EP3553192A1 - Anlaufbeständige 14k-goldlegierung und herstellungsverfahren davon - Google Patents

Anlaufbeständige 14k-goldlegierung und herstellungsverfahren davon Download PDF

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Publication number
EP3553192A1
EP3553192A1 EP19169009.8A EP19169009A EP3553192A1 EP 3553192 A1 EP3553192 A1 EP 3553192A1 EP 19169009 A EP19169009 A EP 19169009A EP 3553192 A1 EP3553192 A1 EP 3553192A1
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Prior art keywords
weight
amount
gold
alloy
comprised
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EP19169009.8A
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French (fr)
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EP3553192B1 (de
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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 CH00465/18A external-priority patent/CH714882B1/it
Priority claimed from IT102018000004444A external-priority patent/IT201800004444A1/it
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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 uniquely measured 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, 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 alloy in particular for jewelry, characterized in that it comprises:
  • jewelry alloy an alloy, in particular a Gold alloy, in which there are no materials toxic to humans and the formulation of which is suitable for, specifically designed for, making jewels, or parts thereof.
  • a jewelry alloy is an alloy that shows, in absence of work hardening, a hardness, measured on a Vickers scale and in particular with the HV5 method, higher than 95, preferably higher than 98.
  • the alloy according to the first aspect is a Gold alloy 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. 1 ): Table 4 Color Trichromatic coordinates (2° observer) Nominal values Tolerances L* a* b* L* [MAX/Min] a* b* pearly red 86.1 8 11.60 87.8 6.5 10.8 8.2 10.3 84.3 9.5 12.7 7.7 13.5
  • the alloy according to a first or second aspect is a tarnishing resistant alloy and/or shows a color variation in NaCl saline solution lower, optionally after a time equal to at least 24h of exposure, lower than the color variation underwent by a reference alloy with a title of Silver equal to 40 ⁇ and/or lower than the 5N alloy according to the ISO DIS 8654:2017 standard.
  • the alloy depending on one or more of the preceding aspects, comprises Palladium in the amount comprised between 12 ⁇ , more preferably 15 ⁇ in weight, and 27 ⁇ , more preferably 25 ⁇ in weight.
  • the alloy according to one or more of the preceding aspects comprises also Iron in the amount comprised between 2 ⁇ in weight and 15 ⁇ in weight, more preferably comprised between 4 ⁇ in weight and 13 ⁇ in weight, even more preferably between 5 ⁇ in weight and 10 ⁇ in weight.
  • the alloy according to one or more of the preceding aspects is a ternary or quaternary alloy, and/or the sum of the amounts of Gold, Copper and Palladium is at least equal to 910 ⁇ in weight.
  • ternary or quaternary Gold alloy an alloy wherein there are 3 or 4 components respectively, the amount of which is not negligible, and in particular higher than 2 ⁇ in weight and more preferably higher than 1 ⁇ in weight.
  • quaternary or quinary alloys do not comprise components in excess of 2 ⁇ in weight and more preferably 1 ⁇ in weight in addition to those explicitly mentioned.
  • the alloy according to the sixth aspect shows a sum of the amounts of Gold, Copper and Palladium at least equal to 950 ⁇ in weight, more preferably 960 ⁇ in weight, even more preferably 970 ⁇ in weight.
  • the sum of the amounts of Palladium and Iron is equal to or lower than 37 ⁇ in weight, more preferably lower than 35 ⁇ in weight.
  • the Iron when depending on the 5° aspect, is comprised in the amount comprised between 5 ⁇ and 10 ⁇ .
  • the Gold is present 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 is present between 370 ⁇ and 405 ⁇ in weight and Palladium is comprised between 12%0, more preferably between 15 ⁇ in weight, and 27 ⁇ , more preferably 25 ⁇ in weight.
  • the Gold when depending on the 5° aspect, is present 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 is present between 370 ⁇ and 405 ⁇ in weight and the sum of Palladium and Iron is comprised between 23 ⁇ and 27 ⁇ , even more preferably substantially equal to 25 ⁇ .
  • the Palladium in the alloy according to one of the aspects from 1° to 3° and/or from 5° to 9°, is present in the amount comprised between 13 ⁇ in weight and 17 ⁇ in weight, preferably between 14 ⁇ in weight and 16 ⁇ in weight and even more preferably in the amount substantially equal to 15 ⁇ in weight.
  • the Gold is present 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 is present between 370 ⁇ and 405 ⁇ in weight and the sum of the amounts of Palladium and Iron is comprised between 25 ⁇ and 30 ⁇ .
  • the Gold is present 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 is present between 370 ⁇ and 405 ⁇ in weight and the sum of the amounts of Palladium and Iron is comprised between 30 ⁇ and 35 ⁇ .
  • the alloy according to the 6° aspect comprises also Silver in the amount lower than 40 ⁇ in weight, and/or Zinc in the amount lower than 40 ⁇ in weight or Silver and Zinc the sum of respective amounts in weight is lower than 40 ⁇ .
  • the alloy according to the 10° aspect is free from Iron.
  • the alloy according to one or more of the preceding aspects is an alloy whose color 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 one or more of the preceding aspects is an alloy characterized by the absence of Vanadium and other materials capable to create carbides and oxides, in particular free from Magnesium, Silicon, Titanium, Tungsten, Molybdenum, Niobium, Tantalum, Zirconium, Yttrium, Germanium. Thanks to this aspect, it is possible to prevent the creation of carbides.
  • the alloy according to one or more of the preceding aspects is a Gold alloy for jewelry free from Nickel, Cobalt, Arsenic and Cadmium. Thanks to this aspect, the alloy is a Gold alloy wearable by subjects whose allergic tolerance is significantly low.
  • said step comprises mixing in particular Palladium in the amount comprised between 12 ⁇ , more preferably 15 ⁇ in weight, and 27 ⁇ , more preferably 25 ⁇ in weight.
  • the method comprises in particular mixing, in addition to the preceding elements, also Iron in the amount comprised between 2 ⁇ and 15 ⁇ in weight, more preferably comprised between 4 ⁇ and 13 ⁇ in weight, even more preferably between 5 ⁇ and 10 ⁇ in weight.
  • the sum of the amounts of Gold, Copper and Palladium is at least equal to 910 ⁇ in weight.
  • the step of mixing comprises the mixing of Gold, Copper and Palladium in the amount at least equal to 950 ⁇ in weight, more preferably 960 ⁇ in weight and/or the sum of the amounts of Gold, Copper and Palladium is at least equal to 950 ⁇ in weight, more preferably 960 ⁇ in weight.
  • the alloy according to the 22° aspect comprises the mixing of the above mentioned elements with the amount of the sum of Palladium and Iron equal to or lower than 37 ⁇ in weight, more preferably lower than 35 ⁇ in weight.
  • the method comprises the mixing of Iron in the amount comprised between 5 ⁇ and 10 ⁇ in weight.
  • 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 in the amount comprised between 370 ⁇ and 405 ⁇ in weight and Palladium in the amount comprised between 12 ⁇ , more preferably 15 ⁇ in weight, and 27 ⁇ , more preferably 25 ⁇ in weight.
  • 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 in the amount comprised between 370 ⁇ and 405 ⁇ in weight and the sum of Palladium and Iron in the amount comprised between 23 ⁇ and 27 ⁇ , even more preferably substantially equal to 25 ⁇ in weight.
  • the method comprises the mixing of Palladium in the amount comprised between 13 ⁇ in weight 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 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 in the amount comprised between 370 ⁇ and 405 ⁇ in weight, Palladium and Iron in the amount of which the sum is comprised between 25 ⁇ and 30 ⁇ in weight.
  • the method comprises the mixing of Gold in the amount comprised between 565 ⁇ in weight and 605 ⁇ in weight, and more preferably between 575 ⁇ and 595 ⁇ in weight, and Copper in the amount comprised between 370 ⁇ and 405 ⁇ in weight, and the sum of Palladium and Iron in the amount comprised between 30 ⁇ and 35 ⁇ in weight.
  • the method comprises the obtaining of an alloy whose color, optionally at the moment of the cooling, on the CIELAB1976 color chart shows a coordinate a* comprised in the range [6.5 - 8.8] and a coordinate b* ⁇ 13, preferably comprised in the range [10 - 13].
  • the method excludes the mixing of Vanadium and other materials capable to create carbides and oxides, in particular free from Magnesium, Silicon, Titanium, Tungsten, Molybdenum, Niobium, Tantalum, Zirconium, Yttrium, Germanium.
  • carbides or oxides in particular but non-limiting after the processing, makes the Gold alloy suitable for applications of jewelry and watchmaking where polishing or diamond polishing of finished items is required.
  • the method excludes the mixing of Nickel, Cobalt, Arsenic and Cadmium. Thanks to this aspect, the alloy is a Gold alloy wearable by subjects whose allergic tolerance is significantly low.
  • said homogenization is a discontinuous melting, comprising a step of casting wherein the melted material is casted in a refractory mold or refractory or metallic ingot.
  • the melting pot is subject to a gas controlled atmosphere and in particular is subject, at least temporarily, to a vacuum condition.
  • said melting pot is subject to a controlled atmosphere, to pressures lower than the environmental one.
  • said controlled atmosphere is an inert gas, preferably argon and/or said pressure is a pressure lower than 800mbar, preferably lower than 700mbar.
  • said gas is a reducing gas, preferably a hydrogen-nitrogen mixture and/or said pressure is a pressure lower than 800mbar, preferably lower than 700mbar.
  • said melting is a continuous melting, comprising a step of melting and homogenization in a graphite pot and a subsequent melting step wherein the melted alloy is casted in a die realized in graphite and wherein said alloy is an alloy of metals without chemical affinity to graphite and more specifically, in particular at least free from Vanadium, Magnesium, Silicon, Titanium, Tungsten, Molybdenum, Niobium, Tantalum, Zirconium, Yttrium, Germanium.
  • said alloy is subject to a cooling step followed by one or more hot or cold plastic deformation step and one or more thermal treatments.
  • an item of jewelry comprising a Gold alloy according to one or more of the preceding aspects concerning said Gold alloy.
  • said item of jewelry comprises a jewel or a watch or a watch bracelet or a movement or part of a mechanical movement for watches.
  • said watch or mechanical movement for watches are configured for being respectively worn or installed in wristwatches.
  • a method of production of an item for jewelry or part of an item for jewelry comprising one or more steps of mechanical processing of a Gold alloy according to one or more of the aspects from 1° to 19°.
  • the Gold alloy is 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 Gold alloy according to the invention may consist of: Gold, in the amount comprised between 540 ⁇ and 620 ⁇ in weight; Copper, in the amount comprised between 360 ⁇ and 415 ⁇ in weight; Palladium, in the amount comprised between 10 ⁇ and 30 ⁇ in weight, and, optionally, at least one among Silver in the amount lower than or equal to 80 ⁇ in weight, Iron in the amount lower than or equal to 80 ⁇ in weight, Zinc in the amount lower than or equal to 80 ⁇ in weight, Indium or Ruthenium in the amount lower than or equal to 0.5 ⁇ in weight, Rhenium in the amount lower than or equal to 0.1 ⁇ in weight, Tin in the amount lower than or equal to 20 ⁇ in weight.
  • 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, although quinary formulations may still be possible and include elements not included in the preceding table.
  • 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 preferably 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 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 - in the ranges identified in the preceding family, for Palladium values comprised within the following range: [8 ⁇ - 32 ⁇ ] in weight, and even more preferably 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 ( WO2014/0872216 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 preferably 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.
  • the remaining 100 ⁇ in weight can be of different materials, including Silver or Zinc or combinations of Silver or Zinc in order to vary at least the specific color of the alloy while remaining within the color previously defined as "pearly red”.
  • all the embodiments specifically identified in Table 5 are specific optimized embodiments taken from a subfamily of alloys in which the sum of the amounts of Gold, Copper and Palladium is at least equal to 960 ⁇ in weight and, even more preferably 970 ⁇ in weight; alloys with this last characteristic have an assimilable behavior in the complex, observing the color variations in air, in Thioacetamide and in NaCl solution.
  • 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 ⁇ .
  • Gold alloys according to the above mentioned general formulation wherein Silver is in the amount lower than 40 ⁇ in weight, and/or Zinc in the amount lower than 40 ⁇ in weight or Silver and Zinc the sum of respective amounts in weight is lower than 40 ⁇ .
  • 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.
  • alloys according to 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 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 comprises 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 by more than 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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EP19169009.8A 2018-04-12 2019-04-12 Anlaufbeständige 14k-goldlegierung und herstellungsverfahren davon Active EP3553192B1 (de)

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CH00465/18A CH714882B1 (it) 2018-04-12 2018-04-12 Lega d'oro a 14K resistente al tarnishing e metodo di produzione della medesima.
IT102018000004444A IT201800004444A1 (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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CN112210686A (zh) * 2020-09-18 2021-01-12 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
CN115612887A (zh) * 2022-08-12 2023-01-17 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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112210686A (zh) * 2020-09-18 2021-01-12 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
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
CN115612887A (zh) * 2022-08-12 2023-01-17 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
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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