EP2954080B1 - Roségold-legierung für uhr - Google Patents
Roségold-legierung für uhr Download PDFInfo
- Publication number
- EP2954080B1 EP2954080B1 EP14705988.5A EP14705988A EP2954080B1 EP 2954080 B1 EP2954080 B1 EP 2954080B1 EP 14705988 A EP14705988 A EP 14705988A EP 2954080 B1 EP2954080 B1 EP 2954080B1
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- EP
- European Patent Office
- Prior art keywords
- alloy
- indium
- palladium
- equal
- timepiece
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003353 gold alloy Substances 0.000 title description 13
- 229910001112 rose gold Inorganic materials 0.000 title description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 149
- 229910045601 alloy Inorganic materials 0.000 claims description 94
- 239000000956 alloy Substances 0.000 claims description 94
- 229910052763 palladium Inorganic materials 0.000 claims description 65
- 229910052738 indium Inorganic materials 0.000 claims description 58
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 239000010931 gold Substances 0.000 claims description 28
- 229910052737 gold Inorganic materials 0.000 claims description 26
- 239000011575 calcium Substances 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052712 strontium Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims 6
- 239000010936 titanium Substances 0.000 claims 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 3
- 230000000694 effects Effects 0.000 description 16
- 238000002845 discoloration Methods 0.000 description 12
- 229910052727 yttrium Inorganic materials 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- 229910001020 Au alloy Inorganic materials 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000012926 crystallographic analysis Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000010939 rose gold Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000010930 yellow gold Substances 0.000 description 1
- 229910001097 yellow gold Inorganic materials 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
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 180 ⁇ and a silver content of about 40 ⁇ gives them a red color.
- 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.
- JP11-335755 discloses a pink gold alloy with a weight composition of 75% Au, 22% Cu, 1.5% Au, 1.0 Pd and 0.5 In.
- 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 as defined in claim 1.
- 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 conventionally defined 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 an axis representative 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 differences ⁇ E are defined by the DE2000 (equation 8.36, paragraph 8.3, CIE15: 2004 report).
- 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 figure 2 and the graph of the figure 1 synthesize the results obtained after salt spray aging for various massive gold alloy ingots.
- the tables in Figures 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 the figure 1 . More generally, an alloy composed of at least 750 ⁇ of gold, of copper, and with a Palladium content (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 allows to form a single-phase alloy with Au and Cu.
- the alloy 5In derives little, as it appears on the 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 ⁇ of In, in particular around 10 ⁇ , with a preferred interval between 7 ⁇ ⁇ In 15 ⁇ .
- an alloy composed of at least 750 ⁇ of gold, of copper, and with an indium content (In) defined by: In ⁇ 20 ⁇ or In ⁇ 15 ⁇ , or 5 ⁇ ⁇ In ⁇ 20 ⁇ or 7 ⁇ ⁇ In ⁇ 15 ⁇ is advantageous.
- Quaternary or quinternal alloys containing palladium are also very interesting.
- the alloys 20Pd10In, 10Pd 5In 5Ca, 15Pd 10In 5Ca, 5Pd 10In 5Ca, 10Pd, 5In, 20Pd 10In 0.1Si, 20Pd 10In 1Ca, 20Pd 10In 0.5Ca, 20Pd 10In 0 , 02Si have weak drifts and are interesting.
- AuCuPdIn alloys, such as 20Pd 10In alloy or 10Pd 5In alloy are particularly interesting.
- an alloy composed of at least 750 ⁇ 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 ⁇ , 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 20 ⁇ and 35 ⁇ , and / or when alloy comprises at least 1 ⁇ of Pd and 1 ⁇ of In, or 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 selected from Ca, Zr, or In is of interest, particularly when the sum 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 element (s) Y is in the range between 15 ⁇ and 40 ⁇ , or even 20 ⁇ and 35 ⁇ , and / or when the alloy comprises at least 1 ⁇ of Pd and 1 ⁇ of the element Y or even at least 5 ⁇ of Pd and 5 ⁇ of the element Y.
- 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. , especially 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 ⁇ , even 25 ⁇ , or even 20 ⁇ , or even 17 ⁇ , or even 15 ⁇ , or 13 ⁇ , and / or when the sum of the Pd and Y element (s) is in the range of 15 ⁇ to 40 ⁇ , or even 20 ⁇ to 35 ⁇ , and / or when alloy comprises at least 1 ⁇ Pd and 1 ⁇ or Y elements or even at least 5 ⁇ of Pd and 5 ⁇ or Y elements.
- 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.
- 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 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 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 illustrated by curve 3 of FIG. figure 1 and the results of the different tables of figure 2 to 4 .
- an alloy comprising by weight at least 750 ⁇ of gold, also comprising copper, palladium and indium, the sum of the palladium and indium levels being less than or equal to 45 ⁇ , even lower than or equal to 35 ⁇ , or even lower than or equal to 30 ⁇ , and / or the sum of the palladium and indium levels being between 20 ⁇ and 35 ⁇ , is advantageous.
- Such an alloy may comprise an indium content defined by: 7 ⁇ ⁇ rate of In ⁇ 15 ⁇ .
- 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 ⁇ .
- the figure 5 illustrates the discoloration obtained after 40 days for different alloys, according to the sum of the levels of palladium and indium they comprise. 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 combine several high-performance alloys, and the reduced 25 ⁇ -33 ⁇ range brings together even better results.
- the figure 6 provides further guidance 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 ⁇ and 30 ⁇ , even between 19 ⁇ and 29 ⁇ , and an indium content of between 1 ⁇ and 15 ⁇ inclusive. Note that when using a small amount of indium, for example between 1 ⁇ and 10 ⁇ , or between 1 ⁇ and 6 ⁇ , and even between 1 ⁇ and 4 ⁇ , there is a advantageous significant effect due to its combination with palladium.
- the 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 ⁇ copper, positioned on the right and bottom of the diagram, near the abscissa axis.
- the sum of the palladium and indium levels 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 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 which allow both to reach a satisfactory pink color and a slight discoloration are between 15 ⁇ and 35 ⁇ , or even between 20 ⁇ and 35 ⁇ , even between 25 ⁇ and 33 ⁇ , 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 ⁇ , or even less than or equal to 19 ⁇ or 18 ⁇ , is favorable to the aesthetics of the pink color.
- a palladium level of between 19 ⁇ and 25 ⁇ inclusive forms a good solution.
- the foregoing considerations may be adapted to any amount of copper greater than or equal to 180 ⁇ , especially also for a relatively small quantity of copper, for example between 180 ⁇ and 200 ⁇ .
- the amount of copper Cu is greater than or equal to 200 ⁇ , it is possible to obtain suitable alloys with a palladium content of between 4 ⁇ and 35 ⁇ and an indium content of between 1 ⁇ and 16 ⁇ .
- the invention relates to a timepiece, jewelery or jewelery comprising an alloy comprising by weight at least 750 ⁇ of gold, characterized in that the alloy also comprises at least 200 ⁇ of copper, between 4 ⁇ and 35 ⁇ of palladium and between 1 ⁇ and 16 ⁇ of indium.
- a relatively high palladium content which can then be between 19 ⁇ and 35 ⁇ , or even between 21 ⁇ and 35 ⁇ . 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 level, closer to 30 ⁇ if possible and preferably strictly under 30 ⁇ .
- the optimal ranges taking into account these constraints are then a palladium content 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 a good compromise.
- This grain refining element may 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 modifying the hardness, nor to affect the color, which is advantageous with respect to the desired object.
- 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.
- the sum of the rates of all the elements of the alloy excluding gold and copper is less than or equal to 40 ⁇ .
- 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 quantity especially 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 with the time of the alloys illustrated, without having any noticeable effect on the color itself, since a sufficient copper content, preferably greater than or equal to 180 ⁇ , more preferably greater than or equal to 200 ⁇ , is used .
- this effect of the Ca and Si components is also check on any other pink gold alloy, not necessarily including palladium and / or indium.
- 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.
- silver does not have a very effective effect on the behavior over time of the color, compared to the 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.
- 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, 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.
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Claims (10)
- Zeitmesser, Schmuck- oder Juwelierstück umfassend eine Legierung, die gewichtsbezogen mindestens aus 750‰ Gold besteht, dadurch gekennzeichnet, dass die Legierung darüber hinaus besteht aus:- mindestens 200‰ Kupfer,- zwischen 19‰ und 35‰ Palladium,- zwischen 1‰ und 16‰ Indium,- gegebenenfalls mindestens einem Kornverfeinerungselement, insbesondere gewählt aus Ru, Ir, Re, Co, V und Mo,- gegebenenfalls mindestens einem Element Y gewählt aus Kalzium (Ca), Strontium (Sr), Silizium (Si), Titan (Ti), Zirkonium (Zr) oder Magnesium (Mg).
- Zeitmesser, Schmuck- oder Juwelierstück gemäß dem vorangehenden Anspruch, dadurch gekennzeichnet, dass die Legierung zwischen 21‰ und 35‰, bevorzugt zwischen 23‰ und 31‰, bevorzugt zwischen 23‰ und 27‰ Palladium und zwischen 1‰ und 16‰, bevorzugt zwischen 1‰ und 10‰, bevorzugt zwischen 1‰ und 6‰, bevorzugt zwischen 1‰ und 4‰ Indium umfasst.
- Zeitmesser, Schmuck- oder Juwelierstück gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Legierung kein Silber umfasst und/oder dass die Legierung kein Mangan umfasst.
- Zeitmesser, Schmuck- oder Juwelierstück gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Stück mindestens einen massiven Teil zusammengesetzt aus der genannten Legierung aufweist und eine Dicke größer oder gleich 0,1 mm umfasst.
- Zeitmesser, Schmuck- oder Juwelierstück gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Summe der Anteile an Palladium und Indium in der Legierung kleiner oder gleich 45‰, bevorzugt kleiner oder gleich 35‰, bevorzugt kleiner oder gleich 30‰, bevorzugt kleiner oder gleich 25‰ ist und/oder die Summe der Anteile an Palladium und Indium zwischen 15‰ und 35‰, bevorzugt zwischen 20‰ und 35‰, bevorzugt zwischen 25‰ und 33‰ liegt.
- Zeitmesser, Schmuck- oder Juwelierstück gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass der Anteil der Kornverfeinerungselemente kleiner oder gleich 2‰ oder kleiner oder gleich 1‰ ist.
- Zeitmesser, Schmuck- oder Juwelierstück gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Legierung besteht aus:- Gold, Kupfer, Palladium, Indium, oder aus- Gold, Kupfer, Palladium, Indium und mindestens einem Kornverfeinerungselement, oder aus- Gold, Kupfer, Palladium, Indium, und mindestens einem Element Y gewählt aus Kalzium (Ca), Strontium (Sr), Silizium (Si), Titan (Ti), Zirkonium (Zr) oder Magnesium (Mg), oder aus- Gold, Kupfer, Palladium, Indium und mindestens einem Element Y gewählt aus Kalzium (Ca), Strontium (Sr), Silizium (Si), Titan (Ti), Zirkonium (Zr) oder Magnesium (Mg) und mindestens einem Kornverfeinerungselement.
- Zeitmesser, Schmuck- oder Juwelierstück gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Legierung Kalzium umfasst, mit einem Anteil an Kalzium kleiner oder gleich 10‰, bevorzugt 7‰, bevorzugt 5‰ und/oder Silizium, mit einem Anteil an Silizium kleiner oder gleich 2‰, bevorzugt kleiner oder gleich 0,5‰.
- Zeitmesser, Schmuck- oder Juwelierstück gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Summe der Anteile aller Elemente der Legierung außer Gold und Kupfer kleiner oder gleich 40‰ ist.
- Uhr, dadurch gekennzeichnet, dass sie einen Zeitmesser gemäß einem der vorangehenden Ansprüche umfasst.
Priority Applications (1)
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EP14705988.5A EP2954080B1 (de) | 2013-02-06 | 2014-02-06 | Roségold-legierung für uhr |
Applications Claiming Priority (5)
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EP13154296 | 2013-02-06 | ||
EP13155142 | 2013-02-13 | ||
EP14150827 | 2014-01-10 | ||
PCT/EP2014/052372 WO2014122234A1 (fr) | 2013-02-06 | 2014-02-06 | Piece d'horlogerie en alliage d'or rose |
EP14705988.5A EP2954080B1 (de) | 2013-02-06 | 2014-02-06 | Roségold-legierung für uhr |
Publications (2)
Publication Number | Publication Date |
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EP2954080A1 EP2954080A1 (de) | 2015-12-16 |
EP2954080B1 true EP2954080B1 (de) | 2017-03-15 |
Family
ID=50068996
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14704109.9A Active EP2954079B1 (de) | 2013-02-06 | 2014-02-06 | Roségold-legierung für uhr |
EP14703078.7A Active EP2954078B1 (de) | 2013-02-06 | 2014-02-06 | Roségold-legierung für uhr |
EP14705988.5A Active EP2954080B1 (de) | 2013-02-06 | 2014-02-06 | Roségold-legierung für uhr |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
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EP14704109.9A Active EP2954079B1 (de) | 2013-02-06 | 2014-02-06 | Roségold-legierung für uhr |
EP14703078.7A Active EP2954078B1 (de) | 2013-02-06 | 2014-02-06 | Roségold-legierung für uhr |
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US (3) | US10514661B2 (de) |
EP (3) | EP2954079B1 (de) |
JP (5) | JP6595344B2 (de) |
CN (4) | CN104968813A (de) |
CH (3) | CH707539B1 (de) |
WO (3) | WO2014122234A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH709207B1 (it) | 2012-12-03 | 2018-08-15 | Argor Heraeus Sa | Lega d'oro resistente alla decolorazione. |
EP3040790A1 (de) * | 2014-12-29 | 2016-07-06 | Montres Breguet S.A. | Uhr oder Schmuckgegenstand aus einer leichten hochwertigen Legierung auf Titanbasis |
WO2018178998A1 (en) * | 2017-03-27 | 2018-10-04 | Pethe Subodh | Hard gold alloy with zirconium, titanium and magnesium for jewelry manufacture |
EP3575421B1 (de) | 2018-06-01 | 2022-09-14 | Omega SA | Teil einer uhr oder eines schmuckstückes aus einer legierung auf basis von gold |
CH715203B1 (fr) | 2018-07-26 | 2022-03-15 | Px Services Sa | Alliage à base d'or présentant un changement de couleur et son utilisation dans le domaine de la joaillerie et de l'horlogerie. |
KR102610328B1 (ko) | 2018-12-17 | 2023-12-06 | 현대자동차주식회사 | 로즈골드색 구리 합금 및 이의 용도 |
IT201900001769A1 (it) * | 2019-02-07 | 2020-08-07 | Italfimet Srl | Lega d'oro rosa, procedimento di realizzazione ed uso. |
JP6716071B1 (ja) * | 2019-08-16 | 2020-07-01 | ラブロ コロマー ジャウム | 装飾品 |
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US3769006A (en) | 1972-01-27 | 1973-10-30 | Gold Refining W Co | Bright cast alloy, and composition |
US3861455A (en) | 1972-01-27 | 1975-01-21 | Williams Gold Refining Co | Method of investment casting a bright gold alloy |
SU448239A1 (ru) | 1973-03-05 | 1974-10-30 | Московский Завод По Обрабоке Специальных Сплавов | Сплав на основе золота |
IT1098266B (it) * | 1977-08-29 | 1985-09-07 | Scherico Ltd | 2-sostituti-3-fenilindoli,procedimento per la loro preparazione e per il loro impiego come immunosoppresori |
JPS57120644A (en) | 1981-01-16 | 1982-07-27 | Citizen Watch Co Ltd | Gold alloy with pinkish color tone |
DE3132143C2 (de) * | 1981-08-14 | 1985-07-04 | Degussa Ag, 6000 Frankfurt | Edelmetallegierung zur Herstellung von mit keramischen Massen verblendbaren Kronen und Brücken |
JPH01132728A (ja) | 1987-11-19 | 1989-05-25 | Ishifuku Kinzoku Kogyo Kk | 歯科陶材焼付け用合金 |
DE4031169C1 (de) | 1990-10-03 | 1992-04-23 | Degussa Ag, 6000 Frankfurt, De | |
GB9314292D0 (en) * | 1993-07-10 | 1993-08-25 | Johnson Matthey Plc | Gold alloy |
DE19525361A1 (de) * | 1995-02-16 | 1996-08-22 | Herbst Bremer Goldschlaegerei | Edelmetall-Legierung und Verwendung derselben |
DE19753055B4 (de) | 1997-11-29 | 2005-09-15 | W.C. Heraeus Gmbh | Feinstdraht aus einer Gold-Legierung, Verfahren zu seiner Herstellung und seine Verwendung |
JPH11335755A (ja) * | 1998-05-27 | 1999-12-07 | Ijima Kingin Kogyo Kk | メガネ用合金 |
DE69812652T2 (de) * | 1998-12-14 | 2004-04-29 | Metalor Technologies International Sa | Graue Goldlegierung, ohne Nickel |
SG82596A1 (en) * | 1999-02-02 | 2001-08-21 | Singapore Polytechnic Ventures | Jewellery alloy compositions |
JP2000336439A (ja) * | 1999-05-27 | 2000-12-05 | Mizuho Kogei:Kk | 白色系金合金 |
DE19958800A1 (de) * | 1999-06-30 | 2001-01-04 | Wieland Edelmetalle | Weißgold-Schmucklegierung |
JP2001049364A (ja) * | 2000-07-03 | 2001-02-20 | Kazuo Ogasa | 硬質貴金属合金部材とその製造方法 |
EP1512765B1 (de) | 2003-09-04 | 2006-12-20 | Rolex Sa | Entfärbungsbestängdige Uhr oder Schmuck |
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EP2251444A1 (de) * | 2009-05-06 | 2010-11-17 | Rolex Sa | Graugoldlegierung ohne Nickel und Kupfer |
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2014
- 2014-02-06 CN CN201480007708.8A patent/CN104968813A/zh active Pending
- 2014-02-06 JP JP2015556501A patent/JP6595344B2/ja active Active
- 2014-02-06 EP EP14704109.9A patent/EP2954079B1/de active Active
- 2014-02-06 CH CH00159/14A patent/CH707539B1/fr unknown
- 2014-02-06 CN CN201480007663.4A patent/CN104968812A/zh active Pending
- 2014-02-06 US US14/765,630 patent/US10514661B2/en active Active
- 2014-02-06 US US14/765,648 patent/US20150368757A1/en not_active Abandoned
- 2014-02-06 JP JP2015556500A patent/JP6595343B2/ja active Active
- 2014-02-06 WO PCT/EP2014/052372 patent/WO2014122234A1/fr active Application Filing
- 2014-02-06 CN CN201480007662.XA patent/CN104968811A/zh active Pending
- 2014-02-06 CH CH00157/14A patent/CH707538B1/fr unknown
- 2014-02-06 WO PCT/EP2014/052373 patent/WO2014122235A1/fr active Application Filing
- 2014-02-06 CN CN202010641225.0A patent/CN111809076A/zh active Pending
- 2014-02-06 EP EP14703078.7A patent/EP2954078B1/de active Active
- 2014-02-06 EP EP14705988.5A patent/EP2954080B1/de active Active
- 2014-02-06 CH CH00158/14A patent/CH707537B1/fr unknown
- 2014-02-06 JP JP2015556502A patent/JP2016513176A/ja active Pending
- 2014-02-06 US US14/765,627 patent/US20150368756A1/en not_active Abandoned
- 2014-02-06 WO PCT/EP2014/052371 patent/WO2014122233A1/fr active Application Filing
-
2019
- 2019-02-01 JP JP2019016789A patent/JP2019122776A/ja active Pending
- 2019-02-08 JP JP2019021245A patent/JP2019123943A/ja active Pending
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
US20150368757A1 (en) | 2015-12-24 |
JP2019122776A (ja) | 2019-07-25 |
CH707539A8 (fr) | 2014-10-15 |
CN104968812A (zh) | 2015-10-07 |
EP2954078B1 (de) | 2020-05-06 |
CH707538B1 (fr) | 2017-12-15 |
JP6595344B2 (ja) | 2019-10-23 |
CH707537B1 (fr) | 2017-01-13 |
EP2954080A1 (de) | 2015-12-16 |
WO2014122235A1 (fr) | 2014-08-14 |
EP2954079B1 (de) | 2020-08-19 |
US20150368756A1 (en) | 2015-12-24 |
CH707537A8 (fr) | 2014-10-15 |
CN104968811A (zh) | 2015-10-07 |
CH707538A2 (fr) | 2014-08-15 |
EP2954078A1 (de) | 2015-12-16 |
CH707539B1 (fr) | 2017-01-13 |
JP2016513175A (ja) | 2016-05-12 |
JP2016513176A (ja) | 2016-05-12 |
WO2014122233A1 (fr) | 2014-08-14 |
US20150378311A1 (en) | 2015-12-31 |
CH707539A2 (fr) | 2014-08-15 |
WO2014122234A1 (fr) | 2014-08-14 |
US10514661B2 (en) | 2019-12-24 |
JP2019123943A (ja) | 2019-07-25 |
EP2954079A1 (de) | 2015-12-16 |
JP6595343B2 (ja) | 2019-10-23 |
CH707537A2 (fr) | 2014-08-15 |
CH707538A8 (fr) | 2014-10-15 |
US20160306327A2 (en) | 2016-10-20 |
CN111809076A (zh) | 2020-10-23 |
JP2016514201A (ja) | 2016-05-19 |
CN104968813A (zh) | 2015-10-07 |
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