WO2014108848A1 - Composition d'alliage maître pour la production d'alliages d'or blanc et alliage d'or blanc ainsi obtenu - Google Patents

Composition d'alliage maître pour la production d'alliages d'or blanc et alliage d'or blanc ainsi obtenu Download PDF

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Publication number
WO2014108848A1
WO2014108848A1 PCT/IB2014/058150 IB2014058150W WO2014108848A1 WO 2014108848 A1 WO2014108848 A1 WO 2014108848A1 IB 2014058150 W IB2014058150 W IB 2014058150W WO 2014108848 A1 WO2014108848 A1 WO 2014108848A1
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WIPO (PCT)
Prior art keywords
master alloy
rhodium
alloy composition
nickel
white gold
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Application number
PCT/IB2014/058150
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English (en)
Inventor
Massimo Poliero
Andrea Basso
Original Assignee
Legor Group S.P.A.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Legor Group S.P.A. filed Critical Legor Group S.P.A.
Publication of WO2014108848A1 publication Critical patent/WO2014108848A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • 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
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/05—Alloys based on copper with manganese as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent

Definitions

  • the present invention refers to a master alloy composition for producing gold, specifically white gold, alloy.
  • the present invention concerns a master alloy composition for producing gold, specifically white gold, alloy, mainly used to produce precious jewelry, goldsmith, costume jewelry objects (for instance jewels), as well as coins, medals, frames, swatches and so on.
  • a gold, specifically white gold, alloy including the aforesaid master alloy composition and used to produce precious objects, preferably through micro-casting o mechanical working processes.
  • a “carat” is equivalent to one part of gold on a total of 24 parts of metal constituting the alloy.
  • Such a measure unit is often abbreviated with the acronym formed by the letter “k” directly flanked e subsequent to the number.
  • the wording "18 carats” (18k) specifically indicates that the alloy consists of 18 parts of fine gold and 6 parts of other metals (which form the so-called master alloy), while the wording "14 carats” (14k) indicates that the alloy is composed of 14 parts of fine gold and 10 parts of other metals that make up the master alloy.
  • the highest fineness gold is therefore 24 carats (24 parts of "fine” gold on 24 total ones) and is denoted by the abbreviation 24k.
  • White gold is produced by inserting in the alloy (master alloy + fine gold) some whitening effect metals, i.e. having the ability to undo the typical yellow colour of gold.
  • the whitening effect metal currently most used is nickel which, in addition to possess high whitening properties, is commercially available at a relatively modest cost.
  • the European Union has recently issued a revision of the regulations EN1811, whose entry into force will become final starting from the next April 1 st , 2013; such a revision of the standard EN1811, named EN1811:2011 and published on April 21 st , 2011, will result in deep changes of the use of nickel in jewelry and in the world of costume jewelry.
  • the limits of nickel release remain nominally unchanged (0.5 g/cm 2 /week for articles in contact with the skin; 0.2g/cm 2 /week for objects introduced into pierced parts of the body)
  • the values of release of nickel actually determined must not exceed the values of 0.28 and 0.11 g/cm 2 /week respectively.
  • the new standard EN1811:2011 de facto causes the reduction of the maximum release limit of about 18 times the maximum release limit allowed by the previous version of the standard.
  • the master alloy used to make a white gold alloy with variable carat include about 23.33 ⁇ 43.33% of copper, about 23.33 ⁇ 43.33% of nickel, about 3.33 ⁇ 23.33% of zinc and about 10 ⁇ 30% of silver; another embodiment of a master alloy used to make a white gold alloy with variable carat will include about 43.33 ⁇ 66% of copper, about 8 ⁇ 39.33% of nickel and about 4.67 ⁇ 36.67% of zinc.
  • the present invention starting from the information on the drawbacks and deficiencies of the prior art as well as the restrictions imposed by the standard EN1811:2011, intends to meet these requirements and gives remedy to the current situation.
  • the present invention addresses the problem, which appears to be unsolved or solved in a not yet complete and satisfactory manner by the previous technical solutions, to produce a master alloy composition for the production of gold, specifically white gold alloys, and the resulting white gold alloy obtained with it
  • main purpose of the present invention is to provide a master alloy composition for the production of gold, specifically white gold, alloys which, comprising rhodium, achieves all the purposes set forth above.
  • the Applicant has, indeed, surprisingly discovered that rhodium possesses remarkable whitening properties and is, also, in particular provided with the ability to drastically reduce the release (emission or disposal) values of nickel when the alloy master that comprises them is inserted in nickel-based white gold alloys.
  • the present invention provides a master alloy composition for the production of white gold alloys and a white gold alloy, respectively according to the appended claims 1 and 11, as hereinafter referred for the sake of exhibition brevity.
  • the present invention also provides the use of rhodium as whitening metal in the production of a master alloy composition for the production of white gold alloys and the use of rhodium as whitening metal in white gold alloys respectively according to the appended claims 13 and 14, as hereinafter referred for the sake of exhibition brevity.
  • a first object of the invention possibly independent and usable autonomously in relation to the other aspects of the invention, a master alloy composition for the production of white gold alloys including rhodium as metal provided with high whitening properties.
  • a white gold alloy obtained by a master alloy composition comprising rhodium as metal with high whitening properties and also able to drastically reduce the values of nickel release in conditions of use, in case in which the whitening metal of group 10 of the periodic elements table belonging to the master alloy concerned is nickel.
  • FIG. 1 is a chart comparing the whitening power of rhodium (Rh), nickel (Ni), palladium (Pd) and gallium (Ga) in 750%o (18k) white gold alloys;
  • FIG. 2 shows the optical microscope image (200x) of the crystalline grain of a reference 750%o gold alloy of known type ("REF.” alloy: 17% by weight of nickel in the master alloy composition);
  • FIG. 3 shows the optical microscope image (200x) of the crystalline grain on a first 750%o white gold alloy ("A" alloy: 11% by weight of nickel and 1.5% by weight of rhodium in the master alloy composition) according to the present invention
  • FIG. 4 shows the optical microscope image (200x) of the crystalline grain on a second 750%o white gold alloy ("B" alloy: 11% by weight of nickel and 3% by weight of rhodium in the master alloy composition) according to the present invention
  • FIG. 5 shows the optical microscope image (200x) of the crystalline grain on a third 750%o white gold alloy ("C" alloy: 11% by weight of nickel and 4.5% by weight of rhodium in the master alloy composition) according to the present invention.
  • the present invention is based firstly on the surprising discovery of the significant whitening properties of rhodium (Rh) and, secondly, of its ability to drastically reduce the release values of nickel (Ni) when it is inserted into master alloy compositions containing precisely nickel (as whitening base metal) for white gold alloys.
  • Rhodium (chemical symbol Rh, atomic number 45, atomic weight 102.9) is a metal of extremely white color, the whitest after the silver, with a melting point of around 1,964°C; rhodium is, as known, a noble metal belonging to the so-called “platinum group” (Platinum Group Metals , PGMs).
  • Rhodium has very high stability to corrosion, in general protecting the less noble metals from the chemical reactions with the environment (such as "tarnishing", corrosion in humid environment, etc.).
  • the present invention reveals that the rhodium possesses quite high whitening properties and, however, higher or comparable to those ones possessed by the other whitening elements used for the production of white gold, while not presenting the complications of the latter.
  • rhodium in jewelry has been known for a very long time; it is, indeed, commonly applied as galvanic surface laying in order to give white gold and silver objects a particularly white, bright, with high corrosion and "tarnishing" resistance protective deposit, properties that are stable over time.
  • the chart shown in figure 1 highlights the whitening power of rhodium in 750%o white gold alloys in comparison to the other whitening metallic elements nowadays normally and predominantly utilized for the production of white gold, such as nickel, palladium and gallium.
  • Whitening power is expressed through an index called Yellowness Index (YI), the determination of which is derived from the calculation based on the use of the coordinates of the CIELab colorimeter model.
  • YI Yellowness Index
  • the white gold alloy presents a white color which does not require additional rhodium-plating treatments ("premium white”); if the value of YI lies between 19 and 24.5, the white gold alloy belongs to the category "standard white” and may be necessary, although not essential, a rhodium-plating treatment; if the value of YI exceeds 24.5, the white gold alloy belongs to the category "off white” and it is necessary a final rhodium-plating treatment.
  • the white gold alloys containing rhodium according to the present invention possess very high stability to atmospheric agents, with absence of the effects of yellowing which can be observed in case of white gold alloys containing gallium which, while possessing high whitening properties, yellows quickly when in contact with air, with the obvious negative aspect that this entails.
  • a first alloy of the invention (indicated with “A” and shown in figure 3) contains 11% by weight of nickel and 1.5% by weight of rhodium in the master alloy composition;
  • a second alloy of the invention (indicated with “B” and shown in figure 4) contains 11% by weight of nickel and 3% by weight of rhodium in the master alloy composition;
  • a third alloy of the invention (indicated with “C” and shown in figure 5) contains 11% by weight of nickel and 4.5% by weight of rhodium in the master alloy composition, and
  • a fourth alloy (indicated by "D") , contains 15% by weight of nickel, 3% by weight of gallium and 1% by weight of rhodium in the master alloy composition.
  • master alloy composition "C” (containing 4.5% by weight of rhodium) has a white shade comparable to the reference alloy called “REF.” alloy, but the latter uses a content of 17% by weight of nickel (i.e. 54% higher) compared to 11% by weight of nickel in the master alloy composition "C".
  • the rhodium advantageously acts as an element for homogenization of zinc which, if provided, is the less noble element in a gold alloy.
  • Table III shows also the distribution of zinc in alloy detected by casual (random) observations carried out on the surface through microanalysis (SEM/EDX); it is possible to observe how the variability of the composition (expressed as standard deviation, SD) progressively decreases with the increase of the percentage of rhodium in the white gold alloy.
  • a first alloy according to the invention (indicated by “E"), contains 13.5% by weight of nickel and 1.2% by weight of rhodium in the master alloy composition,
  • a second alloy according to the invention (indicated by "F"), contains 13.5% by weight of nickel and 2.4% by weight of rhodium in the master alloy composition,
  • a third alloy (indicated by "G") contains 13.5% by weight of nickel and 3.6% by weight of rhodium in the master alloy composition.
  • the following table VII compares the crystalline grain dimensions of the 750%o (18k) alloys H, I and J of the invention, with respective master alloy compositions shown in the previous table VII.
  • master alloy compositions are substantially copper (Cu) and rhodium (Rh) based and have whitening base metals alternative to nickel (Ni).
  • a master alloy composition for white gold alloys comprising:
  • one or more whitening base metals in overall percentage in the range between 1% and 60% by weight, selected from one or more of the metals of the group consisting of nickel, palladium, platinum, silver, zinc, manganese and gallium;
  • rhodium is a metallic whitening component (adjuvant the whitening base metal, or whitening base metals, in the whitening action).
  • the master alloy composition of the invention includes a single whitening base metal (for example a metal of group 10 of the periodic table of the elements).
  • the whitening base metal of the master alloy composition of the invention is nickel (Ni), in which case rhodium (Rh) is also advantageously able to reduce the release of nickel (Ni) in contact with the skin of the person wearing the jewel of jewelry and/or goldsmiths obtained through the corresponding white gold alloy comprising such a specific master alloy composition.
  • the weight percentage of nickel (Ni) is in the range between 4% and 60% and it is, for example, equal to 11% in case of 750%o (18k) white gold alloys, or it is equal to 13.5% in case of 585%o (14k) white gold alloys.
  • nickel -free master alloy compositions depicted of nickel
  • the master alloy composition includes a single whitening base metal different from nickel, however, selected from the group of whitening metals consisting of palladium, platinum, silver, zinc, manganese and gallium. It should be, also, understood that in other optional embodiments, here not highlighted by explanatory examples, the master alloy composition of the invention could include a plurality of simultaneously whitening base metals different each other, combined in appropriate respective amount by weight.
  • the master alloy composition of the invention could thus include, as whitening base metals, the following alternatives:
  • one or more metals of group 10 of the periodic table of elements such as nickel (Ni), palladium (Pd) and platinum (Pt) and, in addition, one or more metals of the group consisting of silver (Ag), manganese (Mn), gallium (Ga) and zinc (Zn);
  • At least two metals selected from the group consisting of silver (Ag), manganese (Mn), gallium (Ga) and zinc (Zn).
  • the percentage by weight of rhodium (Rh) is in the range between 1.2 % and 4.5%, while the percentage by weight of copper (Cu) is preferably, but not necessarily, in the range between 72% and 78%.
  • the whitening base metal is also or only palladium (Pd), it is added in a percentage by weight preferably in the range between 4% and 60%.
  • the percentage by weight with which it is added is preferably in the range between 4% and 30%.
  • the percentage by weight of zinc (Zn) in the master alloy composition is equal to 12% in case of 750%o (18k) white gold alloys, or is equal to 7.5% in case of 585%o (14k) white gold alloys.
  • the master alloy composition for the production of white gold alloys, object of the invention includes also or only silver (Ag) as a whitening base metal, it is added in a weight percentage in the range between 2% and 40%.
  • the whitening base metal of the master alloy composition of the invention is also or only manganese (Mn), it is added in a percentage by weight preferably in the range between 1% and 15%.
  • the master alloy composition of the invention includes also or only gallium (Ga) as a whitening base metal, it is added in a weight percentage in the range between 1% and 2%.
  • Ga gallium
  • a 750%o (18k) white gold alloy comprising the above mentioned preferred master alloy composition confers a Yellowness Index in the range between 25 and 30.
  • the aforesaid master alloy composition advantageously allows a quite limited nickel release, in the range between 0.025 and 0.01 ⁇ g/cm 2 /week by the white gold alloy that uses it, in use condition, significantly lower than that one associated with similar nickel-based white gold alloys available nowadays on the market, with the obvious advantages that this entails for people.
  • the aforesaid master alloy composition allows to get a crystalline grain between 16 ⁇ 4 ⁇ and 32 ⁇ 9 ⁇ in the 750 %o white gold alloy, much finer than that one of equivalent nickel- based white gold alloys of the known technique.
  • Integral part of the present invention is, as mentioned, also a white gold alloy comprising: - gold (Au): 333,33 %o (8k) ⁇ 958.33%o (23k) by weight;
  • the aforementioned white gold alloy of the invention provides that the metals of the master alloy composition are bonded together at the production factory of a given supplier company in order to form an intermediate, separated and distinct, compound which is subsequently combined to fine gold (Au), in order to get the final alloy or, more frequently, at the production factory of another company utilizing the master alloy composition produced by the supplier company.
  • the metals of the master alloy composition are bonded directly to gold (Au) during the production phase of the final gold alloy, i.e. without the creation of an intermediate compound, at the production factory of a single well-defined company.
  • Au gold
  • Another aspect of the invention concerns the use of rhodium (Rh) as a whitening metal in the production of a master alloy for the production of white gold alloys as described above.
  • a further aspect of the present invention concerns the use of rhodium (Rh) as a whitening metal in a white gold alloy as described above.
  • a last but not least aspect of the current invention concerns the use of rhodium (Rh) as a whitening metal and is able advantageously to reduce the release of nickel (Ni) in a white gold alloy as just identified above, as well as, according to a further aspect of the invention, to homogenize the distribution of zinc (Zn) in such a white gold alloy.
  • Rh rhodium
  • Ni nickel
  • Zn zinc
  • the master alloy composition for the production of white gold alloys the white gold alloy using such a master alloy composition and the uses of the present invention achieve the purposes and reach the advantages mentioned previously.
  • the master alloy composition (or the relative white gold alloy) of the invention may also comprise one or more of the refining elements, added in quantity lower than 1%, traditionally provided for these industrial products, such as germanium (Ge), indium (In), tin (Sn), iridium (Ir), ruthenium (Ru) and rhenium (Re).
  • the refining elements added in quantity lower than 1%, traditionally provided for these industrial products, such as germanium (Ge), indium (In), tin (Sn), iridium (Ir), ruthenium (Ru) and rhenium (Re).
  • the master alloy composition (or the related white gold alloy) of the invention may also comprise one or more of the deoxidizing elements, added in quantities in the order of 0.01 ⁇ 2.5%, traditionally provided for these industrial products, such as silicon (Si), boron (B), lithium (Li) and phosphorus (P).
  • the deoxidizing elements added in quantities in the order of 0.01 ⁇ 2.5%, traditionally provided for these industrial products, such as silicon (Si), boron (B), lithium (Li) and phosphorus (P).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Adornments (AREA)
  • Materials For Medical Uses (AREA)

Abstract

La présente invention concerne une composition d'alliage maître destinée à la production d'alliages d'or, plus particulièrement d'alliages d'or blanc, utilisée principalement pour produire des objets précieux, ladite composition d'alliage maître comprenant du rhodium (Rh) utilisé comme constituant de couche blanche et susceptible de réduire les valeurs de libération de nickel lors de l'insertion du rhodium (Rh) dans des alliages maîtres contenant du nickel.
PCT/IB2014/058150 2013-01-11 2014-01-09 Composition d'alliage maître pour la production d'alliages d'or blanc et alliage d'or blanc ainsi obtenu WO2014108848A1 (fr)

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ITPD2013A000002 2013-01-11
IT000002A ITPD20130002A1 (it) 2013-01-11 2013-01-11 Composizione di lega madre per la produzione di leghe di oro bianco e lega di oro bianco così ottenuta

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016151228A1 (fr) 2015-03-23 2016-09-29 Centre National De La Recherche Scientifique Alliage monophasique d'or et de tungstene
ITUB20153998A1 (it) * 2015-09-29 2017-03-29 Progold S P A Madreleghe per la realizzazione di leghe di oro a titolo 14 carati di colore rosso russia
IT201900011781A1 (it) * 2019-07-15 2021-01-15 Metaltech S R L Lega madre per la realizzazione di leghe di metalli preziosi e lega d’oro comprendente tale lega madre
IT202200009575A1 (it) * 2022-05-10 2023-11-10 Metaltech S R L Lega madre per la realizzazione di leghe di un metallo prezioso e lega di oro bianco

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JP2002256360A (ja) * 2001-03-01 2002-09-11 Ijima Kingin Kogyo Kk 白色金合金
EP1266974A1 (fr) * 2001-05-30 2002-12-18 Leg.Or S.r.l Alliages d'or et alliages-mères pour leur obtention
US20050100471A1 (en) * 2002-09-13 2005-05-12 Taylor Arthur D. White gold alloy
EP2045343A1 (fr) 2007-09-27 2009-04-08 Legor Group S.r.l. Alliages pour joaillerie pour fabriquer des bijoux en or blanc sans nickel
US20090317291A1 (en) * 2008-06-20 2009-12-24 Annette Gertge Variable karat gold alloys
US20090317292A1 (en) 2008-06-20 2009-12-24 Gertge Annette T Variable karat gold alloys

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JP2002256360A (ja) * 2001-03-01 2002-09-11 Ijima Kingin Kogyo Kk 白色金合金
EP1266974A1 (fr) * 2001-05-30 2002-12-18 Leg.Or S.r.l Alliages d'or et alliages-mères pour leur obtention
US20050100471A1 (en) * 2002-09-13 2005-05-12 Taylor Arthur D. White gold alloy
EP2045343A1 (fr) 2007-09-27 2009-04-08 Legor Group S.r.l. Alliages pour joaillerie pour fabriquer des bijoux en or blanc sans nickel
US20090317291A1 (en) * 2008-06-20 2009-12-24 Annette Gertge Variable karat gold alloys
US20090317292A1 (en) 2008-06-20 2009-12-24 Gertge Annette T Variable karat gold alloys

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Title
RAINER SÜSS, ELMA VAN DER LINGEN, LIZELLE GLANER, MADELEINE DU TOIT: "18 Carat Yellow Gold Alloys with Increased Hardness", GOLD BULLETIN, vol. 37, no. 3-4, 1 September 2004 (2004-09-01), Springer-Verlag, pages 196 - 207, XP002713239, ISSN: 0017-1557, DOI: 10.1007/BF03215213 *
RAINER SUSS; ELMA VAN DER LINEN; LIZELLA GLEANER; MADELEINE DU TOOT: "Gold Bulletin", vol. 37, 1 September 2004, SPRINGER-VERILOG, article "18 Carat Yellow Gold Alloys with Increased Hardness", pages: 196 - 207

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016151228A1 (fr) 2015-03-23 2016-09-29 Centre National De La Recherche Scientifique Alliage monophasique d'or et de tungstene
US10364481B2 (en) 2015-03-23 2019-07-30 Centre National De La Recherche Scientifique (Cnrs) Single-phase alloy of gold and tungsten
ITUB20153998A1 (it) * 2015-09-29 2017-03-29 Progold S P A Madreleghe per la realizzazione di leghe di oro a titolo 14 carati di colore rosso russia
IT201900011781A1 (it) * 2019-07-15 2021-01-15 Metaltech S R L Lega madre per la realizzazione di leghe di metalli preziosi e lega d’oro comprendente tale lega madre
IT202200009575A1 (it) * 2022-05-10 2023-11-10 Metaltech S R L Lega madre per la realizzazione di leghe di un metallo prezioso e lega di oro bianco

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