EP2251444A1 - Graugoldlegierung ohne Nickel und Kupfer - Google Patents

Graugoldlegierung ohne Nickel und Kupfer Download PDF

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Publication number
EP2251444A1
EP2251444A1 EP09405077A EP09405077A EP2251444A1 EP 2251444 A1 EP2251444 A1 EP 2251444A1 EP 09405077 A EP09405077 A EP 09405077A EP 09405077 A EP09405077 A EP 09405077A EP 2251444 A1 EP2251444 A1 EP 2251444A1
Authority
EP
European Patent Office
Prior art keywords
gold alloy
alloy
optionally
gray gold
copper
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.)
Withdrawn
Application number
EP09405077A
Other languages
English (en)
French (fr)
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
Original Assignee
Rolex SA
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 Rolex SA filed Critical Rolex SA
Priority to EP09405077A priority Critical patent/EP2251444A1/de
Priority to EP10716257.0A priority patent/EP2427582B1/de
Priority to CN201080019776.8A priority patent/CN102549179B/zh
Priority to PCT/CH2010/000101 priority patent/WO2010127458A1/fr
Priority to EP11009184.0A priority patent/EP2450461B1/de
Priority to US13/265,655 priority patent/US9650697B2/en
Priority to JP2012508867A priority patent/JP5793136B2/ja
Priority to CH01771/11A priority patent/CH703415B1/fr
Priority to EP11009183.2A priority patent/EP2450460B1/de
Publication of EP2251444A1 publication Critical patent/EP2251444A1/de
Withdrawn legal-status Critical Current

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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.
  • a gold alloy In order not to require rhodium-plating, a gold alloy must, according to ASTM Method D1925, guarantee a value YI: D1925 ⁇ 19 (YI: "yellowness index”), considered as "good white” or "premium” And integrated into 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 the ISO 8654.
  • a YI ⁇ 19 value corresponds in first approximation to [-2 ⁇ a ⁇ 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.
  • 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 (invention) 18-carat ternary golds (% in 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 1.30 4.73 87
  • Each of the ternary alloys 10 to 32 according to the invention therefore has satisfactory L, a, b and HV annealing values.
  • Table III relates to quaternary and quinternal alloys according to the invention.
  • TABLE III (invention) 18-carat gold quaternaries and quinternaries (% by weight) The at b HV casting HV 75% HV annealing 33 At 75.1 Pd 21.0 Nb 1.9 Zr 2.0 80.76 1.18 4.53 167 260 169 34 At 75.1 Pd 21.0 Nb 1.9 Mn 2.0 80.41 1.33 4.79 133 213 147 35 At 75.1 Pd 21.0 Zr 2.0 Mn 1.9 79.95 1.24 4.55 150 237 153 36 At 75.1 Pd 19.0 Nb 2.0 Zr 2.0 Mn 1.9 80.77 1.13 4.16 170 285 255 37 At 75.1 Pd 20.0 Zr 2.0 Pt 2.4 Ga 0.5 79.86 1.20 4.65 185 226 192 38 At 75.1 Pd 20.0 Zr 2.5 Pt 2.4 79.96 1.14 4.31 153 209 188
  • the grain index is established according to ASTM E 112. TABLE IV (invention) Refiner grains Concentration (Ppm) grain index (ASTM E 112) 39 Iridium 500 2 40 Iridium 1000 3 41 Ruthenium 500 4 42 Ruthenium 1000 7 43 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)
EP09405077A 2009-05-06 2009-05-06 Graugoldlegierung ohne Nickel und Kupfer Withdrawn EP2251444A1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP09405077A EP2251444A1 (de) 2009-05-06 2009-05-06 Graugoldlegierung ohne Nickel und Kupfer
EP10716257.0A EP2427582B1 (de) 2009-05-06 2010-04-15 Graugoldlegierung ohne nickel und ohne kupfer
CN201080019776.8A CN102549179B (zh) 2009-05-06 2010-04-15 无镍和铜的白金合金
PCT/CH2010/000101 WO2010127458A1 (fr) 2009-05-06 2010-04-15 Alliage d'or gris sans nickel et sans cuivre
EP11009184.0A EP2450461B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer
US13/265,655 US9650697B2 (en) 2009-05-06 2010-04-15 Gray gold alloy free of nickel and copper
JP2012508867A JP5793136B2 (ja) 2009-05-06 2010-04-15 ニッケルおよび銅を含まないグレーゴールド合金
CH01771/11A CH703415B1 (fr) 2009-05-06 2010-04-15 Alliage d'or gris sans nickel et sans cuivre.
EP11009183.2A EP2450460B1 (de) 2009-05-06 2010-04-15 Weißgoldlegierung ohne Nickel und Kupfer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09405077A EP2251444A1 (de) 2009-05-06 2009-05-06 Graugoldlegierung ohne Nickel und Kupfer

Publications (1)

Publication Number Publication Date
EP2251444A1 true EP2251444A1 (de) 2010-11-17

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
EP10716257.0A Active EP2427582B1 (de) 2009-05-06 2010-04-15 Graugoldlegierung ohne nickel und ohne 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

Family Applications After (3)

Application Number Title Priority Date Filing Date
EP10716257.0A Active EP2427582B1 (de) 2009-05-06 2010-04-15 Graugoldlegierung ohne nickel und ohne 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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014087216A1 (en) 2012-12-03 2014-06-12 Argor-Heraeus Sa Discoloration-resistant gold alloy
EP3315620A1 (de) * 2016-10-25 2018-05-02 Nivarox-FAR S.A. Nichtmagnetische hochwertige legierung für anwendungen in uhren
US10458002B2 (en) * 2016-12-20 2019-10-29 Montres Breguet S.A. Grey gold alloy
WO2020020528A1 (fr) 2018-07-26 2020-01-30 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

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014071583A1 (en) * 2012-11-08 2014-05-15 Heraeus Ltd. Nickel containing gold alloys having low nickel releasing rate, master alloys for obtaining them and use of metal elements therein
JP6595344B2 (ja) * 2013-02-06 2019-10-23 ロレックス・ソシエテ・アノニム ローズゴールド合金から作成される時計
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
EP3571325A4 (de) * 2017-03-27 2020-11-18 Pethe, Subodh Hartgold-legierung mit zirkonium, titan und magnesium zur herstellung von schmuck
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

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716356A (en) * 1970-09-23 1973-02-13 Ney Co J M Rhenium containing gold alloys
DE3211703A1 (de) * 1982-03-30 1983-10-20 C. Hafner GmbH + Co., 7530 Pforzheim Verwendung goldarmer edelmetallegierungen fuer dentalzwecke
JPH083662A (ja) * 1994-06-20 1996-01-09 Mitsubishi Materials Corp 焼結性に優れたＡｕ−Ｐｄ系白色金合金粉末
JPH083663A (ja) * 1994-06-20 1996-01-09 Mitsubishi Materials Corp 焼結性に優れたＡｕ−Ｐｄ−Ａｇ系白色金合金粉末
EP1010768A1 (de) 1998-12-14 2000-06-21 Metaux Precieux Sa Metalor Graue Goldlegierung, ohne Nickel
US6156266A (en) * 2000-01-07 2000-12-05 Argen Corporation Gold alloy for firing on porcelain
JP3130334B2 (ja) 1991-07-18 2001-01-31 シャープ株式会社 耐光性着色薄膜用樹脂組成物
EP1227166A1 (de) 2001-01-26 2002-07-31 Metaux Precieux Sa Metalor Graue Goldlegierung

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GB1110045A (en) * 1964-03-04 1968-04-18 Zh Denki Jiki Zairyo Kenkyusho A method of manufacturing non-magnetic, elastic metallic materials
DE2136373B2 (de) * 1971-07-21 1972-11-30 W.C. Heraeus Gmbh, 6450 Hanau Verwendung einer goldlegierung als werkstoff fuer elektrische widerstaende
DE3132143C2 (de) * 1981-08-14 1985-07-04 Degussa Ag, 6000 Frankfurt Edelmetallegierung zur Herstellung von mit keramischen Massen verblendbaren Kronen und Brücken
DE3711207A1 (de) * 1987-04-02 1988-10-20 Kerstin Koerber Gebrauchsfertige kaeppchen zur zahnstumpfrestauration
JP2611319B2 (ja) * 1988-03-28 1997-05-21 三菱マテリアル株式会社 人工ダイヤモンドコート装飾品用金合金
JP2922228B2 (ja) * 1989-10-16 1999-07-19 株式会社徳力本店 装飾用白色金合金
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CH684616B5 (fr) 1992-08-17 1995-05-15 Metaux Precieux Sa Alliage d'or gris et utilisation de cet alliage.
DE19525361A1 (de) * 1995-02-16 1996-08-22 Herbst Bremer Goldschlaegerei Edelmetall-Legierung und Verwendung derselben
US5919320A (en) * 1997-11-17 1999-07-06 Leach & Garner Company Nickel-free white gold alloy with reversible hardness characteristics
JP2000336439A (ja) * 1999-05-27 2000-12-05 Mizuho Kogei:Kk 白色系金合金
JP2001207226A (ja) * 2000-01-25 2001-07-31 Kyocera Corp １８金合金
EP1447456A1 (de) * 2003-02-11 2004-08-18 Metalor Technologies International SA Dotierte Goldlegierung
JP3139334U (ja) 2007-10-31 2008-02-14 有限会社味 路 餃子形パイ菓子

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716356A (en) * 1970-09-23 1973-02-13 Ney Co J M Rhenium containing gold alloys
DE3211703A1 (de) * 1982-03-30 1983-10-20 C. Hafner GmbH + Co., 7530 Pforzheim Verwendung goldarmer edelmetallegierungen fuer dentalzwecke
JP3130334B2 (ja) 1991-07-18 2001-01-31 シャープ株式会社 耐光性着色薄膜用樹脂組成物
JPH083662A (ja) * 1994-06-20 1996-01-09 Mitsubishi Materials Corp 焼結性に優れたＡｕ−Ｐｄ系白色金合金粉末
JPH083663A (ja) * 1994-06-20 1996-01-09 Mitsubishi Materials Corp 焼結性に優れたＡｕ−Ｐｄ−Ａｇ系白色金合金粉末
EP1010768A1 (de) 1998-12-14 2000-06-21 Metaux Precieux Sa Metalor Graue Goldlegierung, ohne Nickel
US6156266A (en) * 2000-01-07 2000-12-05 Argen Corporation Gold alloy for firing on porcelain
EP1227166A1 (de) 2001-01-26 2002-07-31 Metaux Precieux Sa Metalor Graue Goldlegierung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PROCEEDINGS OF SANTA FE SYMPOSIUM, 2005, pages 103 - 120, Retrieved from the Internet <URL:http://www.utilisegold.com/jewellery technology/colours/whit e guide>

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014087216A1 (en) 2012-12-03 2014-06-12 Argor-Heraeus Sa Discoloration-resistant gold alloy
US10030296B2 (en) 2012-12-03 2018-07-24 Argor-Heraeus Sa Discoloration-resistant gold alloy
US10683570B2 (en) 2012-12-03 2020-06-16 Argor-Heraeus Sa Discoloration-resistant gold alloy
EP3315620A1 (de) * 2016-10-25 2018-05-02 Nivarox-FAR S.A. Nichtmagnetische hochwertige legierung für anwendungen in uhren
US10458002B2 (en) * 2016-12-20 2019-10-29 Montres Breguet S.A. Grey gold alloy
WO2020020528A1 (fr) 2018-07-26 2020-01-30 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

Also Published As

Publication number Publication date
EP2450460A1 (de) 2012-05-09
CN102549179B (zh) 2016-03-30
EP2450461B1 (de) 2014-10-29
JP5793136B2 (ja) 2015-10-14
EP2450460B1 (de) 2013-09-25
WO2010127458A1 (fr) 2010-11-11
US9650697B2 (en) 2017-05-16
JP2012526192A (ja) 2012-10-25
US20120114522A1 (en) 2012-05-10
CN102549179A (zh) 2012-07-04
CH703415B1 (fr) 2014-03-14
WO2010127458A8 (fr) 2011-04-14
EP2427582B1 (de) 2014-03-12
EP2427582A1 (de) 2012-03-14
EP2450461A1 (de) 2012-05-09

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