media.
  • the subject of the invention is a part of timepieces, jewelery or manufactured jewelery in an alloy comprising by weight at least 75% of gold and at least 6% copper, characterized in that the alloy also comprises between 0.5% and 4% platinum.
  • the platinum content makes it possible to increase resistance to a change in the color of the room subjected to the action of tap water, sea water, swimming pool water, salt water or water soap.
  • the timepiece, jewelery or jewelery is made of an alloy comprising in addition to 4% or less of palladium to enhance the effect of resistance to a color change. It is by example the case for a yellow-colored alloy comprising between 6% and 15% copper.
  • Figure 1 shows two experimental curves of discoloration obtained respectively on a red alloy according to the invention, curve (b), and on a 5N red alloy according to the prior art, curve (a).
  • Figures 2a and 2b show two profiles of concentration obtained respectively on both alloys having undergone the fading test illustrated by Figure 1.
  • Table I reports test results from discoloration obtained on different alloys according to the invention.
  • a reference alloy 5N of red color including 75% gold, 21.5% copper and 4.5% silver is subjected to a fading test.
  • the alloy is immersed in a neutral solution saturated with sodium chloride to a temperature of 40 degrees C for several dozens of days.
  • the color is measured according to the standard ISO 7724.
  • the kinetics of discoloration is illustrated by the curve (a) of Figure 1.
  • the abscissa the immersion time in days and ordinates, the standard of ⁇ Elab vector connecting the representative points of the color of the alloy in CIELAB space, between the initial moment and the different immersion times. Compared to the time range explored, discoloration appears continuous and monotonous with immersion time.
  • a red colored alloy comprising according to the invention 76% gold, 21% copper and 3% platinum is tested under the same conditions as those of the alloy reference.
  • the kinetics of discoloration is illustrated by the curve (b).
  • the latter shows that the standard of vector connecting points representative of color of the alloy according to the invention between the initial moment and the different immersion times is less than he is for the reference alloy without platinum. In other words, the presence of platinum increased the resistance to discoloration of the alloy according to the invention.
  • a factor improvement by the ratio between the modifications of color of the reference alloy and alloy according to the invention, considered after the same duration immersion. In this case, the factor improvement is about 3 after a time 60 days immersion.
  • Figures 2a and 2b show the profiles of concentration obtained respectively on the 5N alloy of reference and on the alloy according to the invention, after 60 days of immersion in the test solution.
  • FIG. decrease in copper concentration in proportion to that of gold on a depth of matter included between the first 10 and the first 20 nanometers as well that maintaining the concentration of money on this same depth.
  • concentration copper in proportion to that of gold decreases less strongly and less deeply for the alloy according to the invention.
  • Table I reports the results of the test of discoloration performed on different alloys compositions numbered from 1 to 15.
  • a row of the table indicates the content of the alloy in gold, copper, platinum and palladium and the limit value of discoloration ⁇ ELab and the fading enhancement factor after a 60-day immersion test.
  • Conditions experimental are identical to those experienced previously: immersion in a saturated solution of sodium chloride at neutral pH and at a temperature of 40 degrees Celsius.
  • compositions are referenced from 15 to 9 in Table I evidence of a factor for improving resistance to the discoloration typically between 2 and 4.
  • alloys whose compositions are referenced from 7 to 3 in the Table I show an improvement factor at most equal to 1.
  • the improvement factor depends on the content weight of copper in the alloys according to the invention. This content is preferably between 15% and 18%. More preferably, it is greater than 18% and more particularly between 20% and 22% for a platinum content between 1.5% and 3%.
  • platinum content between 0.5% and 4% confers on timepieces, jewelery or jewelery according to the invention color that it was impossible to get up to present. While copper has a blushing effect and money a greening effect, platinum has an effect whitening.
  • platinum or palladium to the grayish effect allows to gradually move warm, discreet and velvety colors for lowest grades to more technical colors and colder for the higher grades.
  • a timepiece, jewelery or jewelery made of an alloy comprising by weight at least 75% gold, between 20% and 22% of copper, between 1.5% and 3% of platinum and not more than 0,5% of any of the elements selected from silver, cadmium, chromium, cobalt, iron, indium, manganese, nickel or zinc has a color nominal having in space CIELAB, an equal abscissa at 7,41 along the green-red axis, an ordinate equal to 15.67 along the blue-yellow axis and a value of contrast equal to 86.75.
  • these coordinates may vary between 5.71 and 8.51 along the green-red axis and between 13.67 and 16.67 according to the blue-yellow axis for a value of contrast L varying between 76.75 and 96, 75.
  • the invention applies to any room timepieces, jewelery or jewelery manufactured in from an alloy according to the usual methods like machining or lost wax casting.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Adornments (AREA)

Abstract

A watchmaking, jewellery or jewellers items is fabricated in an alloy containing by wt at least 75% of gold and at least 6% of copper together with between 0.5 and 4% of platinum.

Description

L' invention se rapporte à une pièce d'horlogerie, de bijouterie ou de joaillerie fabriquée dans un alliage comprenant en poids au moins 75% d'or et au moins 6% de cuivre.The invention relates to a coin of timepieces, jewelery or manufactured jewelery in an alloy comprising by weight at least 75% of gold and at least 6% copper.

La couleur de tels alliages d'or dépend de leurs teneurs en cuivre et en argent. Une teneur en cuivre supérieure à 18% et une teneur en argent de l'ordre de 4% leur confère une couleur rouge. La couleur évolue vers le rose puis vers le jaune si la teneur en cuivre décroít de 18% à 15% puis de 15% à 6% et si la teneur en argent augmente de 4% à 15%. 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. 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.The color of such gold alloys depends on their copper and silver grades. A copper content greater than 18% and a silver content of around 4% gives them a red color. The color evolves towards the pink then to yellow if the copper content decreases 18% to 15% then 15% to 6% and if the silver content increases from 4% to 15%. The color is defined so conventional by a point of CIELAB space formed of a green-red axis on the abscissa, a blue-yellow axis in ordered and an axis representative of the contrast (cf. ISO 7724 standard established by the International Commission Lighting). The colors of the gold alloys are defined in the tri-chromatic space according to the ISO standard 8654.

La demanderesse a constaté que des boítiers 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 plaintiff has found that enclosures or watch bracelets made in these gold alloys usually tended to change of their color under the action of the water of the faucet, sea water, water pools, water salty or soapy water.

La littérature spécialisée rapporte une étude de ternissement accéléré effectuée sur un alliage destiné à la fabrication de pièces de joaillerie et comprenant 75% d'or, 12% de cuivre et 12% d'argent. Les tests se déroulent en phase gazeuse ou en phase liquide. Le ternissement est déterminé quantitativement par la différence de couleur de l'alliage avant et après le test. Les réactifs au contact desquels l'alliage est exposé comprennent essentiellement du soufre pur ou des composés du soufre. Le ternissement observé est attribué à la formation de sulfure d'argent Ag2S. (cf. "Tarnishing of AuAgCu alloys", 43, pp. 48-55, 1992, Werkstoffe und Korrosion).The specialized literature reports an accelerated tarnishing study performed on an alloy intended for the manufacture of jewelery pieces and comprising 75% gold, 12% copper and 12% silver. The tests take place in the gas phase or in the liquid phase. Tarnishing is quantitatively determined by the color difference of the alloy before and after the test. The reactants in contact with which the alloy is exposed comprise essentially pure sulfur or sulfur compounds. The tarnishing observed is attributed to the formation of silver sulphide Ag 2 S. (See "Tarnishing of AuAgCu alloys", 43, pp. 48-55, 1992, Werkstoffe und Korrosion ).

Une autre étude a porté sur un alliage comprenant au plus 71% d'or, entre 12% et 14% de cuivre, entre 7,5% et 25% d'argent, entre 0,6% et 4% de platine et entre 0,9% et 3,7% de palladium pour en déterminer le caractère biocompatible en vue de l'utiliser pour la fabrication de prothèses dentaires. Des tests de corrosion sont effectués à température ambiante dans une solution aqueuse contenant de l'acide lactique et du chlorure de sodium, à un pH acide d' environ 2,3. Une augmentation de la concentration des ions métalliques montre que le cuivre et l'argent passent en solution. La déplétion des deux constituants est corroborée par une analyse des premières couches atomiques de la surface de l'alliage effectuée par spectroscopie Auger. Dans les conditions pH-métriques expérimentées, la déplétion du cuivre apparaít d'autant plus importante que la teneur en or et en platine décroít. En revanche, la teneur en platine n'a pas d'effet notable sur la dissolution de l'argent (cf. "Biocompatibility of dental alloys", 3(10), 2001, Advanced engineering materials).Another study focused on an alloy with no more than 71% gold, between 12% and 14% copper, between 7.5% and 25% silver, between 0.6% and 4% platinum, and between 0.9% and 3.7% palladium to determine its biocompatible character for use in the manufacture of dental prostheses. Corrosion tests are carried out at room temperature in an aqueous solution containing lactic acid and sodium chloride, at an acid pH of about 2.3. An increase in the concentration of metal ions shows that copper and silver go into solution. The depletion of the two constituents is corroborated by an analysis of the first atomic layers of the surface of the alloy carried out by Auger spectroscopy. Under the pH-metric conditions tested, the depletion of copper appears all the more important as the gold and platinum content decreases. In contrast, platinum content has no significant effect on silver dissolution (see "Biocompatibility of dental alloys", 3 (10), 2001, Advanced engineering materials ).

Enfin, une pièce d'horlogerie, de bijouterie ou de joaillerie fabriquée dans un alliage comprenant au moins 75% d'or et entre 15% et 23% de cuivre est connue de la demande de brevet japonais JP 10245646 publiée en 1998. L'alliage comprend en outre entre 0,3% et 5% de palladium pour présenter une plus grande résistance à la fissuration lors du moulage de la pièce. Finally, a timepiece, jewelery or of jewelery made of an alloy comprising minus 75% gold and between 15% and 23% copper is known of Japanese Patent Application JP 10245646 published in 1998. The alloy also comprises between 0.3% and 5% of palladium to present greater resistance to the cracking during molding of the part.

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 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 color change of a room of timepieces, jewelery or manufactured jewelery in a gold alloy and subjected, in use, to weakly aggressive aqueous media.

A cet effet, l'invention a pour objet une pièce d'horlogerie, de bijouterie ou de joaillerie fabriquée dans un alliage comprenant en poids au moins 75% d'or et au moins 6% de cuivre, caractérisée en ce que l'alliage comprend également entre 0,5% et 4% de platine.For this purpose, the subject of the invention is a part of timepieces, jewelery or manufactured jewelery in an alloy comprising by weight at least 75% of gold and at least 6% copper, characterized in that the alloy also comprises between 0.5% and 4% platinum.

La teneur en platine permet d'augmenter la résistance à une modification de la couleur de la pièce soumise à 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 platinum content makes it possible to increase resistance to a change in the color of the room subjected to the action of tap water, sea water, swimming pool water, salt water or water soap.

Dans un mode particulier d'exécution de l'invention, la pièce d'horlogerie, de bijouterie ou de joaillerie est fabriquée dans un alliage comprenant en outre 4% au plus de palladium pour renforcer l'effet de résistance à une modification de couleur. C'est par exemple le cas pour un alliage de couleur jaune comprenant entre 6% et 15% de cuivre.In a particular mode of execution of the invention, the timepiece, jewelery or jewelery is made of an alloy comprising in addition to 4% or less of palladium to enhance the effect of resistance to a color change. It is by example the case for a yellow-colored alloy comprising between 6% and 15% copper.

D'autres avantages apparaítront à la lumière de la description d'un mode particulier de réalisation de l'invention illustrée par les dessins.Other advantages will appear in the light of the description of a particular embodiment of the invention illustrated by the drawings.

La figure 1 montre deux courbes expérimentales de décoloration obtenues respectivement sur un alliage rouge selon l'invention, courbe (b), et sur un alliage rouge 5N selon l'art antérieur, courbe (a).Figure 1 shows two experimental curves of discoloration obtained respectively on a red alloy according to the invention, curve (b), and on a 5N red alloy according to the prior art, curve (a).

Les figures 2a et 2b montrent deux profils de concentration obtenus respectivement sur les deux alliages ayant subis le test de décoloration illustré par la figure 1.Figures 2a and 2b show two profiles of concentration obtained respectively on both alloys having undergone the fading test illustrated by Figure 1.

Le tableau I rapporte les résultats de tests de décoloration obtenus sur différents alliages selon l'invention.Table I reports test results from discoloration obtained on different alloys according to the invention.

Un alliage de référence 5N de couleur rouge comprenant 75% d'or, 21,5% de cuivre et 4,5% d'argent est soumis à un test de décoloration. L'alliage est immergé dans une solution neutre saturée de chlorure de sodium à une température de 40 degrés °C pendant plusieurs dizaines de jours. La couleur est mesurée selon la norme ISO 7724. La cinétique de décoloration est illustrée par la courbe (a) de la figure 1. En abscisse, on porte le temps d'immersion en jour et en ordonnées, la norme du vecteur ΔElab reliant les points représentatifs de la couleur de l'alliage dans l'espace CIELAB, entre l'instant initial et les différents temps d'immersion. Par rapport à la plage de temps explorée, la décoloration apparaít continue et monotone avec le temps d'immersion.A reference alloy 5N of red color including 75% gold, 21.5% copper and 4.5% silver is subjected to a fading test. The alloy is immersed in a neutral solution saturated with sodium chloride to a temperature of 40 degrees C for several dozens of days. The color is measured according to the standard ISO 7724. The kinetics of discoloration is illustrated by the curve (a) of Figure 1. In the abscissa, the immersion time in days and ordinates, the standard of ΔElab vector connecting the representative points of the color of the alloy in CIELAB space, between the initial moment and the different immersion times. Compared to the time range explored, discoloration appears continuous and monotonous with immersion time.

Un alliage de couleur rouge comprenant selon l'invention 76% d'or, 21% de cuivre et 3% de platine est testé dans les mêmes conditions que celles de l'alliage de référence. La cinétique de décoloration est illustrée par la courbe (b). Cette dernière montre que la norme du vecteur reliant les points représentatifs de la couleur de l'alliage selon l'invention entre l'instant initial et les différents temps d'immersion est inférieur à ce qu'il est pour l'alliage de référence dépourvu de platine. Autrement dit, la présence du platine a augmenté la résistance à la décoloration de l'alliage selon l'invention. Au plan quantitatif, on définit un facteur d'amélioration par le rapport entre les modifications de couleur de l'alliage de référence et de l'alliage selon l'invention, considérées après une même durée d'immersion. Dans le cas présent, le facteur d'amélioration est de 3 environ après un temps d'immersion de 60 jours.A red colored alloy comprising according to the invention 76% gold, 21% copper and 3% platinum is tested under the same conditions as those of the alloy reference. The kinetics of discoloration is illustrated by the curve (b). The latter shows that the standard of vector connecting points representative of color of the alloy according to the invention between the initial moment and the different immersion times is less than he is for the reference alloy without platinum. In other words, the presence of platinum increased the resistance to discoloration of the alloy according to the invention. Quantitatively, we define a factor improvement by the ratio between the modifications of color of the reference alloy and alloy according to the invention, considered after the same duration immersion. In this case, the factor improvement is about 3 after a time 60 days immersion.

Des analyses ont été effectuées par Rutherford Backscattered Spectroscopy pour explorer une profondeur de matière significative par rapport au trajet des ondes lumineuses dans les deux alliages testés précédemment, la part des ondes lumineuses réfléchies déterminant la couleur de l'alliage.Analyzes were performed by Rutherford Backscattered Spectroscopy to explore a depth significant matter compared to the wave path in the two alloys tested previously, the of reflected light waves determining the color of the alloy.

Les figures 2a et 2b montrent les profils de concentration obtenus respectivement sur l'alliage 5N de référence et sur l'alliage selon l'invention, après 60 jours d'immersion dans la solution de test. Pour l'alliage 5N de référence, on observe figure 2a, une diminution de la concentration en cuivre en proportion de celle de l'or sur une profondeur de matière comprise entre les 10 premiers et les 20 premiers nanomètres ainsi que le maintien de la concentration en argent sur cette même profondeur. En revanche, figure 2b, la concentration en cuivre en proportion de celle de l'or diminue moins fortement et moins profondément pour l'alliage selon l'invention.Figures 2a and 2b show the profiles of concentration obtained respectively on the 5N alloy of reference and on the alloy according to the invention, after 60 days of immersion in the test solution. For the reference 5N alloy, FIG. decrease in copper concentration in proportion to that of gold on a depth of matter included between the first 10 and the first 20 nanometers as well that maintaining the concentration of money on this same depth. In contrast, Figure 2b, concentration copper in proportion to that of gold decreases less strongly and less deeply for the alloy according to the invention.

Il ressort de ces analyses que la décoloration de l'alliage 5N de référence est due à une dissolution du cuivre dans une couche profonde de quelques dizaines de nanomètres. La teneur en platine permet de limiter la dissolution du cuivre dans l'alliage selon l'invention et ainsi d'augmenter la résistance de ce dernier à la décoloration dans la solution de test.These analyzes show that the discolouration of the reference 5N alloy is due to a dissolution of the copper in a deep layer of a few dozen nanometers. Platinum content limits the dissolution of the copper in the alloy according to the invention and thus to increase the resistance of the latter to the discoloration in the test solution.

La cinétique de décoloration de l'alliage selon l'invention tend, par référence à la courbe (b) de la figure 1, vers une valeur limite à partir du quinzième jour environ. L'existence de cette valeur limite procède de l'équilibre thermodynamique stable que la composition de l'alliage confère à matière. L'obtention d'une telle stabilisation de la couleur de l'alliage demeure un résultat tout à fait inattendu dans les conditions du test de décoloration utilisé. Ce test peut être utile au plan industriel pour procéder à la finition d'une pièce d'horlogerie, de bijouterie ou de joaillerie fabriquée dans un alliage comprenant en poids au moins 75% d'or, au moins 6% et entre 0,5% et 4% de platine, par lequel on immerge la pièce dans une solution saline saturée à pH neutre pendant une durée et à une température déterminées pour atteindre la valeur d'équilibre de la couleur de la pièce. D'une manière générale, toute solution permettant la dissolution superficielle du cuivre pour atteindre la couleur d'équilibre pourrait être utilisée. Il convient de relever que la valeur limite de décoloration illustrée par la courbe (b) reste en deçà de la limite de perception par l'oeil d'une modification de couleur de la pièce.The kinetics of discoloration of the alloy according to the invention tends, with reference to the curve (b) of the FIG. 1, towards a limit value starting from the fifteenth about day. The existence of this limit value of stable thermodynamic equilibrium that the composition alloy confers matter. Obtaining such a color stabilization of the alloy remains a completely unexpected result in the conditions of the discoloration test used. This test can be useful for industrial plan to finish a part of timepieces, jewelery or manufactured jewelery in an alloy comprising by weight at least 75% of gold, at minus 6% and between 0.5% and 4% of platinum, whereby immerses the piece in a saline solution saturated with pH neutral for a specified time and temperature to achieve the equilibrium value of the color of the room. In general, any solution allowing the surface dissolution of copper to reach the Balance color could be used. It suits to note that the limit value of discoloration illustrated curve (b) remains below the limit of perception by the eye of a color change of the room.

Le tableau I rapporte les résultats du test de décoloration effectué sur des alliages de différentes compositions numérotés de 1 à 15. Une ligne du tableau indique la teneur de l'alliage en or, cuivre, platine et palladium ainsi que la valeur limite de décoloration ΔELab et le facteur d'amélioration de la décoloration après un test d'immersion de 60 jours. Les conditions expérimentales sont identiques à celles expérimentées précédemment : immersion dans une solution saturée de chlorure de sodium à pH neutre et à température de 40 degrés Celsius.Table I reports the results of the test of discoloration performed on different alloys compositions numbered from 1 to 15. A row of the table indicates the content of the alloy in gold, copper, platinum and palladium and the limit value of discoloration ΔELab and the fading enhancement factor after a 60-day immersion test. Conditions experimental are identical to those experienced previously: immersion in a saturated solution of sodium chloride at neutral pH and at a temperature of 40 degrees Celsius.

Les alliages selon l'invention dont les compositions sont référencées de 15 à 9 dans le tableau I attestent d'un facteur d'amélioration de la résistance à la décoloration compris typiquement entre 2 et 4. Alloys according to the invention, the compositions are referenced from 15 to 9 in Table I evidence of a factor for improving resistance to the discoloration typically between 2 and 4.

Un alliage comprenant 91,7% d'or et 8,3% de cuivre présente un facteur d'amélioration inférieur à l'unité, comme indiqué par la référence 8. Ce résultat montre que la simple recherche d'une augmentation de la teneur en or a un effet opposé à celui de l'augmentation de la résistance à la décoloration de l'alliage.An alloy comprising 91.7% of gold and 8.3% of copper has a lower improvement factor than the unit, as indicated by reference 8. This result shows that the simple search for an increase in the gold content has an opposite effect to that of the increase resistance to discoloration of the alloy.

De même, l'ajout d'éléments comme l'aluminium, le niobium, le tantale, le titane ou le silicium en vue de former une couche d'oxyde propre à limiter la dissolution du cuivre dans la solution saline saturée à pH neutre ne conduit pas plus à une amélioration de la résistance à la décoloration des alliages. Au contraire, les alliages dont les compositions sont référencées de 7 à 3 dans le tableau I attestent d'un facteur d'amélioration au plus égal à 1.Similarly, the addition of elements such as aluminum, niobium, tantalum, titanium or silicon for the purpose of form an oxide layer to limit the dissolution copper in saturated saline solution at neutral pH does not leads no more to an improvement in resistance to discoloration of alloys. On the contrary, alloys whose compositions are referenced from 7 to 3 in the Table I show an improvement factor at most equal to 1.

Les résultats indiqués dans le tableau I, référence 2, montrent enfin que l'ajout de zinc dans le but de former une anode sacrificielle à la surface de l'alliage ne conduit pas non plus à une amélioration de la résistance à la décoloration.The results shown in Table I, reference 2, finally show that the addition of zinc in the purpose of forming a sacrificial anode on the surface of the alloy does not lead to an improvement of resistance to fading.

Le facteur d'amélioration dépend de la teneur pondérale du cuivre dans les alliages selon l'invention. De préférence, cette teneur est comprise entre 15% et 18%. De préférence encore, elle supérieure à 18% et plus particulièrement comprise entre 20% et 22% pour une teneur en platine comprise entre 1,5% et 3%.The improvement factor depends on the content weight of copper in the alloys according to the invention. This content is preferably between 15% and 18%. More preferably, it is greater than 18% and more particularly between 20% and 22% for a platinum content between 1.5% and 3%.

De surcroít, la teneur en platine comprise entre 0,5% et 4% confère aux pièces d'horlogerie, de bijouterie ou de joaillerie selon l'invention une couleur qu'il était impossible d'obtenir jusqu'à présent. Alors que le cuivre a un effet rougissant et l'argent un effet verdissant, le platine a un effet blanchissant. L'ajout de platine ou de palladium à l'effet grisaillant permet ainsi de passer graduellement de couleurs chaudes, discrètes et veloutées pour les teneurs les plus faibles à des couleurs plus techniques et plus froides pour les teneurs les plus élevées.In addition, the platinum content between 0.5% and 4% confers on timepieces, jewelery or jewelery according to the invention color that it was impossible to get up to present. While copper has a blushing effect and money a greening effect, platinum has an effect whitening. The addition of platinum or palladium to the grayish effect allows to gradually move warm, discreet and velvety colors for lowest grades to more technical colors and colder for the higher grades.

Plus particulièrement, une pièce d'horlogerie, de bijouterie ou de joaillerie fabriquée dans un alliage comprenant en poids au moins 75% d'or, entre 20% et 22% de cuivre, entre 1,5% et 3% de platine et au plus 0,5% de l'un quelconque des éléments choisis parmi l'argent, le cadmium, le chrome, le cobalt, le fer, l'indium, le manganèse, le nickel ou le zinc possède une couleur nominale ayant dans l'espace CIELAB, une abscisse égale à 7,41 suivant l'axe vert-rouge, une ordonnée égale à 15,67 suivant l'axe bleu-jaune et une valeur de contraste égale à 86,75. En fonction de la composition exacte de l'alliage, ces coordonnées peuvent varier entre 5,71 et 8,51 suivant l'axe vert-rouge et entre 13,67 et 16,67 suivant l'axe bleu-jaune pour une valeur de contraste L variant entre 76,75 et 96, 75.More particularly, a timepiece, jewelery or jewelery made of an alloy comprising by weight at least 75% gold, between 20% and 22% of copper, between 1.5% and 3% of platinum and not more than 0,5% of any of the elements selected from silver, cadmium, chromium, cobalt, iron, indium, manganese, nickel or zinc has a color nominal having in space CIELAB, an equal abscissa at 7,41 along the green-red axis, an ordinate equal to 15.67 along the blue-yellow axis and a value of contrast equal to 86.75. Depending on the composition exact of the alloy, these coordinates may vary between 5.71 and 8.51 along the green-red axis and between 13.67 and 16.67 according to the blue-yellow axis for a value of contrast L varying between 76.75 and 96, 75.

L'invention s'applique à toute pièce d'horlogerie, de bijouterie ou de joaillerie fabriquée à partir d'un alliage selon les procédés usuels à l'instar de l'usinage ou du moulage à la cire perdue.The invention applies to any room timepieces, jewelery or jewelery manufactured in from an alloy according to the usual methods like machining or lost wax casting.

Claims (6)

Pièce d'horlogerie, de bijouterie ou de joaillerie, fabriquée dans un alliage comprenant en poids au moins 75% d'or et au moins 6% de cuivre, caractérisée en ce que l'alliage comprend également entre 0,5% et 4% de platine.Timepiece, jewelery or jewelery, made of an alloy comprising by weight at least 75% gold and at least 6% copper, characterized in that the alloy also comprises between 0.5% and 4% platinum. Pièce d'horlogerie, de bijouterie ou de joaillerie selon la revendication 1, caractérisée en ce que l'alliage comprend au moins 18% de cuivre.Timepiece, jewelery or jewelery according to claim 1, characterized in that the alloy comprises at least 18% copper. Pièce d'horlogerie, de bijouterie ou de joaillerie selon la revendication 2, caractérisée en ce que l'alliage comprend entre 20% et 22% de cuivre et entre 1,5% et 3% de platine.Timepiece, jewelery or jewelery according to claim 2, characterized in that the alloy comprises between 20% and 22% copper and between 1.5% and 3% platinum. Pièce d'horlogerie, de bijouterie ou de joaillerie selon la revendication 1, caractérisée en ce que l'alliage comprend entre 15% et 18% de cuivre.Timepiece, jewelery or jewelery according to claim 1, characterized in that the alloy comprises between 15% and 18% copper. Pièce d'horlogerie, de bijouterie ou de joaillerie selon la revendication 1, caractérisée en ce que l'alliage comprend entre 6% et 15% de cuivre et au plus 4% de palladium.Timepiece, jewelery or jewelery according to claim 1, characterized in that the alloy comprises between 6% and 15% copper and at most 4% palladium. Pièce d'horlogerie, de bijouterie ou de joaillerie selon la revendication 3, caractérisée en ce que l'alliage comprend en poids au plus 0,5% de l'un quelconque des éléments choisis parmi l'argent, le cadmium, le chrome, le cobalt, le fer, l'indium, le manganèse, le nickel ou le zinc.Timepiece, jewelery or jewelery according to claim 3, characterized in that the alloy comprises by weight at most 0.5% of any of the elements selected from silver, cadmium, chromium, cobalt, iron, indium, manganese, nickel or zinc.
EP03405645A 2003-09-04 2003-09-04 Watch or piece of jewellery resistant to decoloration Expired - Lifetime EP1512765B1 (en)

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EP03405645A EP1512765B1 (en) 2003-09-04 2003-09-04 Watch or piece of jewellery resistant to decoloration
DE60310555T DE60310555T2 (en) 2003-09-04 2003-09-04 Decolorative clock or jewelry
DE03405645T DE03405645T1 (en) 2003-09-04 2003-09-04 Decolorative clock or jewelry
US10/916,853 US7311876B2 (en) 2003-09-04 2004-08-12 Discoloration-resistant timepiece or jewelry part
EP04104165A EP1512766A1 (en) 2003-09-04 2004-08-31 Article of watch or jewelry having color resistance
JP2004252708A JP4813028B2 (en) 2003-09-04 2004-08-31 Discoloration resistant watch or precious metal decorative parts
CNB2004100751416A CN100344780C (en) 2003-09-04 2004-09-03 Discoloration-resistant timepiece or jewelry part

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EP03405645A EP1512765B1 (en) 2003-09-04 2003-09-04 Watch or piece of jewellery resistant to decoloration

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DE202011102731U1 (en) 2011-06-08 2011-12-05 C. Hafner Gmbh + Co. Kg gold alloy
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CH714786A1 (en) * 2018-03-15 2019-09-30 Argor Heraeus Sa Gold alloy with color compatible to the 5N standard and its production method.
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DE03405645T1 (en) 2005-09-01
EP1512765B1 (en) 2006-12-20
US20050053514A1 (en) 2005-03-10
CN100344780C (en) 2007-10-24
DE60310555T2 (en) 2007-12-27
US7311876B2 (en) 2007-12-25
DE60310555D1 (en) 2007-02-01
JP4813028B2 (en) 2011-11-09
JP2005120465A (en) 2005-05-12
CN1605645A (en) 2005-04-13

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