Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C5/00—Alloys based on noble metals
  • C22C5/02—Alloys based on gold
• • 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
• • 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

Definitions

• the invention relates to a pink gold alloy, particularly suitable for a timepiece, and a timepiece, jewelery or jewelry as such comprising such an alloy, such as a watch.
• the color of gold alloys depends on their content of alloying elements.
• a copper content greater than 1 80% o and a silver content of about 40 o gives them a red color.
• the color changes to pink then to yellow if the copper content decreases from 180% o to 150% o then from 1 50% o to 60% o and if the silver content increases from 40% o to 150% o .
• watch cases or wristbands made from these common gold alloys tended to undergo a gradual change in their color under the action of tap water, seawater, pool water, salt water or soapy water.
• One of the aims of the invention is to improve the resistance to a color change of a timepiece, jewelery or jewelry made in a pink gold alloy and subjected, during use, to weakly aggressive aqueous media.
• Another object of the invention is to define a pink gold alloy whose pink has an aesthetic appearance as attractive as possible.
• the invention is based on a timepiece, jewelery or jewelery comprising an alloy comprising by weight at least 750% o of gold, characterized in that the alloy comprises copper, and comprises calcium , with a lower calcium than or equal to 10% o, or 7 0, 5 or o and / or silicon, with a silicon lower than or equal to 2 °, or even less than or equal 0.5% 0.
• Figure 1 shows three experimental decolorization curves respectively obtained on an alloy 1 3Pd, (curve 1), 5ln (curve 2) and 20Pd10ln (curve 3).
• Figure 2 shows a table of discoloration test results obtained after 20 days on different alloys.
• Figure 3 shows a table of discoloration test results obtained after 40 days on different alloys.
• FIG. 4 shows the discoloration obtained after 40 days as a function of the sum of the palladium and indium components of different alloys.
• Figure 5 illustrates the discoloration obtained after 40 days for different alloys according to their palladium and indium levels.
• Figure 6 schematically positions several alloys on a graph to illustrate the color obtained for these different alloys.
• ingots are prepared by vacuum static casting (melting in a graphite crucible and cooling under nitrogen). Samples are cut from the ingot in the raw state of casting. The surface is prepared by polishing. A typical sample has a square section of 20mm x 20mm x 5mm.
• the measurements were all performed using the following convention: D65 illuminant and 10 ° standard observer (CIE 964).
• the color deviations ⁇ are defined by the DE2000 (equation 8.36, paragraph 8.3, report Cl E15: 2004).
• a color gap measurement is performed between fresh (cast and polished) samples and accelerated salt spray aging samples, with exposure to NIHS 96-50 at 45 ° C with saline solution at 50g / l pure NaCl.
• the 750Au250Cu alloy serves as a reference base.
• the table in FIG. 2 and the graph of FIG. 1 summarize the results obtained after aging with salt spray for various massive ingots of gold alloy.
• the table in FIG. 3 presents other results obtained on alloys after aging for 40 days in salt spray.
• the 13Pd alloy is very interesting, from the point of view of the color obtained and the discoloration. This discoloration as a function of time is represented by curve 1 of FIG.
• Pd palladium content
• AuCuln alloys are interesting because the results show that In allows to form a single-phase alloy with Au and Cu. In particular, the alloy 5ln derives little, as it appears on the curve 2 of Figure 1, and already shows an improvement over the reference of a 250Cu alloy.
• Quaternary or quinternal alloys containing palladium are also very interesting.
• an alloy composed of at least 750 o of gold, copper, palladium and indium is interesting, particularly when the sum of the Pd and In levels is less than or equal to 45% o, or even 40 o , even 35 o, even 30 o , and / or when the sum of the Pd and In levels is between 15 o and 40 o , or even between 20 o and o 35% 0 , and / or when the alloy comprises at least 1% o of Pd and 1% o of In, or even at least 5 o of Pd and 5% o of In.
• an alloy consisting of at least 750% o gold, copper, palladium and at least one element Y, Y being selected from Ca, Zr,
• Y being selected from Ca, Zr,
• the sum of the rate of Palladium and element (s) Y is less than or equal to 40% o , even 35% o, even 30% o , even 25% c, even 20% o , even 17% 0 , even 15% c, even 13% o, and / or when the sum of the Pd levels and the element or elements ( (s) Y is between 1 5% 0 and 40% o , or between 20% o and 35 o, and / or when the alloy contains at least 1% o of Pd and 1 o of the element (s) Y, or even at least 5 o of Pd and 5% o of the element Y.
• an alloy composed of at least 750 o 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 rates of Palladium and element (s) Y is less than or equal to 40% o, even 35% o, even 30% o , even 25% o, even 20% o , even 17% o, or even 15% o or even 1 3% o, and / or when the sum of the levels of Pd and element (s) Y is in the range between 15% o and 40% o , or even 20 % o and 35% o, and / or when the alloy comprises at least 1% o of Pd and ⁇ % 0 of the Y element (s), or even at least 5% o of Pd and 5% o of the element (s) Y.
• Quaternary or quinternary alloys with In are also interesting. More generally, an alloy composed of at least 750 o of gold, copper, indium and at least one element Y, Y being chosen from Ca, Sr, Si, Ti, Zr, Mg or Pd is interesting.
• the following ternary alloys grading 1 8ct or more are particularly interesting: - AuCuPd with Pd ⁇ 20 0 , more particularly with 5% o ⁇ Pd ⁇ 20% o, more particularly with 5% o ⁇ Pd ⁇ 15% o
• AuCuPdln quaternary alloys grading 1 8ct or more are particularly interesting:
• alloy 20Pd1 Oln in particular the alloy 20Pd1 Oln or the alloy 10Pd5ln.
• AuCuXY where X is Pd or In, and Y is at least one of Pd (if X ⁇ Pd), In (if X ⁇ ln), Ca, Sr, Si, Ti, Zr, or Mg,
• Quinternary AuCuPdInX alloys where X is selected from Ca, Sr, Si, Ti, Zr, Mg are also of interest.
• alloys comprising more than four elements can be equally interesting, for example five or six, obtained by replacing the element Y quaternary compounds previously mentioned by n elements Y 1 , Y 2 , Y n , the elements Y, being preferably chosen from Ca, Sr, Si, Ti, Zr, Mg, Pd or In, and so that the sum of the rates of all the elements out of Au and Cu is less than or equal to 40% o .
• Such alloys include especially alloys comprising the components Au, Cu, Pd, In, and X, where X is at least one member selected from Ca, Sr, Si, Ti, Zr, Mg.
• alloys combining both Palladium and Indium are particularly advantageous compared to alloys comprising only one or other of these components, as shown in curve 3 of FIG. and the results of the tables of Figures 2 and 3. It is also noted that the addition of a small amount of calcium and / or silicon in these alloys provides an improvement in the resistance to fading.
• an alloy comprising by weight at least 750 o of gold, also comprising copper, palladium and indium, the sum of the palladium and indium levels being less than or equal to 45% o or even less than or equal to 35 o, even less than or equal to 30 o , and / or the sum of the palladium and indium levels being between 20% o and 35% o, is advantageous.
• Such an alloy may comprise an indium content defined by: 7% 0 ⁇ rate of In ⁇ 15% 0 .
• such an alloy may comprise gold, copper, palladium and calcium and / or silicon, so that the sum of the rates of all elements out of gold and copper is less than or equal to 40 % o .
• Figures 4 and 5 illustrate in a complementary manner the interest of combining palladium and indium and allow to visualize the optimal amounts.
• Figure 4 illustrates the discoloration obtained after 40 days for different alloys, depending on the sum of the palladium and indium levels they comprise. It appears that the best results are obtained for a sum greater than or equal to 15 o, are further improved for a sum greater than or equal to 20 o .
• the 20% o -35% o ranges combine several high-performance alloys, and the reduced 25% 0 -33% 0 range brings together even better results.
• Figure 5 gives additional indications on the sharing of these levels between the two components palladium and indium. It appears that the best results are obtained for a palladium content of between 15% o and 30% o, even between 19% o and 29% o, and an indium content of between 1 o and 1 5 o inclusive. Note that, when using a small amount of indium, for example between 1 o and 10 o %, or between 1 o and 6 o%, and even between 1% o and 4 o% o there is a significant beneficial effect due to its combination with palladium.
• the coordinate a * is on the abscissa and the coordinate b * on the ordinate.
• this color can be measured against reference colors, and can also be subject to a visual examination, the aesthetic effect obtained being particularly noticeable by visual observation.
• the first reference alloy is a conventional 18-carat yellow gold alloy, positioned on the left and top of the diagram, near the y-axis, corresponding to a strong yellow cast.
• the second reference alloy is an alloy of gold 18K very red, comprising 250% o copper, positioned on the right and lower part of the diagram, near the x-axis.
• the sum of the palladium and indium levels is advantageously included in the intervals between 15% 0 -35% 0 , or even between 20% o and 35 o, or even between 25 o and 33 o%, which represent interesting choices for obtaining a satisfactory pink color of a gold alloy, these terminals can be included or excluded.
• the alloys of rose gold combining palladium and indium are interesting because they allow both to achieve a satisfactory aesthetic color and fade little over time.
• the precise quantities for each of these two components and their sum represent compromises between the reduction of the discoloration and the aesthetics of the desired pink color.
• the intervals for this sum of palladium and indium levels that both achieve a satisfactory pink color and low discoloration are between 15 o and 35 o, or even between 20 o and 35 o. % o, even between 25 o and 33 o, as shown in previous analyzes. In these ranges, a high palladium content, greater than or equal to 15% or even greater than or equal to 19%, is favorable to the reduction of discoloration.
• a low palladium content less than or equal to 20% o or even less than or equal to 19% o or 1 8 o, is favorable to the aesthetics of the pink color.
• a palladium content of between 19% 0 and 25% 0 inclusive forms a good solution.
• the foregoing considerations may be adapted to any amount of copper greater than or equal to 180% o , especially also for a relatively small amount of copper, for example between 180% o and 200% o .
• the amount of copper Cu is greater than or equal to 200% o , it is possible to obtain suitable alloys with a palladium content of between 4% o and 35 o and an indium content between Y / oo and 1 6% o.
• a relatively high palladium content which can then be between 19 Q and 35% o, or even between 21% o and 35% o. If we also want to avoid too much degradation of the aesthetics of the pink color, we can lower the upper threshold of the palladium content, closer to 30% o if possible and preferably strictly under 30% o .
• This grain refining element may be present, for example, at most at the rate of 2% 0 , or even 1% 0 , 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 significantly change the hardness, nor affect the color, which is advantageous compared to the object sought.
• the various figures illustrate a particular technical effect obtained with the addition of calcium Ca and / or silicon Si, in a very small amount, on the reduction of the discoloration of the alloys cited by way of example.
• a very small amount especially less than or equal to 1 0% o , even 7% o, or even 5% o, for calcium, and / or less than or equal to 2% o, or even 0.5% o for silicon, It is sufficient to significantly reduce the discoloration with time of the illustrated alloys, without having any noticeable effect on the color itself, especially since a sufficient copper content, preferably greater than or equal to 200 o, is used.
• the 10Pd 5ln 5Ca alloy is more resistant to discoloration than a 10Pd 5ln alloy.
• an alloy 20Pd 10ln 1 Ca or 20Pd 10ln 0.5Ca or 20Pd 10ln 0.1 Si or 20Pd 1 0ln 0.02Si is better than a 20Pd 10ln alloy.
• Previous studies have highlighted the value of combining calcium or silicon with a combination of palladium and indium in pink gold. However, this favorable effect of the Ca and Si components is also true of any other pink gold alloy, not necessarily including palladium and indium. For example, it can be seen in FIG.
• a 10Pd 5Ca alloy is much better than a 1 3Pd 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 that are more resistant to fading.
• the invention relates to a timepiece, jewelery or jewelery comprising an alloy comprising by weight at least 750% o of gold, characterized in that the alloy also comprises at least 180 o of copper, or even at least 200% o of copper, and comprises calcium, with a calcium level of less than or equal to 10% 0 , or even 7% 0 , or even 5 % 0 , and / or silicon, with a silicon content of less than or equal to 2% 0 , or even 0.5% o.
• the alloys according to the invention could further comprise other components, in addition to the previously mentioned components Au, Cu, Ca and / or Si, in particular Pd and / or In and / or Pt and / or or Ag, and at least one optional grain refiner, and / or other components among Sr, Ti, Zr, Mg.
• the sum of the rates of all the elements of the alloy excluding gold and copper is less than or equal to 40% o .
• the alloy may consist of these only components Au, Cu, Ca and / or Si, or Au, Cu, Pd and / or In and / or Pt and / or Ag, Ca and / or Si, with in these variants one (or more) possible grain refiner
• the upper bounds of preferential concentration are different for Ca and Si, since it appeared that their behavior as a function of the concentration in the alloy is not identical. It is indeed preferable to avoid the formation of precipitates to be able to deform and / or polish the massive alloy.
• the Ca and Si concentration will have to be adjusted by those skilled in the art depending on the composition chosen for the pink gold alloy. As an additional remark, other tests have shown that other elements such as gallium do not have an effect comparable to calcium and / or silicon.
• such a pink 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 making tender this color to an unsightly greenish color, moving it away from the desired pink.
• silver does not have a very effective effect on the behavior over time. of color, compared to other alloys studied. So there are two good reasons to exclude money from all of the achievements proposed above. However, alloys including silver are not completely excluded since they could still take the advantages mentioned above. The same conclusion is obtained for manganese.
• the alloys described will therefore be particularly effective for making all or part of a timepiece, such as a watch case, a bracelet, a watch, etc., or a piece of jewelry or jewelery.
• a timepiece, jewelery or jewelry means the manufacture of all or a significant part of the thickness of a timepiece, not a simple surface coating.
• the tests studied and described previously relate to massive volumes of certain alloys.
• the parts considered comprise a large amount of alloy are advantageously in the form of a massive alloy capable of being deformed and to be polished, including in particular at least a portion of thickness greater than or equal to 0.1 mm .

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• 2014
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