EP3553192B1 - Alliage d'or 14k resistant au ternissage et son procédé de fabrication - Google Patents

Alliage d'or 14k resistant au ternissage et son procédé de fabrication Download PDF

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Publication number
EP3553192B1
EP3553192B1 EP19169009.8A EP19169009A EP3553192B1 EP 3553192 B1 EP3553192 B1 EP 3553192B1 EP 19169009 A EP19169009 A EP 19169009A EP 3553192 B1 EP3553192 B1 EP 3553192B1
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Prior art keywords
alloy
gold
alloys
weight
color
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EP19169009.8A
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German (de)
English (en)
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EP3553192A1 (fr
Inventor
Sergio ARNABOLDI
Marta ROSSINI
Marco NAUER
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Argor Heraeus SA
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Argor Heraeus SA
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Priority claimed from IT102018000004444A external-priority patent/IT201800004444A1/it
Priority claimed from CH00465/18A external-priority patent/CH714882B1/it
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Publication of EP3553192A1 publication Critical patent/EP3553192A1/fr
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon

Definitions

  • the present invention refers to the field of Gold alloys and in particular refers to a Gold alloy with Gold title substantially equal to 14 carats (14K).
  • the present invention also refers to a method for the production of a Gold alloy.
  • the Gold alloy and the method for the production of Gold alloys according to the invention are an alloy and a method for the production of Gold alloys for jewelry and watchmaking applications respectively.
  • Gold is not used in pure form, since it is too ductile.
  • Gold alloys for jewelry or watchmaking characterized by a higher hardness with respect to the Gold in pure form and/or with respect to low hardness or high ductility Gold alloys.
  • Colors for Gold alloys can be measured univocally in the CIELAB 1976 color space, which defines a color on the basis of a first L* parameter, a second a* parameter and a third b* parameter, wherein the first L* parameter identifies the brightness and adopts values comprised between 0 (black) and 100 (white) whereas the second a* parameter and the third b* parameter represent chromaticity parameters.
  • the C ab * parameter is defined as "chroma"; the higher the value of C ab * parameter is, the higher is the color saturation; the lower the value of C ab * parameter is, the lower is the color saturation, that will tend to the grey scale.
  • alloys with a Gold content higher than 750 ⁇ which can be used as such as white or grey Gold alloys and do not require surface rhodium plating, arbitrarily show C ab * values ⁇ 8.
  • the parameter h ab* identifies on the other hand the tonality of the color.
  • the ISO DIS 8654:2017 standard defines seven color designations as for the Gold alloys for jewelry.
  • these alloys are defined according to the following table, wherein the color is defined on a standard reference specified between 0N and 6N.
  • Table 1 Color Designation 0N Yellow-green 1N Dark yellow 2N Light yellow 3N Yellow 4N Pink 5N Red 6N Dark red
  • the ISO DIS 8654 standard specifies that the measuring instrument must comply with the CIE N° 15 publication.
  • the ISO DIS 8654:2017 standard also shows the nominal values L* a* b* as trichromatic coordinates for alloys of 0N-6N standard color, including the tolerances.
  • L* a* b* as trichromatic coordinates for alloys of 0N-6N standard color, including the tolerances.
  • an abstract of the standard wherein are defined the chromatic limits of the alloys defined by the ISO DIS 8654:2017 standard as pink/red.
  • the ISO DIS 8654:2017 standard also proposes chemical compositions recommended for each of the 0N-6N alloys.
  • the compositions are the ones specified in the table: Table 3 Color Chemical composition - % in weight Au Ag Cu 4N 75.0 8.5 - 9.5 Remaining part 5N 75.0 4.5 - 5.5 6N 75.0 0-1.0
  • the pink/red Gold alloys of known type show a substantial color instability, in particular when exposed to environments wherein there are chlorides or sulphides.
  • the Applicant has noted that the 5N ISO DIS 8654:2017 Gold alloy in the formulation that uses the minimum reference value as for the content of Silver exposed to vapors of thioacetamide for 150 hours (according to the UNI EN ISO 4538:1998 standard), shows a variation of color ⁇ E (L* a* b*) equal to 5.6; when exposed to the action of an aqueous solution 50g/liter of sodium chloride (NaCl) at 35°C for 175 hours, the 5N Gold alloy shows a variation of color ⁇ E (L* a* b*) equal to 3.6.
  • alloys including Gold with title equal to or substantially equal to 14K it is known that the presence of Copper has the drawback of being rather prone to vary color especially when the object of jewelry is worn and exposed to human sweating and/or saline environment.
  • the same alloys, including Gold with a title equal to or substantially equal to 14K are known to have significant color variation even just after exposure to air.
  • a first drawback derives from the fact that it is difficult to realize a plating whose color is perfectly superimposable to that of the basic alloy with which the item of jewelry is made.
  • the plating of a jewelry item with high title Gold alloys is expensive, and significantly contributes to the increase in the production cost of the item not only because of the cost of the high title Gold alloy per se, but also because of the further necessary processing on the jewelry item, which incidentally for shapes of jewelry items of considerable complexity, may not be insignificant.
  • the plating representing the surface layer of the item, is the portion the most subject to wear or anyhow removal; with the removal of the plating, the item of jewelry may have exposed portions of alloy with Gold title equal to or substantially equal to 14K, which - exposed to chemically aggressive environments - may have different color than the portions that vice versa still carry the plating alloy.
  • the purpose of the present invention is therefore to describe a Gold alloy, particularly for jewelry and watchmaking, with a Gold title equal to or substantially equal to 14K, which solves the above described drawbacks, in particular being not very prone to turn color when exposed to environments with air, Thioacetamide or NaCl in solution.
  • the purpose of the present invention is also to describe a method of production of an alloy containing Gold with a title equal to or substantially equal to 14K, which solves the above described drawbacks.
  • the purpose of the present invention is finally to describe an item of jewelry or part of an item for jewelry, made with the alloy object of the invention, which does not show the above described drawbacks.
  • An object of the invention is to disclose a Gold alloy and a method of production thereof according the appended claims.
  • the Gold alloy of the present invention is characterized by a pearly red color.
  • pearly red is intended a color that, arbitrarily, on the a* b* color plan according to the CIE 1976 color chart, is not comprised in the spaces defined by the ISO DIS 8654:2017 standard and is enclosed in a polygon at least defined by the following points ( Fig.
  • the Gold alloy may be free from secondary phases, and/or is a homogeneous alloy, and/or is a crystalline alloy, optionally 100% crystalline.
  • free from secondary phases or “free from second phases” is intended an alloy free from elements that can generate said second phases, in particular in a proceeding of melting and subsequent solidification without other thermal treatments; second phases that create in the liquid phase and remain downstream of the alloy solidification, are harmful second phases, for example carbides and/or oxides that during the polishing step are visible at naked eye on the surface of the polished item, and that then prevent to obtain items of high surface quality, compatible with the needs required in the high jewelry field.
  • the alloys that are described in the present invention have been tested in terms of resistance to color variation (tarnishing) in environments comprising Thioacetamide and NaCl solutions (sodium chloride).
  • any reference to tests carried out in an environment comprising Thioacetamide is made according to the indications of the UNI EN ISO4538:1998 standard.
  • the samples are exposed to vapours of Thioacetamide CH 3 CSNH 2 in an atmosphere with relative humidity of 75% kept through the presence of a saturated solution of sodium acetate trihydrate CH 3 COONa • 3H 2 O in a test chamber with a capacity comprised between 2 and 20 litres and wherein all the materials used for the construction of the chamber itself are resistant to volatile sulphides and do not emit any gas or vapour capable of influencing the results of the test.
  • the tests have been carried out by immersing the samples of a Gold alloy in a 50g/L NaCl solution at neutral pH, thermostated at 35°C.
  • the family of Gold alloys object of the invention comprises at least ternary alloys, and more in particular ternary or quaternary alloys. Therefore, the number of elements that are included in a not insignificant amount in the family of Gold alloys object of the invention is at least equal to 3 and, preferably, not higher than 4.
  • the alloys according to the preceding formulations are preferred and non-limiting examples of Gold alloy for jewelry with a title equal to or substantially equal to 14K.
  • the tarnishing resistance tests carried out by the Applicant and reported below have been carried out with respect to a reference alloy, in particular a reference ternary alloy comprising Gold, Copper and Silver, not optimized then for tarnishing resistance due to its composition, hereinafter indicated: Table 6 Reference alloy nominal composition [ ⁇ ] LRS 503 Au Ag Cu Pd Fe Total 585.5 40 374.5 1000
  • the alloys according to the family generally described as the object of the invention and, consequently, the specific realizations described in table 5 are realizations characterized by the absence of Silver.
  • Silver is known to be an element that in these alloys helps to increase the hardness of the alloy.
  • the LRS 503 alloy used as reference test in the absence of work hardening, has a hardness according to HV5 equal to 130, equal to 173 with 25% work hardening, equal to 230 with 50% work hardening and equal to 258 with 75% work hardening.
  • Table 7 % work hardening HV5 0 25 50 75 501 127 173 220 240 502 119 175 231 244 503 130 173 230 258 509 129 171 225 242 510 125 171 232 248 511 135 180 235 251
  • the Applicant has observed that the specific formulations of Gold alloy described in table 7 have hardness, in particular at the annealed stage, compatible with that of alloys for jewelry according to the present invention.
  • the LRS 509 and LRS 511 formulations are respectively the closest to the behavior in terms of hardness possessed by the LRS 503 (whose alignment in the table is offset for ease of representation) used as reference test and even better, at least until the work hardening equal to 50% with respect to the behavior obtained by the LRS 503 alloy.
  • All the alloys according to the general formulation, and in particular all the specific realizations of the alloys according to table 5 have a better behavior, both in NaCl solution and in Thioacetamide, with respect to the LRS 503 alloy used as reference test.
  • the alloy used as a reference test has a color that is not compatible with that of the alloys object of the invention, the latter alloys have a significantly lower trend to change color.
  • the Applicant has observed that the alloys according to the general formulation above mentioned and in particular all the specific embodiments of alloys according to table 5 have a behavior in NaCl saline solution as for the above mentioned specifications even better that the behavior obtained by 5N alloy according to the ISO standard, whose Gold content is significantly higher, being as a matter of fact equal to 18K.
  • the Applicant has observed that the optimization of the alloy behavior in terms of tarnishing is optimized for Palladium values within the range of [10 ⁇ - 30 ⁇ ] in weight.
  • the absolute best behavior in terms of resistance to color variation, in particular for exposures higher than 5h is the one of the LRS 502 alloy, which includes the highest Palladium content among the specific formulations of table 5 and is characterized by the absence of Iron; although Iron is known for optimizing the performances of alloys in an environment containing Thioacetamide ( WO2014/087216 A1 ), the Applicant has surprisingly found that the LRS 509 alloy, as well as the LRS 510 alloy, although both of them have Iron in the measure of 5 ⁇ and 10 ⁇ respectively have performances substantially similar to that of the alloy according to the LRS 502 formulation and better than that of the alloy according to the LRS 501 formulation, ternary, which shows only Palladium in the amount of 20 ⁇ .
  • an alloy such as the ones object of the present invention cannot present a resistance to the variation of color equal to the one which is typical of an 18K Gold alloy such as the 5N ISO, which after 24 hours of exposure presents a variation of color ⁇ E(L*, a* b*) substantially equal to 3.6, while all the tested alloys - and more generally the alloys according to the general formulation above expressed - have a color variation under the same conditions higher than ⁇ E(L*, a* b*)>4.
  • the alloys object of the invention have a significantly better behavior than the LRS 503 alloy used as reference test, which after 24 hours of exposure in Thioacetamide has a color variation equal to 6.20.
  • the Applicant has observed that the alloy must be ternary or quaternary, with the necessary presence of Palladium and with the sum of the amounts of Gold, Copper and Palladium at least equal to 900 ⁇ in weight.
  • alloys were conceived according to a first subfamily that comprises Palladium in the amount between 12 ⁇ , more preferably 15 ⁇ in weight, and 27 ⁇ , more preferably 25 ⁇ in weight.
  • alloys have been developed that include Iron in an amount comprised between 2 ⁇ in weight and 15 ⁇ in weight, more preferably comprised between 4 ⁇ in weight and 13 ⁇ in weight, and even more preferably between 5 ⁇ in weight and 10 ⁇ in weight.
  • Gold is present in the amount between 565 ⁇ in weight and 605 ⁇ in weight, and more preferably between 575 ⁇ in weight and 595 ⁇ in weight, and Copper is present between 370 ⁇ and 405 ⁇ in weight, and Palladium is comprised between 12 ⁇ , more preferably 15 ⁇ in weight, and 27 ⁇ , more preferably 25 ⁇ in weight. All these alloys have a better performance in Thioacetamide and NaCl saline solution than the reference alloy LRS 503 in terms of resistance to color variation.
  • a subfamily of alloys has also been studied in which Gold is present in the amount between 565 ⁇ in weight and 605 ⁇ in weight, and more preferably between 575 ⁇ in weight and 595 ⁇ in weight, and Copper is present between 370 ⁇ and 405 ⁇ in weight, and the sum of the amounts of Palladium and Iron is comprised between 23 ⁇ and 27 ⁇ , even more preferably substantially equal to 25 ⁇ .
  • the presence of Palladium and Iron in the amounts above described contributes to optimize the performances of the alloy in saline solution of NaCl, in particular for low Iron contents, in a measure equal to or substantially equal to 5 ⁇ .
  • Iron is also present, it is possible to create families of alloys in which Gold is present in amount comprised between 565 ⁇ in weight and 605 ⁇ in weight, and more preferably between 575 ⁇ in weight and 595 ⁇ in weight, and Copper is present between 370 ⁇ and 405 ⁇ in weight and the sum of Palladium and Iron is comprised between 25 ⁇ and 30 ⁇ .
  • Palladium is present in the amount between 13 ⁇ and 17 ⁇ in weight, preferably between 14 ⁇ and 16 ⁇ in weight and even more preferably in the amount substantially equal to 15 ⁇ in weight.
  • the amount of Iron is substantially equal to 10 ⁇
  • the performances of the alloy in Thioacetamide are substantially maximized. Therefore, with maximized performances, it is possible to realize Gold alloys for jewelry in which Gold is present in amount comprised between 565 ⁇ in weight and 605 ⁇ in weight, and more preferably between 575 ⁇ in weight and 595 ⁇ in weight, and Copper is present between 370 ⁇ and 405 ⁇ in weight and the sum of Palladium and Iron is comprised between 30 ⁇ and 35 ⁇ .
  • Alloys according to the above mentioned general formulation have a color that, on the CIELAB1976 color chart, shows a coordinate a* comprised in the range [6.5 - 9.5] and a coordinate b* ⁇ 13.5, preferably comprised in the range [10 - 13.5].
  • the alloy according to the invention is also free from Magnesium, Silicon, Titanium, Tungsten, Molybdenum, Niobium, Tantalum, Zirconium, Yttrium, Germanium, and is also free from Nickel, Arsenic and Cobalt. Thanks to this last aspect, the alloy is a Gold alloy compatible with being worn or wearable by subjects whose allergic tolerance is significantly low.
  • some embodiments which are not part of the invention can comprise additional materials in total amount, i.e. in sum, not higher than 2 ⁇ and more preferably not higher than 1 ⁇ ; the list of said additional materials comprises Iridium, Indium, Ruthenium and Rhenium. These materials can have, under certain conditions better explained hereinafter, grain refining properties.
  • Iridium is preferably used in alloys containing high Copper contents, because it binds in particular with the latter element; preferably, but non-limiting thereto, if present, Iridium is present in a maximum amount equal to 0.5 ⁇ in weight.
  • Rarer is the use of Ruthenium and Rhenium, in a sometimes lower amount, but anyway up to 0.5 ⁇ in weight.
  • Ruthenium and Rhenium are preferably used in Gold alloys containing Palladium.
  • Iridium or Rhenium and Ruthenium is subject to the inclusion of these elements in pre-alloys.
  • these elements if not pre-bonded with the material with affinity thereto, but directly introduced into the pot, do not form alloy, thus contributing to a worsening of the characteristics of the alloy.
  • pre-alloy with Copper (Iridium) or Palladium (Rhenium and Ruthenium) taking care to make the pre-alloy bind with the rest of the elements composing the alloy itself, it is possible to refine the grain.
  • Gold alloy in particular a Gold alloy for jewelry, comprising Gold, Copper, Palladium and optionally Iron according to the above description.
  • the Gold alloys object of the invention are made from pure elements, in particular from Gold at 99.99%, Cu at 99.99%, Pd at 99.95%, Fe al 99.99%, Ag at 99.99%.
  • the process of melting of pure elements for the creation of the Gold alloys according to the invention can be in detail a process of discontinuous melting of Gold or a process of continuous melting of Gold.
  • the process of discontinuous melting of Gold is a process in which the mixing is melted and cast into a refractory mold or refractory or metallic ingot mould. In this case the above mentioned elements are melted and cast in a controlled atmosphere. More in particular, the melting operations are carried out only after having preferably conducted at least 3 conditioning cycles of the atmosphere of the melting chamber. This conditioning involves first of all reaching a vacuum level up to pressures lower than 1x10 -2 mbar and a subsequent partial saturation with Argon at 500mbar. During the melting, the Argon pressure is kept at pressure levels between 500mbar and 800mbar.
  • a phase of overheating of the mixture takes place, in which the mixture is heated up to a temperature of about 1250°C, and in any case to a temperature above 1200°C, in order to homogenize the chemical composition of the metal bath.
  • the pressure value in the melting chamber reaches again a vacuum level lower than 1x10 -2 mbar, useful to eliminate part of the residues produced by the melting of the pure elements.
  • the melted material is casted into a mould or ingot mould realized in graphite and the melting chamber is again pressurized with an inert gas, preferably argon, injected at a pressure lower than 800mbar and in particular lower than 700mbar.
  • an inert gas preferably argon
  • the bars or casts are extracted from the bracket.
  • the alloy is solidified, from the mold in graphite are obtained Gold bars or Gold alloy casts which are subjected to quick cooling by means of a step of immersion in water, in order to reduce and possibly avoid solid state phase transformations.
  • the bars or casts are subjected to a quick cooling phase, preferably but non-limiting in water, in order to avoid phase variations in the solid state.
  • the production process of the Gold alloy according to the invention comprises, starting from the pure elements according to the above, a mixing step of the elements and a step of introduction of the mixture in a melting pot, and a subsequent melting through heating until melting.
  • the process of continuous melting is a process in which solidification and extraction of the solidified Gold are continuously carried out from one free end of a Gold bar or cast.
  • a graphite die is used in the continuous melting process.
  • the use of graphite dies is known, since graphite is a solid lubricant, and typically has low friction between its surfaces and those of the solidified metal, permitting to obtain an easy extraction of the element contained therein without fractures and with the minimum amount of defects present on its surface.
  • the production process may comprise a step of realizing of a pre-alloy, in which said pre-alloy comprises:
  • the bars or casts obtained by discontinuous or continuous melting are subject to a step of cold plastic deformation, preferably but non-limiting to flat rolling.
  • the different compositions synthesized according to the previously described melting procedure are deformed up to 70% and then subjected to a thermal treatment of solubilization at a temperature higher than 680°C, in order to be subsequently cooled.
  • Particular embodiments of the previously described method include an initial step in which are mixed in particular Palladium in the amount comprised between 12 ⁇ , more preferably 15 ⁇ , and 27 ⁇ , more preferably 25 ⁇ in weight and/or, in addition to the preceding elements, also Iron comprised between 2 ⁇ in weight and 15 ⁇ in weight, more preferably between 4 ⁇ in weight and 13 ⁇ in weight.
  • Iron can be comprised between 5 ⁇ and 10 ⁇ in weight.
  • the method comprises the mixing of Gold, Copper and Palladium such as that the sum in thousandth of their weights is at least equal to 910 ⁇ , more preferably 950 ⁇ , and even more preferably 960 ⁇ or even 970 ⁇ .
  • the sum of the amounts of Gold, Copper and Palladium is at least equal to 900 ⁇ in weight, and more in particular in the amount at least equal to 960 ⁇ in weight, more preferably 970 ⁇ in weight.
  • the sum of Palladium and Iron is lower than 37 ⁇ in weight, and more preferably lower than 35 ⁇ in weight, wherein Iron is comprised in the amount between 5 ⁇ and 10 ⁇ in weight.
  • Another specific embodiment of the method comprises the mixing of Gold in the amount comprised between 565 ⁇ in weight and 605 ⁇ in weight, and more preferably between 575 ⁇ in weight and 595 ⁇ in weight, and Copper between 370 ⁇ and 405 ⁇ in weight and Palladium between 12 ⁇ , more preferably 15 ⁇ in weight, and 27 ⁇ , more preferably 25 ⁇ in weight, or alternatively Gold in the amount comprised between 565 ⁇ and 605 ⁇ in weight, and more preferably between 575 ⁇ and 595 ⁇ in weight, and Copper between 370 ⁇ and 405 ⁇ in weight, with the sum of the amounts of Palladium and Iron comprised between 23 ⁇ and 27 ⁇ , even more preferably equal to 25 ⁇ .
  • the advantages offered by the alloy object of the invention are clear in the light of the above obtained description.
  • the alloys are characterized by a low tendency to tarnishing for the environments in which an item of jewelry is typically found to be used, consequently it allows to realize items of jewelry or parts of items for jewelry resistant to tarnishing, in substantially red color as above defined, without the need for subsequent plating with high title Gold alloys. Consequently, the item of jewelry thus created is less expensive and less demanding to be processed as well as characterized by a substantially more uniform color even after wear.
  • the alloys according to the present disclosure are alloys without secondary phases.
  • the alloys according to the present disclosure are homogeneous Gold alloys, free from second phases, and in particular free from carbides and/or oxides and/or are crystalline alloys, in particular 100% crystalline. This permits to have a high strength and quality and surface uniformity.
  • free from secondary phases or “free from second phases” is intended an alloy free from elements that can generate them, in particular in a process of melting and subsequent solidification without other thermal treatments; second phases that create in the liquid phase and remain downstream of the alloy solidification, are harmful second phases, for example carbides and/or oxides that during the polishing step are visible at naked eye on the surface of the polished item, and that then prevent to obtain items with high surface quality, compatible with the needs required in the high jewelry field.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Claims (4)

  1. Alliage, en particulier pour la joaillerie, caractérisé en ce qu'il est constitué de :
    - or, en la quantité comprise entre 540 %o et 620 %o en poids ;
    - cuivre, en la quantité comprise entre 360 %o et 415 %o en poids ;
    - palladium, en la quantité comprise entre 10 %o et 30 %o en poids ;
    et, éventuellement, du fer en la quantité inférieure ou égale à 15 %o en poids ;
    l'alliage comprenant une couleur qui, sur la charte de couleur CIELAB1976, présente une coordonnée a* comprise dans l'intervalle [6,5 à 9,5] et une coordonnée b* < 13,5, préférablement comprise dans l'intervalle [10 à 13,5].
  2. Alliage selon la revendication 1, caractérisé en ce que le fer est présent en la quantité comprise entre 2 %o en poids et 15 %o en poids.
  3. Procédé de production d'un alliage d'or selon la revendication 1 ; ledit procédé étant caractérisé en ce qu'il comprend :
    a) une étape d'homogénéisation dans laquelle tous les éléments purs constituant l'alliage sont fondus d'une manière à obtenir une solution ou un mélange homogène, et
    b) une étape d'introduction du mélange dans un creuset, et une fusion ultérieure à travers le chauffage jusqu'à la fusion.
  4. Article de joaillerie, réalisé au moins partiellement à travers un alliage d'or selon l'une ou plusieurs des revendications 1 à 2.
EP19169009.8A 2018-04-12 2019-04-12 Alliage d'or 14k resistant au ternissage et son procédé de fabrication Active EP3553192B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102018000004444A IT201800004444A1 (it) 2018-04-12 2018-04-12 Lega d’oro a 14k resistente al tarnishing e metodo di produzione della medesima
CH00465/18A CH714882B1 (it) 2018-04-12 2018-04-12 Lega d'oro a 14K resistente al tarnishing e metodo di produzione della medesima.

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EP3553192B1 true EP3553192B1 (fr) 2021-07-14

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Publication number Priority date Publication date Assignee Title
CN112210686B (zh) * 2020-09-18 2022-03-11 国金黄金股份有限公司 一种低导热金材料及其制备方法、金器
CN115612887B (zh) * 2022-08-12 2024-04-12 深圳市沃尔弗斯珠宝实业股份有限公司 一种高强度k金首饰及其制备方法

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JPH02225655A (ja) * 1989-02-28 1990-09-07 Agency Of Ind Science & Technol 光沢のある黒色に着色する金合金とその着色法
US5340529A (en) * 1993-07-01 1994-08-23 Dewitt Troy C Gold jewelry alloy
CN105008561B (zh) 2012-12-03 2018-07-03 Argor-Heraeus股份有限公司 抗褪色的金合金

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