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EP1245688B1 - Grey-coloured gold alloy, without nickel - Google Patents

Grey-coloured gold alloy, without nickel Download PDF

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Publication number
EP1245688B1
EP1245688B1 EP02005157A EP02005157A EP1245688B1 EP 1245688 B1 EP1245688 B1 EP 1245688B1 EP 02005157 A EP02005157 A EP 02005157A EP 02005157 A EP02005157 A EP 02005157A EP 1245688 B1 EP1245688 B1 EP 1245688B1
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European Patent Office
Prior art keywords
alloy
nickel
weight
grey
gold alloy
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Expired - Lifetime
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EP02005157A
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German (de)
French (fr)
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EP1245688A2 (en
EP1245688A3 (en
Inventor
Denis Vincent
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Metalor Technologies International SA
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Metalor Technologies International 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
    • 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

Definitions

  • the present invention relates to a gold alloy nickel free gray comprising 75-76% by weight of Au.
  • the nickel allergy problem has leads to the limitation, even to the total prohibition of the presence of nickel in white or gray gold alloys. In more, these alloys are excessively hard and not very deformable so they don't lend themselves well to work in the jewelry and watchmaking in particular.
  • CH-684 616 has already proposed a gold alloy nickel-free gray with good deformability, comprising generally in this case essentially between 15% and 17% by weight of Pd, between 3 and 5% of Mn and between 5 and 7% in Cu weight.
  • Pd is a very expensive metal and whose prices fluctuate enormously.
  • the lowering of the proportion of Pd, and the addition of Ag in the above-mentioned alloy leads to low deformability.
  • a percentage too high Ag causes tarnishing of the alloy.
  • JP-A-9078160 has also proposed a ternary gray gold alloy with more than 10% by weight of Pd and more than 10% by weight of Cu.
  • a ternary alloy does not in particular the molding properties, allowing its use with the technique known as lost wax.
  • JP-A-10 245646 relates to a gold alloy containing 15.0-23.0% Cu and 0.3-5.0% Pd, especially an alloy containing 75% Au, 4.5% Ag, 15% Cu and 5.5% Pd.
  • JP-A-60 258435 offers a gold alloy containing 4-7% Pd, 15-30% Cu, 5-25% Ag, especially an alloy containing 75% Au, 5.0% Ag, 15% Cu and 5.0% Pd.
  • the object of the present invention is to substantially improve white or gray gold alloys allowing reduce the proportion of Pd without reducing its properties deformability, as well as its metallurgical properties allowing it to be used in casting techniques by lost wax.
  • this invention relates to an alloy white gold or gray gray nickel free according to claim 1.
  • Some other items are added to the items main of this alloy, to improve its properties metallurgical, in particular to lower its temperature melting, improving the fineness of grain as well as for avoid porosities.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Adornments (AREA)
  • Dental Preparations (AREA)
  • Silicon Compounds (AREA)
  • Powder Metallurgy (AREA)

Description

La présente invention se rapporte à un alliage d'or gris sans nickel comprenant 75-76% en poids d'Au.The present invention relates to a gold alloy nickel free gray comprising 75-76% by weight of Au.

Le problème lié à l'allergie provoquée par le nickel a conduit à la limitation, voire à l'interdiction totale de la présence de nickel dans les alliages d'or blanc ou gris. En plus, ces alliages sont excessivement durs et peu déformables de sorte qu'ils se prêtent mal au travail dans le domaine de la bijouterie et de l'horlogerie en particulier.The nickel allergy problem has leads to the limitation, even to the total prohibition of the presence of nickel in white or gray gold alloys. In more, these alloys are excessively hard and not very deformable so they don't lend themselves well to work in the jewelry and watchmaking in particular.

On a déjà proposé dans le CH-684 616 un alliage d'or gris sans nickel présentant une bonne déformabilité, comprenant généralement dans ce cas essentiellement entre 15% et 17% en poids de Pd, entre 3 et 5% de Mn et entre 5 et 7% en poids de Cu. Le Pd est un métal très cher et dont les cours fluctuent énormément. L'abaissement de la proportion de Pd, et l'adjonction d'Ag dans l'alliage susmentionné conduit à une faible déformabilité. En outre, un pourcentage trop élevé d'Ag provoque un ternissement de l'alliage.CH-684 616 has already proposed a gold alloy nickel-free gray with good deformability, comprising generally in this case essentially between 15% and 17% by weight of Pd, between 3 and 5% of Mn and between 5 and 7% in Cu weight. Pd is a very expensive metal and whose prices fluctuate enormously. The lowering of the proportion of Pd, and the addition of Ag in the above-mentioned alloy leads to low deformability. In addition, a percentage too high Ag causes tarnishing of the alloy.

On a proposé par ailleurs dans le JP-A-9078160 un alliage d'or gris ternaire avec plus de 10% en poids de Pd et plus de 10% en poids de Cu. Un tel alliage ternaire ne présente pas les propriétés de moulage notamment, permettant son utilisation avec la technique dite de la cire perdue.JP-A-9078160 has also proposed a ternary gray gold alloy with more than 10% by weight of Pd and more than 10% by weight of Cu. Such a ternary alloy does not in particular the molding properties, allowing its use with the technique known as lost wax.

Le JP-A-10 245646 se rapporte à un alliage d'or contenant 15,0-23,0% Cu et 0,3-5,0% Pd, notamment un alliage contenant 75% Au, 4,5% Ag, 15% Cu et 5,5% Pd. Le JP-A-60 258435 propose un alliage d'or contenant 4-7% Pd, 15-30% Cu, 5-25% Ag, notamment un alliage contenant 75% Au, 5,0% Ag, 15% Cu et 5,0% Pd. JP-A-10 245646 relates to a gold alloy containing 15.0-23.0% Cu and 0.3-5.0% Pd, especially an alloy containing 75% Au, 4.5% Ag, 15% Cu and 5.5% Pd. JP-A-60 258435 offers a gold alloy containing 4-7% Pd, 15-30% Cu, 5-25% Ag, especially an alloy containing 75% Au, 5.0% Ag, 15% Cu and 5.0% Pd.

Le but de la présente invention est d'améliorer substantiellement les alliages d'or blanc ou gris en permettant de réduire la proportion de Pd sans réduire ses propriétés de déformabilité, ainsi que ses propriété métallurgiques permettant de l'utiliser dans les techniques de coulée par cire perdue.The object of the present invention is to substantially improve white or gray gold alloys allowing reduce the proportion of Pd without reducing its properties deformability, as well as its metallurgical properties allowing it to be used in casting techniques by lost wax.

A cet effet, cette invention a pour objet un alliage d'or blanc ou gris gris sans nickel selon la revendication 1.To this end, this invention relates to an alloy white gold or gray gray nickel free according to claim 1.

Il a été constaté de manière surprenante qu'il était possible de limiter, voire de réduire de manière importante la proportion de Pd sans nuire ni à la blancheur de l'alliage ni à ses propriétés métallurgiques et mécaniques, qui peuvent même être améliorées, par une augmentation substantielle de la proportion de Cu. On a même pu constater que moins on met de Pd, plus on peut augmenter la proportion de Cu sans nuire à la couleur ni aux propriétés de déformabilité recherchées.It was surprisingly found that he was possible to significantly limit or even reduce the proportion of Pd without harming or whiteness of the alloy nor to its metallurgical and mechanical properties, which can even be improved, by a substantial increase of the proportion of Cu. We even saw that the less Pd, the more we can increase the proportion of Cu without affecting color or deformability properties sought.

En outre, on évite également d'incorporer des métaux ferreux pour que l'alliage puisse être utilisé avec des techniques de coulées classiques dans la bijouterie, l'horlogerie, ainsi que dans l'art de la prothèse dentaire, où l'on utilise la technique dite de la cire perdue qui est la plus avantageuse pour les petites séries voire la production de pièces uniques.In addition, it also avoids incorporating metals ferrous so that the alloy can be used with classic casting techniques in jewelry, watchmaking, as well as in the art of dentures where we use the technique known as lost wax which is the more advantageous for small series or even production unique pieces.

Certains autres éléments sont ajoutés aux éléments principaux de cet alliage, pour améliorer ses propriétés métallurgiques, en particulier pour abaisser sa température de fusion, améliorer la finesse de grain ainsi que pour éviter les porosités.Some other items are added to the items main of this alloy, to improve its properties metallurgical, in particular to lower its temperature melting, improving the fineness of grain as well as for avoid porosities.

L'invention sera décrite maintenant à l'aide d'une série d'exemples, axée sur une proportion se situant autour de 7% de Pd. Comme on pourra le constater, le rôle du cuivre est déterminant. La forte réduction de la teneur en Pd est en partie compensée par une adjonction d'Ag et Zn et une forte proportion de Cu.The invention will now be described using a series of examples, focused on a proportion around 7% Pd. As we can see, the role of copper is decisive. The large reduction in Pd content is partly offset by an addition of Ag and Zn and a high proportion of Cu.

Différents autres éléments sont incorporés dans des proportions faibles voire très faibles, pour améliorer les propriétés de l'alliage. On peut ajouter Ir et Re en tant qu'affineurs de grain, In permet d'abaisser le point de fusion. Cet abaissement du point de fusion présente une grande importance dans la coulée avec des moules classiques en SiO2 et plâtre de Paris, puisqu'il permet d'éviter la réaction entre les composants du moule et en particulier la production de SO2 qui empoisonne l'alliage d'or. Various other elements are incorporated in low or very low proportions, to improve the properties of the alloy. Ir and Re can be added as grain refiners, In lowers the melting point. This lowering of the melting point is of great importance in casting with conventional molds of SiO 2 and plaster of Paris, since it makes it possible to avoid the reaction between the components of the mold and in particular the production of SO 2 which poisons the 'gold alloy.

On peut encore ajouter, pour améliorer l'état de surface, l'un des éléments suivants: Ti, Zr, Nb, Si ou Ta, dans une proportion d'environ 100 ppm. Bien que l'on cherche à abaisser la température de fusion de l'alliage, comme on l'a expliqué ci-dessus, il s'agit d'une mesure supplémentaire de sécurité.We can also add, to improve the surface condition, one of the following: Ti, Zr, Nb, Si or Ta, in a proportion of approximately 100 ppm. Although we seek to lower the melting temperature of the alloy, as we have explained above, this is an additional measure of security.

Les exemples du tableau I qui va suivre, outre la composition des alliages donnée en % en poids, des indications relatives à la dureté de l'alliage à l'état moulé recuit et écroui sont données, ainsi qu'à la couleur mesurée dans un système de coordonnées à trois axes. Ce système'de mesure à trois dimensions dénommé CIELab, CIE étant le sigle de la Commission Internationale de l'Eclairage et Lab les trois axes de coordonnées, l'axe L mesurant la composante blanc-noir (noir = 0; blanc = 100), l'axe a mesurant la composante rouge-vert (rouge = +a vert = -a) et l'axe b mesurant la composante jaune-bleu (jaune = +b bleu = -b). Pour plus de détails sur ce système de mesure, on peut se reporter à l'article « The Colour of Gold-Silver-Copper Alloys » de R.M.German, M.M.Guzowski et D.C.Wright, Gold Bulletin 1980, 13, (3), pages 113-116.The examples in Table I which will follow, in addition to the composition alloys given in% by weight, indications relating to the hardness of the alloy in the annealed molded state and hardened are given, as well as to the color measured in a three-axis coordinate system. This measurement system three dimensions called CIELab, CIE being the acronym of the International Lighting Commission and Lab the three coordinate axes, the L axis measuring the white-black component (black = 0; white = 100), the axis a measuring the component red-green (red = + a green = -a) and the b axis measuring the yellow-blue component (yellow = + b blue = -b). For more than details on this measurement system, we can refer to the article "The Color of Gold-Silver-Copper Alloys" by R.M.German, M.M.Guzowski and D.C.Wright, Gold Bulletin 1980, 13, (3), pages 113-116.

Enfin, ce tableau indique encore dans les deux colonnes F, les intervalles de fusion exprimés en °C, ainsi que les pourcentages de déformation (% déf).Finally, this table still indicates in the two columns F, the melting intervals expressed in ° C, as well as the deformation percentages (% def).

On constate dans ce tableau qu'une trop forte proportion d'Ag augmente la valeur de b* (saturation en jaune). Pour ce type d'alliages, il est souhaitable que la valeur b* n'excède pas 13, de sorte que le pourcentage d'Ag est de préférence < 5%.

Figure 00050001
We see in this table that too high a proportion of Ag increases the value of b * (saturation in yellow). For this type of alloy, it is desirable that the value b * does not exceed 13, so that the percentage of Ag is preferably <5%.
Figure 00050001

Claims (6)

  1. Nickel-free white or grey gold alloy comprising, expressed by weight, Au 75-76%, Pd between 5 and 7%, between 10 and 17% Cu, ≤ 4% Ag, < 7% Zn, the balance being formed by at least one of the elements Ir, In, Ta, Ti, Si, Ga, Re, Nb.
  2. Alloy according to Claim 1, containing at least one of the elements Ir, Ta, Si in a proportion of between 0.002 and 0.015% by weight.
  3. Alloy according to Claim 2 containing between 0.2 and 0.4% by weight Ga.
  4. Alloy according to claim 1 containing between 20 and 200 ppm Ti.
  5. Alloy according to Claim 1 containing 0.002% by weight Re.
  6. Alloy according to Claim 1 containing 2% by weight In.
EP02005157A 1998-12-14 1998-12-14 Grey-coloured gold alloy, without nickel Expired - Lifetime EP1245688B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02005157A EP1245688B1 (en) 1998-12-14 1998-12-14 Grey-coloured gold alloy, without nickel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP02005157A EP1245688B1 (en) 1998-12-14 1998-12-14 Grey-coloured gold alloy, without nickel
EP98811224A EP1010768B1 (en) 1998-12-14 1998-12-14 Grey-colored gold alloy, without nickel

Related Parent Applications (1)

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Publications (3)

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EP1245688A2 EP1245688A2 (en) 2002-10-02
EP1245688A3 EP1245688A3 (en) 2002-10-30
EP1245688B1 true EP1245688B1 (en) 2004-05-12

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US (2) US6342182B1 (en)
EP (2) EP1245688B1 (en)
JP (1) JP2000178669A (en)
DE (2) DE69812652T2 (en)
ES (2) ES2195300T3 (en)

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ES2220846T3 (en) 2004-12-16
ES2195300T3 (en) 2003-12-01
EP1010768A1 (en) 2000-06-21
EP1245688A2 (en) 2002-10-02
JP2000178669A (en) 2000-06-27
US6787102B2 (en) 2004-09-07
EP1245688A3 (en) 2002-10-30
EP1010768B1 (en) 2003-03-26
US6342182B1 (en) 2002-01-29
DE69812652T2 (en) 2004-04-29
DE69823891T2 (en) 2005-05-19
DE69823891D1 (en) 2004-06-17
DE69812652D1 (en) 2003-04-30
US20020127134A1 (en) 2002-09-12

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