EP2427582B1 - Graugoldlegierung ohne nickel und ohne kupfer - Google Patents

Graugoldlegierung ohne nickel und ohne kupfer Download PDF

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Publication number
EP2427582B1
EP2427582B1 EP10716257.0A EP10716257A EP2427582B1 EP 2427582 B1 EP2427582 B1 EP 2427582B1 EP 10716257 A EP10716257 A EP 10716257A EP 2427582 B1 EP2427582 B1 EP 2427582B1
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EP
European Patent Office
Prior art keywords
gold alloy
alloy
optionally
gray gold
element chosen
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP10716257.0A
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English (en)
French (fr)
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EP2427582A1 (de
Inventor
Michèle Reigner
Jean-François Ricard
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.)
Rolex SA
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Rolex SA
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Publication date
Application filed by Rolex SA filed Critical Rolex SA
Priority to EP11009184.0A priority Critical patent/EP2450461B1/de
Priority to EP10716257.0A priority patent/EP2427582B1/de
Priority to EP11009183.2A priority patent/EP2450460B1/de
Publication of EP2427582A1 publication Critical patent/EP2427582A1/de
Application granted granted Critical
Publication of EP2427582B1 publication Critical patent/EP2427582B1/de
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Classifications

    • 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 a nickel-free and copper-free gray gold alloy having a hardness particularly suitable for watchmakers, jewelers and jewelers.
  • the invention also relates to a process for preparing this alloy.
  • gray gold alloys There are two main types of gray gold alloys on the market, nickel alloys and palladium alloys, in which both are used as whiteners.
  • Nickel with its allergenic potential tends to be abandoned.
  • its alloys exhibit reduced hardness and deformability that lend themselves poorly to the fields of jewelery and watchmaking.
  • the increase in the copper concentration is to the detriment of other elements having whitening effects.
  • the Japanese patent application published under the number JP-A-8-003662 discloses white gold alloys of the Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi types. These alloys are intended for the preparation of metal clays, that is to say of clays of precious metals.
  • Metal clays are indeed generally defined as being a raw material for the manufacture of jewelery or works of art and comprising a very fine powder of precious metals, an organic binder and water. After forming, they are dried and burned to remove the organic binder, so that only the sintered metals remain.
  • This Japanese patent application therefore relates to a white gold alloy powder of Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi type to have excellent sinterability. Concretely, by mixing this powder with water, a binder (plasticizer: di-n-butyl phthalate) and a surfactant (ethyl-cellulose), one should obtain a metal clay with a high degree of sintering.
  • a gold alloy In order not to require rhodium-plating, a gold alloy must guarantee, according to ASTM Method D1925, a YI value: D1925 ⁇ 19 (YI: "yellowness index”), regarded as "good white” or "premium” and included in the Grade 1 category (see also http://www.utilisegold.com/jewellery technology / colors / whit e guide and Proceedings of Santa Fe Symposium 2005, pp. 103-120 ).
  • the colors of the gold alloys are defined in the tri-chromatic space according to ISO 8654.
  • a YI ⁇ 19 value corresponds in first approximation to [-2 ⁇ 2; b ⁇ 10].
  • the object of the present invention is to provide a nickel-free and copper-free gray gold alloy having satisfactory mechanical properties as well as a high whiteness (Grade 1) while not requiring rhodium-plating.
  • Elements such as Si and Ti are known to those skilled in the art to improve, when added in small amounts, the surface condition and brightness and reduce the risk of corrosion, without substantially modifying the hardness or affect the colour.
  • Elements such as Ir, Re or Ru are known to improve the metallurgical properties, in particular to guarantee the fineness of the grain and to avoid the porosities, without appreciably modifying the hardness or affecting the color.
  • the alloy according to the invention always meets the following conditions: - 2 ⁇ at ⁇ 2 b ⁇ 10 and HV annealed (Vickers hardness value after annealing)> 85.
  • Table I groups together 18-carat white gold alloys of the state of the art that are commercially available.
  • this table gives indications relating to the Vickers HV hardness index of the alloy in the cast state (HV cast), hardened to 75% (HV 75%) and annealed ( HV annealing), as well as to the color measured in the CIELab system.
  • alloy No. 6 has a hardly satisfactory HV value, although it contains copper.
  • Alloy No. 9 which is composed only of gold and palladium and is therefore free of copper, has a very low annealed HV value.
  • Table II below includes gray gold alloys according to the invention which are ternary. TABLE II (Alloys 23-26: Invention.) Ternary 18-carat gold (% by weight) The at b HV casting HV 75% HV annealing 10 At 75.1 Pd 21.0 In 3.9 78.79 1.49 5.68 80 175 115 11 At 75.1 Pd 22.0 V 2.9 81.04 1.33 5.36 115 195 127 12 At 75.1 Pd 20.0 V 4.9 82.15 1.10 5.03 125 230 157 13 At 75.1 Pd 21.0 Ta 3.9 80.15 1.35 5.14 135 213 164 14 At 75.1 Pd 23.0 V 1.9 79.34 1.38 5.05 90 182 112 15 At 75.1 Pd 22.0 Sn 2.9 79.54 1.37 5.14 128 202 118 16 At 75.1 Pd 22.0 Zn 2.9 79.36 1.37 4.84 80 156 108 17 At 75.1 Pd 23.5 Zr 1.4 80.06 1.
  • Each of the ternary alloys Nos. 10 to 32 therefore has satisfactory L, a, b and HV annealing values.
  • Quaternary alloys Nos. 33 to 35 and 38 and Quinternaries Nos. 36 and 37 all have satisfactory L, a, b and HV annealing values.
  • the grain index is established according to ASTM E 112. TABLE IV (invention) Grain refiner Concentration (ppm) grain index (ASTM E 112) 39 Iridium 500 2 40 Iridium 1000 3 91 Ruthenium 500 4 92 Ruthenium 1000 7 93 Rhenium 20 5 44 Rhenium 50 6
  • the alloys 39 and 40 show a grain structure in columns oriented in the direction of solidification.
  • the other alloys exhibit an equiaxed microstructure.
  • Ruthenium has the most pronounced grain refining effect, however, there are many inclusions that can penalize polishing.
  • Rhenium shows a capacity of refinement of the grain without formation of inclusions. The addition of rhenium at 20 to 60 ppm therefore gives excellent polishing ability.

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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)
  • Adornments (AREA)

Claims (13)

  1. Weißgoldlegierung ohne Nickel und ohne Kupfer, gebildet aus (in Massenanteilen)
    - mehr als 75% Au,
    - mehr als 18% bis weniger als 24% Pd,
    - mehr als 1% und weniger als 6% Mn,
    - gegebenenfalls von mehr als 1% bis weniger als 6% wenigstens eines aus Hf, Nb, Pt, Ta, V, Zn und Zr ausgewählten Elementes,
    - gegebenenfalls höchstens 0,5% wenigstens eines aus Si, Ga und Ti ausgewählten Elementes und
    - gegebenenfalls höchstens 0,2% wenigstens eines aus Ru, Ir und Re ausgewählten Elementes.
  2. Weißgoldlegierung nach Anspruch 1 gebildet aus (in Massenanteilen)
    - mehr als 75% Au,
    - von 19% bis 23,5% Pd,
    - von 1,4% bis 5,9% Mn,
    - gegebenenfalls von 1,4% bis 5,9% wenigstens eines aus Hf, Nb, Pt, Ta, V, Zn und Zr ausgewählten Elementes,
    - gegebenenfalls höchstens 0,5% wenigstens eines aus Si, Ga und Ti ausgewählten Elementes und
    - gegebenenfalls höchstens 0,1% wenigstens eines aus Ru, Ir und Re ausgewählten Elementes.
  3. Weißgoldlegierung nach Anspruch 1 oder 2 mit wenigstens 20% Pd.
  4. Weißgoldlegierung nach einem der Ansprüche 1 bis 3 mit wenigstens 1,5% Zr oder Nb.
  5. Weißgoldlegierung nach einem der Ansprüche 1 bis 4 mit 0,002% bis 0,006% (20 bis 60 ppm) Re.
  6. Weißgoldlegierung nach einem der Ansprüche 1 bis 5 mit etwa 75,1 % Au.
  7. Verfahren zum Herstellen einer Weißgoldlegierung nach einem der Ansprüche 1 bis 6, bei dem
    - die Bestandteile der Weißgoldlegierung in einen Schmelztiegel eingebracht werden,
    - der Schmelztiegel bis zum Verflüssigen der Bestandteile erhitzt wird,
    - die geschmolzene Legierung abgekühlt wird,
    - sie sich verfestigen gelassen wird,
    - sie einer Wasserabschreckung unterworfen wird,
    - sie wenigstens einem Kaltwalzen unterworfen wird und
    - sie unter Reduzieren der Atmosphäre getempert wird.
  8. Verfahren nach Anspruch 7, bei dem das Erhitzen durch Induktion in einem dichten Ofen unter Edelgaspartialdruck erfolgt.
  9. Verfahren nach Anspruch 8, bei dem das Edelgas Ar ist.
  10. Verfahren nach einem der Ansprüche 7 bis 9, bei dem das Tempern unter einer aus einer Mischung von N2 und H2 gebildeten reduzierenden Atmosphäre durchgeführt wird.
  11. Verfahren nach Anspruch 10, bei dem die Mischung aus N2 und H2 durch etwa 80% N2 und 20% H2 gebildet ist.
  12. Verfahren nach einem der Ansprüche 7 bis 11, bei dem das Tempern über etwa 30 Minuten durchgeführt wird.
  13. Verfahren nach einem der Ansprüche 7 bis 12, bei dem das Tempern bei etwa 850°C durchgeführt wird.
EP10716257.0A 2009-05-06 2010-04-15 Graugoldlegierung ohne nickel und ohne kupfer Active EP2427582B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP11009184.0A EP2450461B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer
EP10716257.0A EP2427582B1 (de) 2009-05-06 2010-04-15 Graugoldlegierung ohne nickel und ohne kupfer
EP11009183.2A EP2450460B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09405077A EP2251444A1 (de) 2009-05-06 2009-05-06 Graugoldlegierung ohne Nickel und Kupfer
PCT/CH2010/000101 WO2010127458A1 (fr) 2009-05-06 2010-04-15 Alliage d'or gris sans nickel et sans cuivre
EP10716257.0A EP2427582B1 (de) 2009-05-06 2010-04-15 Graugoldlegierung ohne nickel und ohne kupfer

Related Child Applications (5)

Application Number Title Priority Date Filing Date
EP11009184.0A Division-Into EP2450461B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer
EP11009184.0A Division EP2450461B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer
EP11009183.2A Division-Into EP2450460B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer
EP11009183.2 Division-Into 2011-11-19
EP11009184.0 Division-Into 2011-11-19

Publications (2)

Publication Number Publication Date
EP2427582A1 EP2427582A1 (de) 2012-03-14
EP2427582B1 true EP2427582B1 (de) 2014-03-12

Family

ID=41127638

Family Applications (4)

Application Number Title Priority Date Filing Date
EP09405077A Withdrawn EP2251444A1 (de) 2009-05-06 2009-05-06 Graugoldlegierung ohne Nickel und Kupfer
EP11009183.2A Active EP2450460B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer
EP11009184.0A Active EP2450461B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer
EP10716257.0A Active EP2427582B1 (de) 2009-05-06 2010-04-15 Graugoldlegierung ohne nickel und ohne kupfer

Family Applications Before (3)

Application Number Title Priority Date Filing Date
EP09405077A Withdrawn EP2251444A1 (de) 2009-05-06 2009-05-06 Graugoldlegierung ohne Nickel und Kupfer
EP11009183.2A Active EP2450460B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer
EP11009184.0A Active EP2450461B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer

Country Status (6)

Country Link
US (1) US9650697B2 (de)
EP (4) EP2251444A1 (de)
JP (1) JP5793136B2 (de)
CN (1) CN102549179B (de)
CH (1) CH703415B1 (de)
WO (1) WO2010127458A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3339455A1 (de) 2016-12-20 2018-06-27 Montres Breguet S.A. Weissgoldlegierung

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CN104884650B (zh) * 2012-11-08 2017-09-05 贺利氏有限公司 具有低镍释放速率的含镍金合金、用于获得所述含镍金合金的中间合金以及其中金属元素的用途
JP2016505710A (ja) 2012-12-03 2016-02-25 アルゴー−ヘラエウス エスエー 耐変色性金合金
CH707539B1 (fr) * 2013-02-06 2017-01-13 Rolex Sa Alliage d'or rose pour pièce d'horlogerie.
EP3020835B1 (de) 2014-11-17 2021-04-21 Omega SA Uhr, Schmuckstück oder edler Schmuck, umfassend eine Komponente aus einer Legierung auf Palladiumbasis
EP3070182B1 (de) * 2015-03-17 2017-08-30 The Swatch Group Research and Development Ltd. Weissgoldlegierung
FR3034106B1 (fr) 2015-03-23 2022-07-22 Centre Nat Rech Scient Alliage monophasique d'or et de tungstene
EP3315620B1 (de) * 2016-10-25 2020-06-24 Nivarox-FAR S.A. Nichtmagnetische hochwertige legierung für anwendungen in uhren
CN110446794B (zh) * 2017-03-27 2021-03-26 派特·古普塔 用于珠宝制造的含锆、钛和镁的硬质金合金
CH715203B1 (fr) 2018-07-26 2022-03-15 Px Services Sa Alliage à base d'or présentant un changement de couleur et son utilisation dans le domaine de la joaillerie et de l'horlogerie.
CN109136625A (zh) * 2018-09-14 2019-01-04 深圳市品越珠宝有限公司 一种高硬度合金及其制备方法
CN110629062A (zh) * 2019-05-16 2019-12-31 杭州辰卓科技有限公司 一种具有斯斑效应20k耐腐蚀耐脆断金合金及其工艺
JP6789528B1 (ja) * 2019-09-26 2020-11-25 田中貴金属工業株式会社 医療用Ａｕ−Ｐｔ−Ｐｄ合金
EP3808865B1 (de) 2019-10-17 2023-01-18 Richemont International S.A. Weissgoldlegierung und ihr herstellungsverfahren

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3339455A1 (de) 2016-12-20 2018-06-27 Montres Breguet S.A. Weissgoldlegierung

Also Published As

Publication number Publication date
CH703415B1 (fr) 2014-03-14
JP2012526192A (ja) 2012-10-25
EP2450460B1 (de) 2013-09-25
CN102549179B (zh) 2016-03-30
WO2010127458A8 (fr) 2011-04-14
EP2427582A1 (de) 2012-03-14
JP5793136B2 (ja) 2015-10-14
EP2450461A1 (de) 2012-05-09
EP2450460A1 (de) 2012-05-09
EP2450461B1 (de) 2014-10-29
EP2251444A1 (de) 2010-11-17
WO2010127458A1 (fr) 2010-11-11
CN102549179A (zh) 2012-07-04
US9650697B2 (en) 2017-05-16
US20120114522A1 (en) 2012-05-10

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