EP2954080A1

EP2954080A1 - Timepiece made from rose gold alloy

Info

Publication number: EP2954080A1
Application number: EP14705988.5A
Authority: EP
Inventors: Pascal Dubos; Jean-François Ricard
Original assignee: Rolex SA
Current assignee: Rolex SA
Priority date: 2013-02-06
Filing date: 2014-02-06
Publication date: 2015-12-16
Anticipated expiration: 2034-02-06
Also published as: US20160306327A2; WO2014122234A1; JP2019122776A; JP2019123943A; JP2016513176A; CH707537A8; EP2954079A1; CN104968811A; JP6595343B2; EP2954079B1; CH707539A2; US20150368756A1; WO2014122235A1; CN104968812A; CH707539A8; WO2014122233A1; CH707537A2; US10514661B2; EP2954078B1; CN104968813A

Abstract

The invention relates to a timepiece or piece of jewellery comprising an alloy containing at least 750 wt.-‰ gold, characterised in that the alloy comprises at least 200‰ copper, 4‰ - 35‰ palladium and 1‰ - 16‰ indium.

Description

WATCH PIECE IN ROSE GOLD ALLOY

Introduction 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.

State of the art

The color of gold alloys depends on their content of alloying elements. For AuCuAg 18ct alloys for example, a copper content greater than 180 _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 and then from 150 _o to 60 _o and if the silver content increases from 40 _o to 150 _o . We found that 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. Brief description of the invention For this purpose, 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 at least 200 _o of copper, between 4 o and 35 o of palladium and between 1% ₀ and 16 o of indium.

The invention is precisely defined by the claims.

BRIEF DESCRIPTION OF THE DRAWINGS These objects, features and advantages of the present invention will be set forth in detail in the following description of particular embodiments made in a non-limiting manner in relation to the attached figures among which:

Figure 1 shows three experimental decolorization curves respectively obtained on an alloy 13Pd (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.

Figures 3 and 4 are tables of discoloration test results obtained after 40 days on different alloys. FIG. 5 shows the discoloration obtained after 40 days as a function of the sum of the palladium and indium components of different alloys.

Figure 6 illustrates the discoloration obtained after 40 days for different alloys according to their palladium and indium levels. Figure 7 schematically positions several alloys on a graph to illustrate the color obtained for these different alloys.

Embodiments of the invention will now be presented, based on specific examples and results of empirical experiments. For this, 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. All tests are carried out on casting alloys without subsequent deformation or heat treatment, and without the addition of usual grain refiners. The crystallographic analysis of the samples is carried out with an X-ray diffractometer with Cu anode. Metallographic control and phase stoichiometry analysis are performed by SEM - EDX scanning electron microscopy. The color variations are measured with a spectrophotometer with integrating sphere. The color is defined conventionally by a point in the CIELAB space consisting of a green-red axis on the abscissa, a yellow-blue axis on the y-axis and a representative axis of the contrast (see CIE15 report: 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 deviations ΔΕ are defined by the DE2000 (equation 8.36, paragraph 8.3, CIE15 report: 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 following convention is used for designations of alloys:

- For 18ct alloys (750Au), indication of the content of the additive elements in weight percent before the symbol of the element. 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% _o , or even greater than or equal to 200 _o . Example: 10ln corresponds to an alloy 750Au240Cu10In;

- For non-18ct alloys, indication of the Au content in percent of weight before the element and then indication of the additive elements according to the previous point;

- The ranges of value that will be mentioned later can include or exclude their terminals, which will not always be specified.

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 tables in FIGS. 3 and 4 show 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.

More generally, an alloy composed of at least 750 _o of gold, of copper, and with a Palladium (Pd) level defined by: Pd <20 _o or Pd <15 o, or 5% o <Pd <1,570 or 8% o <Pd <15% o, or 1 1% o <Pd <15% o, is preferred. 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. Indeed, the tests carried out show that there is an optimum at the level of the color drift between 5 and 20 _o of In, in particular around 10 _o , with a preferred interval between 7 o <In <15% o . More generally, an alloy composed of at least 750 _o of gold, of copper, and with a level of Indium (In) defined by: In <20 _o or In <15 o, or 5 o <In <20 o or where <0 <0 is advantageous.

Quaternary or quinternal alloys containing palladium are also very interesting. In particular, as is apparent from the results of FIGS. 2 to 4 relating to the resistance over time to the discoloration, the alloys 20Pd10In, 10Pd 5In 5Ca, 15Pd 10In 5Ca, 5Pd 10In 5Ca, 10Pd 5In, 20Pd 10In 0.1 Si, 20Pd 10ln 1 Ca, 20Pd 10ln 0.5Ca, 20Pd 10ln 0.02Si show weak drifts and are interesting. AuCuPdln alloys, such as 20Pd alloy 10ln or alloy 10Pd 5ln, are particularly interesting.

More generally, an alloy composed of at least 750 _o of gold, copper, palladium and indium is interesting, especially when the sum of the Pd and In levels is less than or equal to 45 o, or even 40 _o , or even 35 o, even 30 _o , and / or when the sum of the Pd and In levels is in the range of 15% o to 40 _o , or even 20 _{o to} 35 o, 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.

More generally, an alloy composed of at least 750 _o of gold, copper, palladium and at least one element Y, Y being selected from Ca, Zr, or In is of interest, particularly when the sum of Palladium and or element (s) Y is less than or equal to 40 _o or 35 o or 30 _o or 25 o or 20 _o or 17% ₀ or 15% o, or 13% 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 to} 35 o, and / or when the alloy comprises at least 1% o of Pd and 1% o of the Y element (s), or even at least 5 o of Pd and 5 o of the Y element (s).

More generally, 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. , especially when the sum of the Palladium and Y element (s) is less than or equal to 40 o, even 35 o, even 30 _o , even 25 o, even 20 _o , or even 17 o, or even 15 o, or even 13 o, and / or when the sum of Pd and element (s) Y is in the range of 15% o to 40 _o , or even 20 o to 35 o, and / or when alloy comprises at least 1 o of Pd and 1 o of the element or elements Y, or at least 5 o of Pd and 5 o of the element or elements 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. , especially when the sum of the rates of Indium and element Y is less than or equal to 40 _o , even 35 o, even 30 o, even 25 o, even 20 _o , even 17 o, even 15 o, even 13 o, and / or when the sum of the levels of In and element (s) Y is in the range of between 15% o and 40 _o , or even 20 _{o to} 35 o, and / or when the alloy comprises at least minus 1 o of In and 1 o of element Y or elements, or at least 5 o of In and 5 o of Y element (s). The following ternary alloys titrating 18ct or more are particularly interesting: AuCuPd with Pd <20 ₀ , more particularly with 5 o≤Pd <20 ₀ , more particularly with 5 o≤Pd <15 o

- AuCuIn with ln <20 ₀ , more particularly with 5 o≤ln <20 ₀ , more particularly with 7% o≤ln≤15 o

AuCuPdln quaternary alloys containing 18ct or more are particularly interesting:

- in particular with the sum of the Pd and In levels less than or equal to 45 o, even 40 o, even 35 o, even 30 _o ;

- and / or with the sum of Pd rate and In in the range between 15 o and 40 o or 20 _o to 35 _0;

and / or with at least 1 o of Pd and 1 o of In, or even at least 5 o of Pd and

in particular the 20Pd10ln alloy or the 10Pd5ln alloy.

Quaternary or Quinternary alloys with 18 and above 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 ≠ ln), Ca, Sr, Si, Ti, Zr, or Mg,

- in particular with the sum of the rates X + Y≤40 _o

and / or with the concentrations for Pd, In and element (s) Y: Pd, In <40 _o and Y (Y ≠ ln, Pd) <10% ";

and / or with at least 1% o of Pd and 1% o of the element or elements Y, or even at least 5 o of Pd and 5 o of the element or elements Y.

Quinternary AuCuPdInX alloys where X is selected from Ca, Sr, Si, Ti, Zr, Mg are also of interest.

Finally, it should be noted that other 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.

Finally, it is noted that the 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 different tables in Figures 2 to 4.

In particular, it appears that 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, even less than or equal to 35 o or 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: ## EQU1 ## On the other hand, 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 5 and 6 illustrate in a complementary manner the interest of combining palladium and indium and allow to visualize the optimal amounts.

Figure 5 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 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 intervals group together several high-performance alloys, and the reduced interval 25 ₀ -33 ₀ groups together still optimized results.

Figure 6 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, or even between 19% o and 29 o, and an indium content of between 1% ₀ and 15% 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, there is a advantageous significant effect due to its combination with palladium. In addition to the very important previous 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 an alloy considered, and particularly the aesthetics of the alloy. pink color obtained. Indeed, the addition of the various components mentioned above has an effect not only on the maintenance in time of the color, but also on the color itself of the alloy. For example, the addition of palladium in a pink gold alloy has the effect of desaturating the pink color, even to make the color of the alloy to gray, and the addition of indium has the effect of drifting towards the yellow of a pink alloy.

Figure 7 schematically illustrates these remarks. The coordinate a ^* is on the abscissa and the coordinate b ^{* on} the ordinate. Note that 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 18K yellow gold alloy, positioned on the left and upper part of the diagram, close to the y-axis, corresponding to a strong yellow cast. The second reference alloy is a very red 18-carat gold alloy, comprising 250 _o of copper, positioned on the right and bottom part of the diagram, close to the abscissa axis. It is noted that the addition of a relatively large amount of palladium, as illustrated by the example of the 40 Pd alloy, has the effect of greatly attenuating 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 o to maintain a satisfactory pink color, which is manifested by a positioning in the zone 5 highlighted in FIG. 7. Thus, an alloy 20Pd is positioned for example at a satisfactory pink color. It is noted that the addition of a small amount of indium to this alloy 20Pd has little effect on the color, as schematically illustrates the positioning of the 20Pd10ln alloy in FIG. 7, which is very close to the 20Pd alloy. As a note, if we had added 10Pd to the alloy 20Pd, to obtain a 30Pd alloy, replacing the 10ln added, the desaturation of the pink color would have been very pronounced. This also suggests that from the point of view of color, 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 rose will be degraded compared to the desired pink. It is thus preferable to remain less than or equal to 35 o, even 33 o, 30 _o , 29 o or 25 o, these values representing different levels, all satisfactory, but allowing successively to improve the result. In addition, it is also interesting to choose a sufficient minimum amount of the sum of the levels of the palladium and indium components, to avoid that the pink color tends to red. For this, it appears that a minimum of 15% o is strongly recommended, and that it is necessary to choose preferably a value greater than or equal to 20 _o , or even 25 o. In summary of the foregoing, the sum of rates palladium and indium is preferably in the interval between 15 ₀ -35 _0, or even between 20 _o and 35 o, or even between 25 o and 33 o, which represent choices interesting for obtaining a satisfactory pink color of a gold alloy, these terminals can be included or excluded.

Finally, 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. We note, however, that the intervals for this sum of palladium and indium levels that both achieve satisfactory pink color and low discoloration are between 15% o and 35 o, or even between 20 _o and 35 o , or between 25 o and 33 o, as is apparent from previous analyzes. In these ranges, a high palladium content, greater than or equal to 15 o, or even greater than or equal to 19 o, is favorable to the reduction of discoloration. On the contrary, a low palladium content, less than or equal to 20 _o , or even less than or equal to 19% o or 18 o, is favorable to the aesthetics of the pink color. In compromise, a palladium content of between 19% o and 25 o inclusive forms a good solution. The foregoing considerations may be adapted to any quantity of copper greater than or equal to 180 _o , in particular also for a relatively small amount of copper, for example between 180 _o and 200 _o . However, we note that it is possible to relax some of the previous ranges in the event that a significant amount of copper is imposed, especially greater than or equal to 200 _o . Indeed, in this case, a pink color can be more easily obtained, even using larger quantities of the palladium and indium components tending to degrade, as explained above. As a result, if the quantity of Cu copper is greater than or equal to 200 _o , it is possible to obtain suitable alloys with a palladium content between 4 o and 35 o and an indium content of between 1% ₀ and 1 6 o.

Thus, 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 200 _o of copper, between 4 o and 35 o of palladium and between 1% ₀ and 1 6 o of indium.

In any case, if it is desired to guarantee the optimal anti-fading (anti-aging over time) effect, it then becomes advantageous to choose a relatively high palladium content, which can then be between 19% and 35%, even between 21% _Q 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 . The optimal ranges taking into account these constraints are then a palladium content of between 23 o and 31% ₀ inclusive, or even between 23 o and 29 o inclusive, or even between 23 o and 27 o inclusive, to converge around a value of 25 o which appears a good compromise. Note that, when using a small amount of indium, for example between 1% o and 1 0 _o , or between 1% o and 6 o, and even between 1% o and 4 o there is a significant advantageous effect due to its combination with palladium according to the above rates.

The foregoing considerations were made from example of 18-carat pink gold, 750 _o of gold. Alternatively, the results remain relevant for a higher amount of gold, especially between 750% o and 8007oo, or 750 o and 770 o. The above compositions mention only the majority elements of the alloy, to which at least one grain refining element can be added according to the knowledge of those skilled in the art, which gives other variant embodiments of the invention. . This grain refining element can be present, for example, at most at the rate of 2 o, even 1% ₀ , 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 modifying the hardness, nor to affect the color, which is advantageous with respect to the desired object.

On the other hand, as explained above, the alloys could further comprise other components, in addition to the aforementioned components Au, Cu, Pd and In, and any grain refiners, among Ca, Sr, Si , Ti, Zr, Mg. Advantageously, the sum of the rates of all the elements of the alloy excluding gold and copper is less than or equal to 40 _o . Alternatively, the alloy may consist of these only four components Au, Cu, Pd, In, with one (or more) possible (s) refiner (s) grain.

The different figures also illustrate a particular technical effect obtained with the addition of calcium Ca and / or silicon Si, in a very small amount, on reducing the discoloration of the alloys mentioned by way of example. A very small amount, especially less than or equal to 10 _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, is sufficient to significantly reduce discoloration with time the alloys illustrated, without having any noticeable effect on the color itself, since a sufficient copper content, preferably greater than or equal to 180 _o , more preferably greater than or equal to 200 o, is used . As a note, this effect of the Ca and Si components is also check on any other pink gold alloy, not necessarily including palladium and / or indium.

As an additional remark, it is noted that such a pink gold alloy according to the embodiments of the invention advantageously does not include silver, which would induce the negative effect of yellowing the color of the alloy and even stretch this color towards an unsightly greenish color, moving it away from the desired pink. Moreover, as appears at the bottom of the table of FIG. 3 from a test carried out with an example of alloy 40Ag, it appears that the 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 containing small amounts of money are not totally excluded since they could still take back the advantages mentioned above, if they are preponderant over the effect of money. The same conclusion is obtained for manganese. Other tests have also shown that zinc, chromium, or iron have no effect on the behavior over time of the color.

Finally, in all the preceding embodiments, 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. Naturally, this realization of 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. Thus, the parts considered comprise a large amount of alloy, advantageously in the form of a solid alloy capable of being deformed and to be polished, especially comprising at least a portion of thickness greater than or equal to 0.1 mm.

Claims

claims

1. Timepiece, jewelery or jewelery comprising an alloy comprising by weight at least 750 _o of gold characterized in that the alloy comprises at least 200 _o of copper, between 4 o and 35 o of palladium and between 1% ₀ and 16% indium.

2. Timepiece, jewelery or jewelery according to the preceding claim, characterized in that the alloy comprises between 19% o and 35 o, or between 21% ₀ and 35 o, or between 23 o and 31 o ₀ or even between 23 o and 27 o, of palladium and between 1% o and 16% o of indium, or even between 1% o and 10% o of indium, or even between 1% o and 6 o indium, or between 1% o and 4 o of indium.

3. Timepiece, jewelery or jewelry according to one of the preceding claims, characterized in that the alloy does not include silver and / or in that the alloy does not include manganese.

4. Timepiece, jewelery or jewelery according to one of the preceding claims, characterized in that the piece has at least one solid part composed of said alloy and comprising a thickness greater than or equal to 0.1 mm.

5. Timepiece, jewelery or jewelery according to one of the preceding claims, characterized in that the sum of the palladium and indium levels of the alloy is less than or equal to 45 o, or even less than or equal to at 35 o, even lower than or equal to 30 _o , or even less than or equal to 25 o, and / or the sum of the palladium and indium levels is between 15% o and 35 o, or even between 20 _o and 35 o or even 25% o and 33% o.

6. Timepiece, jewelery or jewelery according to one of the preceding claims, characterized in that the alloy further comprises at least one grain refining element, in particular selected from Ru, Ir, Re, Co, V and Mo.

7. Timepiece, jewelery or jewelery according to the preceding claim, characterized in that the rate of grain refining elements is less than or equal to 2 o, or less than or equal to 1% o.

8. Timepiece, jewelery or jewelery according to one of the preceding claims, characterized in that the alloy consists of

- gold, copper, palladium, indium, or

gold, copper, palladium, indium and at least one grain refining element, or

- gold, copper, palladium, indium, and at least one element

Y selected from calcium (Ca), strontium (Sr), silicon (Si), titanium (Ti), zirconium (Zr) or magnesium (Mg), or

- gold, copper, palladium, indium, and at least one element

Y selected from calcium (Ca), strontium (Sr), silicon (Si), titanium (Ti), zirconium (Zr) or magnesium (Mg), and at least one grain refining element.

9. Timepiece, jewelery or jewelery according to one of claims 1 to 7, characterized in that the alloy comprises gold, copper, palladium, indium, and at least one Y element, Y being selected from Ca, Sr, Si, Ti, Zr, and / or Mg.

10. Timepiece, jewelery or jewelery according to claim 8 or 9, characterized in that the alloy comprises calcium, with a calcium level of less than or equal to 10% o, even 7 o, even And / or silicon, with a silicon content of less than or equal to 2 o, or even less than or equal to 0.5% ₀ .

1 1. Timepiece, jewelery or jewelery according to one of the preceding claims, characterized in that the sum of the rates of all the elements of the alloy excluding gold and copper is less than or equal to

12. Watch, characterized in that it comprises a timepiece according to one of the preceding claims.