EP2546371B1 - Or gris 18 carats - Google Patents

Or gris 18 carats Download PDF

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Publication number
EP2546371B1
EP2546371B1 EP12176002.9A EP12176002A EP2546371B1 EP 2546371 B1 EP2546371 B1 EP 2546371B1 EP 12176002 A EP12176002 A EP 12176002A EP 2546371 B1 EP2546371 B1 EP 2546371B1
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EP
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Prior art keywords
gold
alloy
essentially
composition
component
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EP12176002.9A
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German (de)
English (en)
French (fr)
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EP2546371A1 (fr
Inventor
Niklaus Baltzer
Thierry Copponnex
Kangping Huang Guo
Laurence Simonet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cendres and Metaux SA
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Cendres and Metaux SA
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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
    • 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 relates to an 18-carat white gold having a white color comparable to that of rhodium-plated gold and having good polishing ability for applications in jewelery, watchmaking, jewelery, or for writing instruments.
  • 18ct white gold alloys also known as white gold usually consist of gold, copper and elements that have the power to whiten gold. These whitening elements are often found in group VIII of the periodic table of the elements, such as Ni, Pd, Co and Fe. The whitening effect of certain metals on gold has been the subject of studies since the 1970s. as described in reference 1: " Improvement of 18 carat white gold alloys ", GP O'Connor, Gold Bull 11, 2 (1978) ).
  • gray gold alloys are distinguished into two categories: palladium gold and nickel gold.
  • Nickel brings an interesting color and is economically advantageous, but its allergenic effect has almost proscribed luxury applications (jewelry, watchmaking).
  • the Applicant has studied various metallurgical systems in order to develop an 18-carat gray gold.
  • the alloys studied are based on the Au-Pd system with usual additive elements such as Ag, Ga, Zn, Sn, Fe and Rh, but without nickel and without copper. This is a classic composition for a jewelery alloy.
  • the whitest alloy obtained consists of 75% Au, 21% Pd, 2% Ag and 2% Rh.
  • Table 1 gives the colorimetric measurements on the L * a * b * scale, according to the CIE 1976 model, of different compositions of 18cts gray alloys on the market.
  • the value of the Yellowness Index (YI), or yellow index is also specified.
  • This parameter is commonly used to characterize the white color of an alloy (What is a white gold? Progress on the issues! Dr. Christopher W. Corti, Santa Fe Symposium Proceedings, May 2005 ).
  • the World Gold Council has defined several grades of gray gold: Non-White (YI>32); Off-White (24.5 ⁇ YI ⁇ 32); Standard-White (19 ⁇ YI ⁇ 24.5); Premium-White (YI ⁇ 19).
  • the Applicant has also studied the development of a gray gold in the Au-In system.
  • it has studied the feasibility of industrial exploitation of the Au75In25 alloy as an alloy for jewelery.
  • Au75In25 is in the zone ( ⁇ ) which is an intermetallic phase (Au3In2).
  • Au3In2 an intermetallic phase
  • This alloy gives the alloy an extraordinarily white color, but its intermetallic structure gives it a very great fragility.
  • This alloy is unfortunately practically unusable.
  • the addition of elements like Sn, Al, Zn, Cr and Nb has also been considered in order to obtain 18-carat gold ternary alloys based on the Au-In system. It has been shown that the addition of an element comprising one of: Sn, Al, Zn, Cr and Nb, however, gives rise to either a loss of color or an inhomogeneous structure, and does not sufficiently improve the ductility of the alloy.
  • the whitening power of chromium on gold is a known feature which is cited in a number of publications such as reference 1, reference 2: " Mechanical properties of Au-Fe-Cr white gold, T. Suzuki, Y. Kaneko, S. Hashimoto, J. Japan Inst Metals, 67, No. 11 (2003) ); and reference 3: " White gold alloys for investment casting ", M. Poliero, Gold Technology, No. 31 (2001) ). From this observation, the plaintiff chose to direct her research towards the Au-Cr system.
  • the patent application WO2009 / 092920 also cites the use of Cr to whiten gold.
  • it discloses the combination of gold with a refractory metal of columns IVB, VB and VIB of the periodic table (including Cr), without specifying the contents of refractory element.
  • the patent application JPH0657356 discloses a decorative gold alloy containing, by weight, 75% Au, 15 to 24% of at least one of Fe and Cr, and 1 to 10% of Ni.
  • the alloy is subjected to a treatment at a temperature between 250 and 500 ° C with an oxidizing flame so as to obtain a color ranging from yellow, red, purple, blue, green to gray.
  • the whitening power of Cr has already been demonstrated, its use is limited because of its partial miscibility with gold. Indeed, if the limit of solubility of Cr in Au is exceeded, the alloy becomes inhomogeneous. The Cr precipitates present in the material deteriorate the polishing ability of the alloy, which then becomes unusable for an application in jewelery / watchmaking. The difficulty of developing a gray gold at Cr then consists in introducing additional alloying elements making it possible to increase the solubility of Cr in gold, without altering the white color.
  • An object of the present invention is to provide an 18-carat gray gold alloy free from the limitations of known gray gold.
  • Another object of the invention is to obtain an alloy of 18 carat gold of white color, in the mass, comparable to that of a gold rhodium, and having a good surface quality after a mirror polishing.
  • gray gold alloy comprising by weight: essentially 75% of gold; between 13% and 17% of Cr; between 5% and 10% of Pd; and between 1% and 5% Fe.
  • the alloy comprises by weight 75% Au, 17% Cr, and 8% Pd.
  • This alloy is characterized by a color L * a * b * having the component L * of about 82, the component a * of about 0.56 and the component b * of about 3.7.
  • the Cr composition is between 13% and 16%; the composition of the Pd is between 5% and 8%; and the composition of the Fe is between 1% and 4%.
  • the alloy comprises by weight essentially 75% Au, essentially 15% Cr, essentially 7% Pd, and essentially 3% Fe.
  • This alloy is characterized by a color The color L * a * b * with a component L * of about 82, a component a * of about 0.45 and a component b * of about 3.0 .
  • the present disclosure also relates to a timepiece, jewelery, jewelery or writing instrument, comprising at least one component made with the alloy of the invention.
  • This solution has the particular advantage over the prior art of obtaining an 18-carat gold alloy making it possible to produce compositions combining a color close to rhodium-plated gold and a polishing ability that makes it possible to produce jewelery pieces. watchmaking, jewelery, or writing instruments.
  • the good surface quality is directly related to the homogeneity of the alloy. If the alloy has a multiphase structure, inhomogeneities will appear on the surface of the mirror-polish.
  • an 18-carat white gold alloy comprising by weight: at least 75% gold; between 13% and 23% of Cr; between 2% and 12% of at least one element selected from: Pd, Fe, Ru, Pt, Co, Ga, Ge, Mn, V, Ni.
  • the composition of Cr may be between 15% and 20% and the composition of said at least one element chosen from: Pd, Fe, Ru, Pt, Co, Ga, Ge, Mn, V, Ni is between 5% and 10%.
  • the alloy comprises between 2% and 12% of Pd and at most 5% of at least one element chosen from Fe, Ru, Pt, Co, Ga, Ge and Mn.
  • the composition of the Cr can be between 13% and 18%.
  • the composition of the Pd can be between 5% and 10%.
  • the good surface quality is directly related to the homogeneity of the alloy. If the alloy has a multiphase structure, inhomogeneities will appear on the surface of the mirror-polish.
  • an 18-carat white gold alloy comprising by weight: at least 75% gold; between 13% and 23% of Cr; between 2% and 12% of at least one element selected from: Pd, Fe, Ru, Pt, Co, Ga, Ge, Mn, V, Ni.
  • the composition of Cr may be between 15% and 20% and the composition of said at least one element chosen from: Pd, Fe, Ru, Pt, Co, Ga, Ge, Mn, V, Ni is between 5% and 10%.
  • the alloy comprises between 2% and 12% of Pd and at most 5% of at least one element chosen from Fe, Ru, Pt, Co, Ga, Ge and Mn.
  • the composition of the Cr can be between 13% and 18%.
  • the composition of the Pd can be between 5% and 10%.
  • the alloy further comprises at most 1% of an element chosen from refining elements: Ir, Rh, Re, W, Mo, among the neutral elements: Nb, Ta, Ni, V , Ti, Zn, and among the deoxidizing elements: Zr, Si and B.
  • refining elements Ir, Rh, Re, W, Mo
  • neutral elements means elements that have no significant effect on the main characteristics of the alloy as described herein. above and including these neutral elements.
  • the 18-carat white gold alloy comprises by weight: at least 75% Au, essentially 17% Cr, and essentially 8% Pd.
  • the whitening effect of Pd is widely used in conventional 18K gray golds.
  • Cr having a significant solubility in Pd this element has been introduced as a secondary addition element in different proportions in order to improve the homogeneity of the material.
  • the use of this element makes it possible, in fact, to maintain high levels of Cr without altering the white color.
  • the polishing ability has been improved but is not optimal because Cr precipitates are sometimes present from the casting.
  • the most favorable composition contains essentially 17% Cr and essentially 8% Pd (see Table 2).
  • the Au-Cr-Pd-Fe system has also been studied.
  • Fe has indeed a high solubility in Cr and Pd at high temperature.
  • it is a known element for bleaching gold (see references 2 and 3).
  • the substitution of a few mass percents of Cr in favor of Fe has considerably improved the homogeneity of the material and thus the polishing ability, while maintaining a very interesting color.
  • the 18-carat white gold alloy comprises by weight: at least 75% gold; between 13% and 17% of Cr; between 5% and 10% of Pd; and between 1% and 5% Fe.
  • the Cr composition is between 13% and 16%; and the composition of the Pd is between 5% and 8%.
  • the gold alloy comprises by weight: at least 75% Au, essentially 15% Cr, and essentially 7% Pd and essentially 3% Fe. This latter alloy has the best compromise between color and polishing ability. .
  • Table 2 reports results of measurements on the L * a * b * scale according to the CIE 1976 model. and the Yellowness Index (YI), or yellow index, measured according to ASTM D-1925 for each of these alloys, as well as observations on the quality of the polishing.
  • Table 2 reports colorimetric measurements and observations on the polishing quality of four conventional gray gold alloys (Nos. 1 to 4) and seven examples of gold alloys according to the invention (Nos. 5 to 11). The compositions are expressed in% by weight.
  • the measurements have shown in particular that the alloy comprises by weight: at least 75% of gold; between 13% and 23% of Cr; between 2% and 12% of at least one element selected from: Pd, Fe, Ru, Pt, Co, Ga, Ge, Mn, V, Ni, is characterized by a yellow index being less than 10. a yellow index of less than 10 for the other alloys of the invention.
  • the color is in the mass of the alloy and can not be damaged by surface wear.
  • a color L * a * b * is measured with the L * component of about 82, the component a * d about 0.56 and the b * component about 3.7.
  • a color L * a * b * is measured with the L * component of about 82%. , the component a * of about 0.45 and the component b * of about 3.0.
  • compositions AuCr17Pd8 at least 75% Au, essentially 17% Cr, and essentially 8% Pd
  • AuCr15Pd7Fe3 at least 75% Au, essentially 15% Cr, essentially 7% Pd, and essentially 3% Fe
  • the composition containing Fe has the most promising characteristics for an application in the field of luxury (jewelery, watchmaking) because it combines both a very white color and good polishing ability.
  • Corrosion test results according to the dental standard were performed on seven alloys to evaluate the release rate (in ⁇ g / cm 2 x7d) of the ions of sensitive elements such as Ni and Cr (Table 3).
  • the ISO 10271-2001 standard limits the total release rate to 200 ⁇ g / cm 2 x 7d. According to these tests, the two alloys AuCr17Pd8 and AuCr15Pd7Fe have a very good resistance to corrosion.
  • Table 4 gives a summary of our studies in the Au-Cr-X and Au-Cr-Pd-Fe systems as well as the characteristics of the two preferred alloys.
  • X corresponds to at least one element chosen from: Pd, Fe, Ru, Pt, Co, Ga, Ge, Mn, V, Ni.
  • the study of the Au-Cr-Pd ternary system has made it possible to develop 18-carat alloys with a white color comparable to that of rhodium-plated gold.
  • the best composition corresponds to: at least 75% Au, essentially 17% Cr and essentially 8% Pd.
  • the Au-Cr-Pd-Fe quaternary system made 18cts alloys with even more attractive properties in terms of color, polishing ability, ductility and price.
  • the best composition corresponds to: at least: 75% Au, essentially 15% Cr, essentially 7% Pd and essentially 3% Fe.
  • Cr is introduced as the main bleaching element.
  • Pd and Fe are introduced to improve the solubility of chromium in gold, without altering the desired white color. Only the combination of the three elements of alloy Cr, Pd and Fe has made it possible to develop compositions combining a color close to rhodium-plated golds and a polishing ability allowing the production of pieces of jewelery, timepieces, jewelery, or jewelry. writing instruments.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
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EP12176002.9A 2011-07-12 2012-07-11 Or gris 18 carats Active EP2546371B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH11652011 2011-07-12

Publications (2)

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EP2546371A1 EP2546371A1 (fr) 2013-01-16
EP2546371B1 true EP2546371B1 (fr) 2016-12-21

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EP12176002.9A Active EP2546371B1 (fr) 2011-07-12 2012-07-11 Or gris 18 carats

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EP (1) EP2546371B1 (pt)
DK (1) DK2546371T3 (pt)
ES (1) ES2616542T3 (pt)
PT (1) PT2546371T (pt)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3020835B1 (fr) 2014-11-17 2021-04-21 Omega SA Pièce d'horlogerie, de bijouterie ou de joaillerie comportant un composant réalisé dans un alliage à base de palladium
EP3040790A1 (fr) 2014-12-29 2016-07-06 Montres Breguet S.A. Pièce d'horlogerie ou de bijouterie en alliage précieux léger à base de titane
EP3070182B1 (fr) 2015-03-17 2017-08-30 The Swatch Group Research and Development Ltd. Alliage d'or gris
EP3339455B1 (fr) 2016-12-20 2020-02-05 Montres Breguet S.A. Alliage d'or gris
EP3808865B1 (fr) 2019-10-17 2023-01-18 Richemont International S.A. Alliage d'or blanc et son procede de fabrication
CN115896527B (zh) * 2022-12-16 2024-05-03 深圳市华悦珠宝科技有限公司 一种16k金、弹簧的制作方法、弹簧及首饰

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0657356A (ja) * 1991-11-14 1994-03-01 Nippon Kogyo Ginkou:Kk 装飾用金合金
DE10027605A1 (de) 2000-06-06 2001-12-20 Hafner C Gmbh & Co Weißgold-Legierungen
JP2002256360A (ja) * 2001-03-01 2002-09-11 Ijima Kingin Kogyo Kk 白色金合金
FR2923492A1 (fr) 2007-11-12 2009-05-15 Gerard Bienvenu Alliages d'or massif, de couleur blanche, eclatante dans toute la masse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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PT2546371T (pt) 2017-02-14
ES2616542T3 (es) 2017-06-13
DK2546371T3 (en) 2017-04-03
EP2546371A1 (fr) 2013-01-16

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