EP3812477A1 - Alliage métallique comprenant de l'or - Google Patents

Alliage métallique comprenant de l'or Download PDF

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Publication number
EP3812477A1
EP3812477A1 EP19306367.4A EP19306367A EP3812477A1 EP 3812477 A1 EP3812477 A1 EP 3812477A1 EP 19306367 A EP19306367 A EP 19306367A EP 3812477 A1 EP3812477 A1 EP 3812477A1
Authority
EP
European Patent Office
Prior art keywords
metal alloy
metallic elements
gold
alloy
alloy according
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.)
Granted
Application number
EP19306367.4A
Other languages
German (de)
English (en)
Other versions
EP3812477B1 (fr
Inventor
Fanny LALIRE
Louis THEDY
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.)
Richemont International SA
Original Assignee
Richemont International 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 Richemont International SA filed Critical Richemont International SA
Priority to EP19306367.4A priority Critical patent/EP3812477B1/fr
Publication of EP3812477A1 publication Critical patent/EP3812477A1/fr
Application granted granted Critical
Publication of EP3812477B1 publication Critical patent/EP3812477B1/fr
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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
    • 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
    • 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 metal alloy comprising several metallic elements including gold (Au), and a process of manufacturing said metal alloy.
  • the metal alloy is used to manufacture luxury goods.
  • metal alloys used to manufacture luxury goods such as a time-piece or a jewel.
  • the present invention seeks to provide a new metal alloy, having optimized mechanical properties, while being easy to shape.
  • an object of the present invention is a metal alloy comprising at least four metallic elements different from gold (Au), each of said metallic elements being in an amount from 1.0 to 55.0 atomic percent (at%), characterized in that the metal alloy further comprises gold (Au) in an amount of at least 58.3% by weight over the total weight of the metal alloy.
  • the present invention advantageously provides a metal alloy with an improved hardness, while guaranteeing a good ductility.
  • the hardness of the metal alloy can advantageously be of at least 150 Vickers hardness (HV) (i.e. kilograms-force per square millimeter), more preferably of at least 200 HV, and even more preferably of at least 250 HV.
  • HV Vickers hardness
  • the metal alloy is also advantageously easy to shape, especially to manufacture luxury good.
  • the metal alloy of the present invention has advantageously a high entropy.
  • the entropy of the metal alloy can be of at least 0.69R, more preferably at least 1.00R, and even more preferably at least 1.20R, R being the molar gas constant.
  • ⁇ S conf - R ⁇ X i In(X i ), where X i represents the atomic fraction of element i and R is the molar gas constant.
  • a high entropy can favor the formation of a solid solution, which may help to improve the ductility of the metal alloy.
  • the metal alloy of the present invention can be a solid solution.
  • a solid solution is well known in the art and can be considered as a solid-state solution comprising several metallic elements wherein the metallic elements remain in a single homogeneous phase in the metal alloy.
  • the metal alloy of the invention can preferably be a single-phase alloy.
  • gold is used as main metallic element among the at least five metallic elements constituting the metal alloy.
  • the metal alloy comprises an amount of gold (Au) superior or equal to 58.3 % by weight over the total weight of the metal alloy.
  • An amount of gold (Au) of at least 58.3 % by weight over the total weight of the metal alloy is particularly advantageous since it corresponds to an amount of 583 ⁇ (per mille) by weight of gold (Au) over the total weight of the metal alloy.
  • the metal alloy can be considered as a precious material of 14-karat gold (i.e. 14k), under the karat standard system for gold alloy.
  • the metal alloy can comprise at least 70.0 % by weight of gold (Au), and more preferably 75.0 % by weight of gold (Au), over the total weight of the metal alloy.
  • An amount of gold (Au) of at least 75.0 % by weight over the total weight of the metal alloy is particularly advantageous since it corresponds to an amount of 750 ⁇ (per mille) by weight of gold (Au) over the total weight of the metal alloy.
  • the metal alloy can be considered as a precious material of 18-karat gold (i.e. 18k), under the karat standard system for gold alloy.
  • the metal alloy comprises at least four metallic elements different from gold (Au), each of said four metallic elements being in an amount from 1.0 to 55.0 atomic percent (at%), and more preferably from 5.0 to 30.0 atomic percent.
  • the atomic percent of each metallic elements constituting the metal alloy is expressed over the total atomic percent (100%) of the metallic elements constituting the metal alloy.
  • the four metallic elements can be selected among silver (Ag), aluminum (Al), manganese (Mn), copper (Cu), palladium (Pd), iron (Fe), and chromium (Cr), platinum (Pt), and cobalt (Co).
  • the four metallic elements can be copper (Cu), silver (Ag), manganese (Mn), and aluminum (Al).
  • the metal alloy can be for example, in at%, Au 34.4 Cu 25.9 Ag 22.8 Mn 9.6 Al 7.3 or Au 52.5 Cu 20.3 Ag 15.2 Mn 6.5 Al 5.5 .
  • the four metallic elements can be palladium (Pd), silver (Ag), chromium (Cr), and iron (Fe).
  • the metal alloy can be for example, in at%, Au 36.6 Pd 16.4 Ag 16.2 Cr 15.4 Fe 15.4 .
  • the four metallic elements can be silver (Ag), chromium (Cr), palladium (Pd), and cobalt (Co).
  • the metal alloy can be for example, in at%, Au 38.0 Ag 15.5 Cr 15.5 Pd 15.5 Co 15.5 .
  • the four metallic elements can be silver (Ag), cobalt (Co), palladium (Pd), and iron (Fe).
  • the metal alloy can be for example, in at%, Au 38.0 Ag 15.5 Co 15.5 Pd 15.5 Fe 15.5 .
  • the four metallic elements can be silver (Ag), platinum (Pt), palladium (Pd), and iron (Fe).
  • the metal alloy can be for example, in at%, Au 67.0 Ag 8.25 Pt 8.25 Pd 8.25 Fe 8.25 .
  • the gold (Au) used in the metal alloy of the invention can preferably have a purity of at least 99.5 %, and more preferably of at least 99.9 % and even more preferably of at least 99.99 %.
  • the metallic elements different from gold (Au) can also have a purity of at least 99.0 %, and more preferably of at least 99.9 %.
  • Another object of the present invention is a process of manufacturing said metal alloy, the process comprising the following steps:
  • the step i can include a mixture of the metallic elements as such and/or one or several pre-alloy(s).
  • the step i can be done in using an arc furnace, classically in placing the metallic elements and/or the pre-alloy(s) in a crucible, and submitting then with an electric arc producing a temperature of up to 3000°C. This process makes it possible to produce alloys from pure elements with different melting temperatures.
  • the metallic element mixture can then be cooled to room temperature (around 25°C).
  • the step i can be done in using an induction furnace, classically in placing the metallic elements and/or the pre-alloy(s) in a crucible, and submitting then with an induction heating.
  • the metallic element mixture can then be cooled to room temperature (around 25°C).
  • a pre-alloy can be a mixture of at least two metallic elements having similar melting temperature.
  • a pre-alloy can be formed with two metallic elements having a melting temperature difference inferior or equal to 150°C, and more preferable inferior or equal to 100°C.
  • the pre-alloys can be formed in using an arc furnace.
  • the metallic element mixture can then be cooled to room temperature (around 25°C).
  • the alloy obtained in step i is then rolled in order to increase its mechanical properties and modify its internal structure.
  • the rolling step can be done at room temperature (around 25°C) in using a rolling mill.
  • the rolling step can usually be performed after cooling to room temperature (around 25°C) the alloy obtained in step i.
  • the step iii can be advantageously done to improve the yield strength and the hardness of the alloy, especially when several cold rolling passes are done.
  • the temperature and annealing time depend on the nature of the alloy, the rate of cold work previously applied and the properties required, according to the conditions well-known in the art.
  • the annealing step can be done at a temperature around 750°C, during 30 minutes.
  • step iii when the step iii is performed, the step iii can be followed by one or several steps of cold rolling as detailed in step ii.
  • Another object of the present invention is an item obtained from the metal alloy.
  • the item can comprise or consist of the metal alloy according to the present invention.
  • the metal alloy can be used in order to manufacture luxury goods, such as for example a time-piece and/or a jewel.
  • the time-piece and/or the jewel can have a part or a component comprising the metal alloy according to the present invention.
  • the item according to the present invention can be a jewel, a leather good, or a clothing accessory. It may also be a watch, a writing accessory, or a decorative item.
  • the item can be any of the followings: ring; ear ring; necklace; bracelet; pendant; watch such as case, bezel, caseback, crown, bracelet links, clasp, buckle, automatic movement rotor; buckle (e.g. belt or purse); tie bar; cuff links; money clip; hair pin; pen; paper knife.
  • watch such as case, bezel, caseback, crown, bracelet links, clasp, buckle, automatic movement rotor; buckle (e.g. belt or purse); tie bar; cuff links; money clip; hair pin; pen; paper knife.
  • Metal alloy 1 Metal alloy 2
  • Metal alloy 3 Metal alloy 4
  • Metal alloy 5 Metal alloy 5
  • Metal alloy 1, Metal alloy 3 and Metal alloy 4 can be considered as a precious alloy of 14-karat gold
  • Metal alloy 2 and Metal alloy 5 can be considered as a precious alloy of 18-karat gold.
  • a molten alloy is formed (step i) in using an arc furnace, in placing and mixing all the metallic elements constituting a metal alloy, in a crucible.
  • step ii After cooling to room temperature (around 25°C) the alloy obtained in step i, a rolling step is performed (step ii) at room temperature (around 25°C), with several passes, in using a roller mill.
  • the rolling step is of:
  • the rolled alloy is under the form of a bar.
  • Some properties of the metal alloys obtained in the preparation as described above can be easily determined, such as entropy, ⁇ E and hardness.
  • ⁇ S conf - R ⁇ X i In(X i ), where X i represents the atomic fraction of element i and R is the molar gas constant.
  • CIELAB coordinates which are well known as color space specified by the International Commission on Illumination (known in French with the acronym CIE), are used.
  • ⁇ E* corresponds to the distance between two colors placed in the CIELAB color space which is calculated with the formula of the Euclidian distance.
  • ⁇ E* can also be written ⁇ E or ⁇ E ab .
  • the illuminant used to evaluate the metal alloy color is the CIE D65 standard illuminant, with a viewing angle of 10°.
  • the evolution of the metal alloy color is studied according to the test Tuccillo-Nielsen wheel method, which aims at evaluating the tarnish testing of an alloy in contact with the skin.
  • the metal alloy is immersed during 30 seconds in artificial sweet and then dried in the open air during 30 seconds, in a continuous way.
  • the hardness of the metal alloy can advantageously be of at least 200 HV, more preferably of at least 250 HV, and even more preferably of at least 300 HV. Said hardness (i.e. final hardness) is more particularly the one determined on the metal alloy obtained after the steps i, ii and optionally iii.
  • the alloy obtained before the step ii can have a hardness of at least 200 HV.
  • Said hardness i.e. raw hardness
  • Table 6 The amounts in Table 6 are expressed in weight percent (wt%) over the total weight of the metal alloy.
  • the preparation of said Metal alloy 6 is similar to the preparation described in the above item 1, except that the rolling step (step ii) is of 75%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adornments (AREA)
EP19306367.4A 2019-10-21 2019-10-21 Alliage métallique comprenant de l'or Active EP3812477B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19306367.4A EP3812477B1 (fr) 2019-10-21 2019-10-21 Alliage métallique comprenant de l'or

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19306367.4A EP3812477B1 (fr) 2019-10-21 2019-10-21 Alliage métallique comprenant de l'or

Publications (2)

Publication Number Publication Date
EP3812477A1 true EP3812477A1 (fr) 2021-04-28
EP3812477B1 EP3812477B1 (fr) 2023-01-11

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Family Applications (1)

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EP (1) EP3812477B1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB372236A (en) * 1931-03-10 1932-05-05 Cartier Sa Gold alloy
EP0008975A1 (fr) * 1978-08-31 1980-03-19 Comptoir Lyon-Alemand - Louyot Alliage jaune à base d'or pouvant être utilisé notamment comme alliage dentaire revêtu éventuellement d'un matériau céramique et procédé de durcissement d'un tel alliage
US5221207A (en) * 1990-10-03 1993-06-22 Degussa Aktiengesellschaft Yellow dental alloy with a high gold content
JP2001207226A (ja) * 2000-01-25 2001-07-31 Kyocera Corp １８金合金
US20140328718A1 (en) * 2013-05-06 2014-11-06 Richline Group, Inc. 18K Ni-FREE AGE HARDENABLE WHITE GOLD ALLOY
US20180171436A1 (en) * 2016-12-20 2018-06-21 Montres Breguet S.A. Grey gold alloy
CN108588467A (zh) * 2018-06-02 2018-09-28 北京椿树电子材料有限公司 一种金基银铜合金材料
WO2019073023A1 (fr) 2017-10-13 2019-04-18 Hublot Sa, Genève Alliage a haute entropie

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69812652T2 (de) * 1998-12-14 2004-04-29 Metalor Technologies International Sa Graue Goldlegierung, ohne Nickel
DE60310555T2 (de) * 2003-09-04 2007-12-27 Rolex Sa Entfärbungsbestängdige Uhr oder Schmuck
CH714785B1 (it) * 2018-03-15 2022-05-13 Argor Heraeus Sa Lega d'oro resistente alla decolorazione e metodo di produzione della medesima.

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB372236A (en) * 1931-03-10 1932-05-05 Cartier Sa Gold alloy
EP0008975A1 (fr) * 1978-08-31 1980-03-19 Comptoir Lyon-Alemand - Louyot Alliage jaune à base d'or pouvant être utilisé notamment comme alliage dentaire revêtu éventuellement d'un matériau céramique et procédé de durcissement d'un tel alliage
US5221207A (en) * 1990-10-03 1993-06-22 Degussa Aktiengesellschaft Yellow dental alloy with a high gold content
JP2001207226A (ja) * 2000-01-25 2001-07-31 Kyocera Corp １８金合金
US20140328718A1 (en) * 2013-05-06 2014-11-06 Richline Group, Inc. 18K Ni-FREE AGE HARDENABLE WHITE GOLD ALLOY
US20180171436A1 (en) * 2016-12-20 2018-06-21 Montres Breguet S.A. Grey gold alloy
WO2019073023A1 (fr) 2017-10-13 2019-04-18 Hublot Sa, Genève Alliage a haute entropie
CN108588467A (zh) * 2018-06-02 2018-09-28 北京椿树电子材料有限公司 一种金基银铜合金材料

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