EP1227166B1 - Grey gold alloy - Google Patents

Grey gold alloy Download PDF

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Publication number
EP1227166B1
EP1227166B1 EP01810074A EP01810074A EP1227166B1 EP 1227166 B1 EP1227166 B1 EP 1227166B1 EP 01810074 A EP01810074 A EP 01810074A EP 01810074 A EP01810074 A EP 01810074A EP 1227166 B1 EP1227166 B1 EP 1227166B1
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Prior art keywords
gold alloy
weight
alloy
grey gold
free
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EP01810074A
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German (de)
French (fr)
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EP1227166A1 (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 EP01810074A priority Critical patent/EP1227166B1/en
Priority to DE60141941T priority patent/DE60141941D1/en
Priority to AT01810074T priority patent/ATE466115T1/en
Publication of EP1227166A1 publication Critical patent/EP1227166A1/en
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Classifications

    • 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
    • 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
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold

Abstract

A grey gold alloy without nickel, cobalt, iron and silver comprises, by weight: (a) Au : 75 to 76 %; (b) Cu ≥ 17 %; (c) Mn less than 7 %; (d) Zn ≤ 2 %. This gold alloy may also contain, by weight: (a) Si ≤ 0.5 %; (b) at least one of the elements Ti less than 0.3 % or Ta less than 0.3 %; (c) 0 % Pd and at most 2 % Pt.

Description

La présente invention se rapporte à un alliage d'or gris sans nickel, sans cobalt, sans fer et sans argent.The present invention relates to a nickel-free, cobalt-free, iron-free and non-silver-free gray alloy.

Il existe sur le marché principalement deux sortes d'alliages d'or gris, les alliages dans lesquels le métal de blanchiment de l'or est le nickel et ceux où ce métal est le palladium.There are mainly two types of white gold alloys on the market, the alloys in which the gold bleaching metal is nickel and those in which the metal is palladium.

Chacun de ces alliages présente cependant des inconvénients. Outre le fait que les alliages au nickel produisent des allergies et sont proscrits pour cette raison, ils sont excessivement durs et peu déformables de sorte qu'ils se prêtent mal aux conditions de travail des bijoutiers et des fabricants de boîtes de montres, principaux utilisateurs de ces alliages. Les alliages au palladium sont par contre trop mous et en plus sont très chers compte tenu du prix du palladium et de la proportion substantielle qu'il en faut pour blanchir l'or.Each of these alloys, however, has disadvantages. In addition to the fact that nickel alloys produce allergies and are prohibited for this reason, they are excessively hard and not very deformable so that they do not lend themselves to the working conditions of jewelers and watchbox manufacturers, the main users of these alloys. On the other hand, palladium alloys are too soft and in addition are very expensive given the price of palladium and the substantial proportion that is needed to launder gold.

En plus des propriétés mécaniques de ces alliages et des problèmes d'allergies, un critère essentiel entre en ligne de compte, celui de la couleur et de l'éclat du métal.In addition to the mechanical properties of these alloys and allergy problems, an essential criterion comes into play, that of the color and brightness of the metal.

On a déjà proposé de remédier au problème du nickel en lui substituant du palladium et du manganèse, par exemple dans le CH 684 616 . On a également proposé dans le EP 1 010 768 un alliage d'or gris 18 carats comprenant de 5 à 14% en poids de Pd et entre 7 et 17% en poids de Cu, la proportion de Cu étant sensiblement inversement proportionnelle à celle de Pd, le reste étant formé de différents éléments destinés à améliorer les propriétés de l'alliage.It has already been proposed to remedy the nickel problem by replacing it with palladium and manganese, for example in the CH 684 616 . It has also been proposed in EP 1 010 768 an 18-carat white gold alloy comprising from 5 to 14% by weight of Pd and from 7 to 17% by weight of Cu, the proportion of Cu being substantially inversely proportional to that of Pd, the rest being formed of different elements intended to to improve the properties of the alloy.

Compte tenu de l'évolution du cours du palladium, on a proposé, en particulier dans le FR 2 764 906 , un alliage d'or 18 carats sans nickel, palladium, argent ou cobalt, comprenant entre 7-13% en poids de manganèse et le solde en cuivre.Given the evolution of the price of palladium, it has been proposed, in particular in the FR 2 764 906 , a nickel-free 18k gold alloy, palladium, silver or cobalt, comprising between 7-13% by weight of manganese and the balance of copper.

On cherche à éliminer l'argent de ces alliages en raison du risque de corrosion sous tension. Or, avec le manganèse qu'on lui substitue, on a également un risque de corrosion sous tension.We try to eliminate silver from these alloys because of the risk of corrosion under tension. However, with the manganese that is substituted for it, there is also a risk of corrosion under tension.

On avait déjà constaté avec étonnement dans le EP 1 010 768 susmentionné que l'on pouvait réduire la proportion de Pd en augmentant celle de Cu. Dans le FR 2 764 906 on avait constaté que l'on pouvait supprimer le Pd mais avec une importante proportion de 7-13% de Mn.We had already noticed with astonishment in the EP 1 010 768 mentioned that the proportion of Pd could be reduced by increasing that of Cu. In the FR 2 764 906 it was found that Pd could be suppressed but with a significant proportion of 7-13% Mn.

Le but de la présente invention est non seulement de réduire, voire de supprimer le Pd, mais aussi de réduire le Mn sans ajouter d'autre élément blanchissant, mais en augmentant le cuivre.The object of the present invention is not only to reduce or even eliminate the Pd, but also to reduce the Mn without adding other whitening element, but by increasing the copper.

A cet effet, l'objet de la présente invention est un alliage d'or gris tel que défini par la revendication 1.For this purpose, the object of the present invention is a gray gold alloy as defined by claim 1.

Dans le cas de cet alliage, on a constaté qu'avec au maximum 5% en poids de Pd, pourcentage pouvant avantageusement être nul et Mn > 0% et moins de 7% en poids de Mn, avantageusement 5%, avec au moins 17% en poids de Cu et avec 2% Zn au maximum, on obtient un alliage d'or gris répondant à l'ensemble des critères requis pour des alliages destinés à la bijouterie ou à l'horlogerie en particulier, aussi bien du point de vue de l'éclat et de la couleur que de celui de la résistance à la corrosion et de la capacité à être travaillé.In the case of this alloy, it has been found that with a maximum of 5% by weight of Pd, a percentage which can advantageously be zero and Mn> 0% and less than 7% by weight of Mn, advantageously 5%, with at least 17% by weight. % by weight of Cu and with a maximum of 2% Zn, a gray gold alloy is obtained which satisfies all the criteria required for alloys intended for jewelery or watchmaking in particular, both from the point of view of brilliance and color than that of corrosion resistance and the ability to be worked.

Un tel alliage répond donc à l'ensemble des critères requis dans le domaine de l'horlogerie et de la bijouterie en particulier, aussi bien en ce qui concerne les critères techniques, métallurgiques qu'économiques.Such an alloy therefore meets all the criteria required in the field of watchmaking and jewelery in particular, as well as with regard to technical, metallurgical and economic criteria.

Contrairement à ce qui a été proposé dans l'état de la technique, la réduction, voire la suppression du Pd ne s'obtient ni par une augmentation de la teneur en argent qui est absent de l'alliage, ni par celle de la teneur en Mn ou en Zn, ce dernier élément étant ajouté en faible proportion pour faciliter la coulée de l'alliage.Contrary to what has been proposed in the state of the art, the reduction or even the suppression of the Pd is obtained nor by an increase in the silver content which is absent from the alloy, nor by that of the content of Mn or Zn, the latter element being added in a small proportion to facilitate the casting of the alloy.

D'autres éléments tels que Ti, Ta, Si, peuvent être ajoutés dans de faibles proportions, typiquement < 1%, pour améliorer l'état de surface de l'alliage.Other elements such as Ti, Ta, Si can be added in small proportions, typically <1%, to improve the surface state of the alloy.

Différents autres éléments habituels peuvent être ajoutés en très faibles proportions, de l'ordre de quelques dizaines, voire quelques centaines de ppm, tel que Ir et Re en tant qu'affineur de grain, In pour abaisser le point de fusion et éviter ainsi la réaction entre les composants du moule et en particulier la production de SO2 dans les moules classiques en SiO2 et en plâtre de Paris. Toutefois, comme on pourra le constater dans les exemples qui vont suivre, les températures de solidus et de liquidus des alliages d'or gris selon l'invention sont généralement relativement basses et ne nécessitent pas d'adjonctions d'indium.Various other usual elements can be added in very small proportions, of the order of a few tens or even a few hundred ppm, such as Ir and Re as a grain refiner, In to lower the melting point and thus avoid the reaction between the mold components and in particular the production of SO 2 in conventional SiO 2 and plaster of Paris molds. However, as will be seen in the examples that follow, the solidus and liquidus temperatures of the gray gold alloys according to the invention are generally relatively low and do not require indium additions.

Les alliages selon l'invention sont préparés dans les conditions suivantes :The alloys according to the invention are prepared under the following conditions:

Les principaux éléments entrant dans la composition de l'alliage ont une pureté de 999, 9‰ et sont désoxydés.The main elements in the composition of the alloy have a purity of 999.9 ‰ and are deoxidized.

L'alliage est obtenu par fusion des éléments qui le composent dans un creuset en graphite. Le chauffage est obtenu par induction dans un four étanche sous pression partielle d'azote. L'alliage en fusion est ensuite coulé dans une lingotière en graphite. Après solidification, le lingot est démoulé, sorti de l'enceinte étanche pour être rapidement refroidi par une trempe à l'eau.The alloy is obtained by melting the elements that compose it in a graphite crucible. The heating is obtained by induction in a sealed furnace under partial pressure of nitrogen. The molten alloy is then cast in a graphite mold. After solidification, the ingot is demolded out of the sealed chamber to be rapidly cooled by quenching with water.

L'alliage ainsi obtenu est ensuite laminé à froid. Le taux d'écrouissage entre chaque recuit est 75 à 80%.The alloy thus obtained is then cold rolled. The hardening rate between each annealing is 75 to 80%.

Après chaque écrouissage, l'alliage est recuit durant .. minutes sous une atmosphère réductrice (20% H2 - 80% N2). Les recuits sont effectués à une température de 700°C. Le refroidissement est réalisé par trempe à l'eau.After each cold working, the alloy is annealed for 1 minute under a reducing atmosphere (20% H 2 - 80% N 2 ). Annealing is carried out at a temperature of 700 ° C. The cooling is carried out by quenching with water.

Tous les exemples qui vont suivre ont été réalisés conformément à ces conditions et se rapportent tous à des alliages d'or 18 carats. Les proportions indiquées sont exprimées en pourcentage en poids.All of the following examples have been made in accordance with these conditions and all relate to 18-carat gold alloys. The proportions indicated are expressed as percentage by weight.

Exemples :

  1. 1) Au 75-Cu 19,9-Mn 4,9
  2. 2) Au 75-Cu 18,8-Mn 5,0-Zn 1,0
  3. 3) Au 75-Cu 17,8-Mn 5,0-Zn 2,0
  4. 4) Au 75-Cu 18,0-Mn 5,0-Zn 1.8-Si 0,1
  5. 5) Au 75-Cu 18,0-Mn 5,0-Zn 1,6-Si 0,1-Ta 0,1-Ti 0,1
  6. 6) Au 75-Cu 18,0-Mn 5,0-Zn 1,4-Si 0,3-Ta 0,1-Ti 0,1
  7. 7) Au 75-Cu 18,0-Mn 5,0-Zn 1,9-Si 0,1
  8. 8) Au 75-Cu 18,0-Mn 5,0-Zn 1,7-Si 0,2
  9. 9) Au 75-Cu 17,5-Mn 5,5-Zn 1,6-Si 0,3
  10. 10) exemple comparatif Au 75-Cu 18,9-Mn 0,0-Zn 1.0- Pd 5,0
  11. 11) Au 75-Cu 18,0-Mn 5,0- Si 0,1 Pt 2,0
Examples:
  1. 1) At 75-Cu 19.9-Mn 4.9
  2. 2) At 75-Cu 18.8-Mn 5.0-Zn 1.0
  3. 3) At 75-Cu 17.8-Mn 5.0-Zn 2.0
  4. 4) At 75-Cu 18.0-Mn 5.0-Zn 1.8-Si 0.1
  5. 5) At 75-Cu 18.0-Mn 5.0-Zn 1.6-Si 0.1-Ta 0.1-Ti 0.1
  6. 6) At 75-Cu 18.0-Mn 5.0-Zn 1,4-Si 0.3-Ta 0.1-Ti 0.1
  7. 7) At 75-Cu 18.0-Mn 5.0-Zn 1.9-Si 0.1
  8. 8) At 75-Cu 18.0-Mn 5.0-Zn 1.7-Si 0.2
  9. 9) At 75-Cu 17.5-Mn 5.5-Zn 1.6-Si 0.3
  10. 10) Comparative Example At 75-Cu 18.9-Mn 0.0-Zn 1.0-Pd 5.0
  11. 11) At 75-Cu 18.0-Mn 5.0- If 0.1 Pt 2.0

L'absence d'argent et la teneur limitée en manganèse évitent la corrosion sous tension.The absence of silver and the limited content of manganese prevent stress corrosion.

La présence de silicium permet de limiter l'oxydation du manganèse et du cuivre, qui dégrade la surface de l'alliage lors des traitements thermiques, de la coulée et du moulage à la cire perdue.The presence of silicon limits the oxidation of manganese and copper, which degrades the surface of the alloy during heat treatments, casting and lost wax casting.

La présence de zinc améliore la coulabilité de l'alliage.The presence of zinc improves the flowability of the alloy.

On trouvera dans le tableau qui suit les différentes propriétés des alliages obtenus selon les exemples susmentionnés. Ce tableau donne en particulier les 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). TABLEAU N° Potentiel oxydation Solidus °C Liquidus °C L a b Hv coulé HVR HVE Ecr.% 1 -0,73 900 915 86,17 5,03 12,15 135 155 274 74 2 -0,70 895 910 85,46 3,82 10,12 140 150 274 80 3 -0,68 890 910 84,07 3,03 10,04 136 145 274 80 4 -0,69 880 890 88,2 3,6 11,8 171 165 274 80 5 -0,68 880 905 85,14 3,73 12,95 155 160 274 80 6 -0,68 860 890 87,3 2,6 12,6 185 178 294 80 7 -0,69 880 905 86,29 3,45 12,87 155 165 274 80 8 -0,69 860 890 87,54 3,24 11,98 178 165 287 70 9 -0,67 10 -0,95 935 965 86,35 5,83 11,23 155 155 252 74 11 -0,74 785 910 86 4,5 11,65 The following table shows the different properties of the alloys obtained according to the examples mentioned above. This table gives in particular the indications relating to the hardness of the alloy in the molded state annealed and hardened, as well as the color measured in a coordinate system with three axes. This three-dimensional measuring system called CIELab, CIE being the acronym of the Commission International & Light Lab the three coordinate axes, the axis L measuring the white-black component (black = 0; white = 100), the axis measuring the red-green component (red = green + a = -a) and the b axis measuring the yellow-blue component (yellow = + b blue = -b). <U> Table </ u> No. Potential oxidation Solidus ° C Liquidus ° C The at b Hv poured HVR HVE Esq.% 1 -0.73 900 915 86.17 5.03 12.15 135 155 274 74 2 -0.70 895 910 85.46 3.82 10.12 140 150 274 80 3 -0.68 890 910 84,07 3.03 10.04 136 145 274 80 4 -0.69 880 890 88.2 3.6 11.8 171 165 274 80 5 -0.68 880 905 85.14 3.73 12.95 155 160 274 80 6 -0.68 860 890 87.3 2.6 12.6 185 178 294 80 7 -0.69 880 905 86.29 3.45 12.87 155 165 274 80 8 -0.69 860 890 87.54 3.24 11.98 178 165 287 70 9 -0.67 10 -0.95 935 965 86.35 5.83 11.23 155 155 252 74 11 -0.74 785 910 86 4.5 11.65

Claims (6)

  1. Grey gold alloy that is nickel-free, cobalt-free, iron-free and silver-free and that has a limited content of manganese, characterized in that it consists, expressed by weight, of Au 75-76%, Cu > 17%, Mn > 0% and Mn < 7%, Pd 0-5%, Zn ≤ 2% and, optionally, small proportions of less than 1% of Ti, Ta and Si, a proportion of Pt of at most 2%, the balance being Cu and inevitable impurities.
  2. Grey gold alloy according to Claim 1, characterized in that it comprises at most 5% by weight of Mn.
  3. Grey gold alloy according to either of the preceding claims, characterized in that it comprises 5% by weight of Mn.
  4. Grey gold alloy according to one of the preceding claims, characterized in that it comprises, expressed by weight, Si < 0.5%.
  5. Grey gold alloy according to one of the preceding claims, characterized in that it comprises, expressed by weight, at least one of the elements Ti < 0.3%, Ta < 0.3%.
  6. Grey gold alloy according to one of the preceding claims, characterized in that it comprises 0% by weight of Pd and at most 2% of Pt.
EP01810074A 2001-01-26 2001-01-26 Grey gold alloy Expired - Lifetime EP1227166B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP01810074A EP1227166B1 (en) 2001-01-26 2001-01-26 Grey gold alloy
DE60141941T DE60141941D1 (en) 2001-01-26 2001-01-26 Gray gold alloy
AT01810074T ATE466115T1 (en) 2001-01-26 2001-01-26 GRAY GOLD ALLOY

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01810074A EP1227166B1 (en) 2001-01-26 2001-01-26 Grey gold alloy

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EP1227166A1 EP1227166A1 (en) 2002-07-31
EP1227166B1 true EP1227166B1 (en) 2010-04-28

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AT (1) ATE466115T1 (en)
DE (1) DE60141941D1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202200009575A1 (en) * 2022-05-10 2023-11-10 Metaltech S R L Master alloy for the production of precious metal alloys and white gold alloys

Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
FR2815044B1 (en) * 2000-10-06 2003-03-21 Cookson Metaux Precieux Sa 18K GRAY GOLD ALLOY FOR JEWELERY, NICKEL FREE AND PALLADIUM FREE
EP1447456A1 (en) * 2003-02-11 2004-08-18 Metalor Technologies International SA Gold doped alloy
EP1512765B1 (en) 2003-09-04 2006-12-20 Rolex Sa Watch or piece of jewellery resistant to decoloration
EP2135972A4 (en) * 2007-03-02 2011-08-24 Citizen Tohoku Co Ltd Gold alloy coating, gold alloy coating clad laminate and gold alloy coating clad member
EP2251444A1 (en) 2009-05-06 2010-11-17 Rolex Sa Grey gold alloy with no nickel and no copper
CN105008561B (en) * 2012-12-03 2018-07-03 Argor-Heraeus股份有限公司 The billon of anti-colour fading
CN104032273A (en) * 2014-06-09 2014-09-10 励福实业（江门）贵金属有限公司 Fastness rose gold target and preparation method thereof
EP3070182B1 (en) 2015-03-17 2017-08-30 The Swatch Group Research and Development Ltd. White-gold alloy
EP3339455B1 (en) 2016-12-20 2020-02-05 Montres Breguet S.A. Grey-gold alloy
CH715203B1 (en) * 2018-07-26 2022-03-15 Px Services Sa Gold-based alloy exhibiting a color change and its use in the field of jewelery and watchmaking.

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Publication number Priority date Publication date Assignee Title
FR2764906B1 (en) * 1997-06-18 1999-09-10 Engelhard Clal Sas 18 AND 14 CARAT GRAY GOLD ALLOYS FOR JEWELERY, NICKEL FREE AND PALLADIUM FREE
JPH11323461A (en) * 1998-05-08 1999-11-26 Tokuriki Honten Co Ltd White gold
RU2135618C1 (en) * 1998-08-10 1999-08-27 Открытое акционерное общество "Екатеринбургский завод по обработке цветных металлов" White-gold alloy
ES2195300T3 (en) * 1998-12-14 2003-12-01 Metalor Technologies Int GRAY GOLD ALLOY WITHOUT NICKEL.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202200009575A1 (en) * 2022-05-10 2023-11-10 Metaltech S R L Master alloy for the production of precious metal alloys and white gold alloys

Also Published As

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EP1227166A1 (en) 2002-07-31
ATE466115T1 (en) 2010-05-15
DE60141941D1 (en) 2010-06-10

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