EP1010768B1 - Grey-colored gold alloy, without nickel - Google Patents

Grey-colored gold alloy, without nickel Download PDF

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Publication number
EP1010768B1
EP1010768B1 EP98811224A EP98811224A EP1010768B1 EP 1010768 B1 EP1010768 B1 EP 1010768B1 EP 98811224 A EP98811224 A EP 98811224A EP 98811224 A EP98811224 A EP 98811224A EP 1010768 B1 EP1010768 B1 EP 1010768B1
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Prior art keywords
alloy
nickel
weight
grey
gold
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Expired - Lifetime
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EP98811224A
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German (de)
French (fr)
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EP1010768A1 (en
Inventor
Denis Vincent
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Metalor Technologies International SA
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Metalor Technologies International SA
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Priority to DE69823891T priority Critical patent/DE69823891T2/en
Priority to ES02005157T priority patent/ES2220846T3/en
Priority to EP02005157A priority patent/EP1245688B1/en
Priority to DE69812652T priority patent/DE69812652T2/en
Priority to ES98811224T priority patent/ES2195300T3/en
Priority to EP98811224A priority patent/EP1010768B1/en
Application filed by Metalor Technologies International SA filed Critical Metalor Technologies International SA
Priority to JP11354255A priority patent/JP2000178669A/en
Priority to US09/460,471 priority patent/US6342182B1/en
Publication of EP1010768A1 publication Critical patent/EP1010768A1/en
Priority to US10/054,571 priority patent/US6787102B2/en
Application granted granted Critical
Publication of EP1010768B1 publication Critical patent/EP1010768B1/en
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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 gray nickel free comprising 75-76% by weight of Au and between 12 and 14% by weight of Pd.
  • 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, the amounts of Pd and Cu preferably being the same, which means that the higher the the higher the Pd content, the higher the copper content and vice versa.
  • a ternary gray gold alloy with more than 10% by weight of Pd and more than 10% by weight of Cu, the amounts of Pd and Cu preferably being the same, which means that the higher the higher the Pd content, the higher the copper content and vice versa.
  • the respective contents of Pd and Cu can only be 12.5% respectively.
  • such a ternary alloy does not not in particular the molding properties, allowing its use with the technique known as lost wax.
  • JP 03 130 333 A has also proposed an alloy white gold comprising between 10 and 35% by weight of Pd to which is added Ga and In in order to improve the flowability properties and to make it easier to to work.
  • this alloy contains between 1 and 10% in weight of Ag intended to reduce the proportion of Pd.
  • the addition of Ag in such an alloy causes tarnishing of its color.
  • 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 nickel-free gray gold 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.
  • the table gives indications relating to the hardness of the alloy in the molded annealed and work-hardened state, as well as color measured in a three-axis coordinate system.
  • examples 2, 3, 4 show a relatively low deformability, so these alloys do not lend themselves to applications where good deformability is required.
  • Examples 4, 8, and 11 show saturation in yellow expressed by the value b * relatively high, compared to references and other alloys of the same category, i.e. including between 12 and 14% Pd.

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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 et entre 12 et 14% en poids de Pd.The present invention relates to a gold alloy gray nickel free comprising 75-76% by weight of Au and between 12 and 14% by weight of Pd.

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, les quantités de Pd et de Cu étant de préférence les mêmes, ce qui signifie que plus la teneur en Pd est élevée plus celle de cuivre augmente et inversement. Ceci revient à dire que pour un alliage 18ct, les teneurs respectives de Pd et de Cu ne peuvent être que de 12,5% respectivement. En outre 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, the amounts of Pd and Cu preferably being the same, which means that the higher the the higher the Pd content, the higher the copper content and vice versa. This amounts to saying that for an 18ct alloy, the respective contents of Pd and Cu can only be 12.5% respectively. Furthermore, such a ternary alloy does not not in particular the molding properties, allowing its use with the technique known as lost wax.

On a également proposé dans le JP 03 130 333 A un alliage d'or blanc comprenant entre 10 et 35% en poids de Pd auquel est ajouté du Ga et de l'In en vue d'améliorer les propriétés de coulabilité et pour le rendre plus facile à travailler. Toutefois cet alliage comporte entre 1 et 10% en poids d'Ag destinée à permettre de réduire 1a proportion de Pd. L'adjonction d'Ag dans un tel alliage provoque un ternissement de sa couleur.JP 03 130 333 A has also proposed an alloy white gold comprising between 10 and 35% by weight of Pd to which is added Ga and In in order to improve the flowability properties and to make it easier to to work. However, this alloy contains between 1 and 10% in weight of Ag intended to reduce the proportion of Pd. The addition of Ag in such an alloy causes tarnishing of its color.

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 gris sans nickel selon la revendication 1.To this end, this invention relates to an alloy nickel-free gray gold 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 series 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 13% de Pd. Comme on pourra le constater, le rôle du cuivre est déterminant. The invention will now be described using a series of examples, focused out of a proportion around 13% Pd. As we can see, the role of copper is decisive.

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 ajoute, 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 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.

Outre la composition des alliages donnée en % en poids, le tableau donne des indications relatives à la dureté de l'alliage à l'état moulé recuit et écroui, 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. In addition to the composition of the alloys given in% by weight, the table gives indications relating to the hardness of the alloy in the molded annealed and work-hardened state, as well as color measured in a three-axis coordinate system. This three-dimensional measurement system 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), axis a measuring the red-green component (red = + a green = -a) and axis b measuring the yellow-blue component (yellow = + b blue = -b). For more details on this measurement system, you can see 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 again indicates in the two columns F, the melting intervals expressed in ° C, as well than the deformation percentages (% def).

Dans le tableau, les exemples 2, 3, 4 présentent une déformabilité relativement faible, de sorte que ces alliages ne se prêtent pas à des applications où une bonne déformabilité est requise.In the table, examples 2, 3, 4 show a relatively low deformability, so these alloys do not lend themselves to applications where good deformability is required.

Les exemples 4, 8, et 11 présentent une saturation en jaune exprimée par la valeur b* relativement élevée, par rapport aux références et aux autres alliages de la même catégorie, c'est-à-dire comprenant entre 12 et 14% de Pd.Examples 4, 8, and 11 show saturation in yellow expressed by the value b * relatively high, compared to references and other alloys of the same category, i.e. including between 12 and 14% Pd.

Quant aux exemples 2 et 6, on constate qu'ils sont relativement mous après coulée.As for examples 2 and 6, we see that they are relatively soft after casting.

Enfin, les exemples 1 à 3, 6, 7 9 et 13 sortent du champ de la présente invention.

Figure 00060001
Finally, Examples 1 to 3, 6, 7 9 and 13 are outside the scope of the present invention.
Figure 00060001

Claims (3)

  1. Nickel-free white gold alloy, intended in particular for the technique of lost-wax casting, containing, by weight, 75-76% gold and between 12 and 14% Pd, between 7 and 11% Cu, between 1 and 4% In and between 0.2 and 0.4% Ga, the balance being formed by a proportion of between 0.01 and 4% of at least one of the elements Ir, Re, Zn, Nb, Si, Ta, Ti.
  2. Alloy according to Claim 1, containing between 20 and 200 ppm Ti.
  3. Alloy according to Claim 1 or 2, containing, by weight, 13% Pd, 10% Cu, 1.5 In and 0.35% Ga.
EP98811224A 1998-12-14 1998-12-14 Grey-colored gold alloy, without nickel Expired - Lifetime EP1010768B1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP02005157A EP1245688B1 (en) 1998-12-14 1998-12-14 Grey-coloured gold alloy, without nickel
DE69812652T DE69812652T2 (en) 1998-12-14 1998-12-14 Gray gold alloy, without nickel
ES98811224T ES2195300T3 (en) 1998-12-14 1998-12-14 GRAY GOLD ALLOY WITHOUT NICKEL.
EP98811224A EP1010768B1 (en) 1998-12-14 1998-12-14 Grey-colored gold alloy, without nickel
DE69823891T DE69823891T2 (en) 1998-12-14 1998-12-14 Gray gold alloy, without nickel
ES02005157T ES2220846T3 (en) 1998-12-14 1998-12-14 GRAY GOLD ALLOY WITHOUT NICKEL.
JP11354255A JP2000178669A (en) 1998-12-14 1999-12-14 White gold alloy
US09/460,471 US6342182B1 (en) 1998-12-14 1999-12-14 Nickel-free grey gold alloy
US10/054,571 US6787102B2 (en) 1998-12-14 2001-11-12 Nickel-free grey gold alloy

Applications Claiming Priority (1)

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

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EP1010768A1 EP1010768A1 (en) 2000-06-21
EP1010768B1 true EP1010768B1 (en) 2003-03-26

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ES2220846T3 (en) 2004-12-16
JP2000178669A (en) 2000-06-27
ES2195300T3 (en) 2003-12-01
DE69823891T2 (en) 2005-05-19
EP1245688B1 (en) 2004-05-12
EP1245688A2 (en) 2002-10-02
US20020127134A1 (en) 2002-09-12
DE69812652T2 (en) 2004-04-29
DE69812652D1 (en) 2003-04-30
EP1010768A1 (en) 2000-06-21
US6342182B1 (en) 2002-01-29
US6787102B2 (en) 2004-09-07
DE69823891D1 (en) 2004-06-17
EP1245688A3 (en) 2002-10-30

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