EP2402467B1 - Goldlegierung mit verbesserter Härte - Google Patents

Goldlegierung mit verbesserter Härte Download PDF

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Publication number
EP2402467B1
EP2402467B1 EP10167859.7A EP10167859A EP2402467B1 EP 2402467 B1 EP2402467 B1 EP 2402467B1 EP 10167859 A EP10167859 A EP 10167859A EP 2402467 B1 EP2402467 B1 EP 2402467B1
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EP
European Patent Office
Prior art keywords
gold
aluminium
precipitate
alloy
additional metal
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EP10167859.7A
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English (en)
French (fr)
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EP2402467A1 (de
Inventor
Jean-François DIONNE
Stewes Bourban
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Swatch Group Research and Development SA
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Swatch Group Research and Development SA
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Publication date
Priority to EP10167859.7A priority Critical patent/EP2402467B1/de
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to EP11725466.4A priority patent/EP2588635B1/de
Priority to PCT/EP2011/060041 priority patent/WO2012000803A2/fr
Priority to JP2013517158A priority patent/JP2013531736A/ja
Priority to CN201180032311.0A priority patent/CN103038377B/zh
Priority to CH03002/12A priority patent/CH705500B1/fr
Priority to US13/805,230 priority patent/US20130153097A1/en
Publication of EP2402467A1 publication Critical patent/EP2402467A1/de
Priority to HK13111451.4A priority patent/HK1184198A1/zh
Application granted granted Critical
Publication of EP2402467B1 publication Critical patent/EP2402467B1/de
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    • 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

Definitions

  • the invention relates to the use of a precipitate for curing an 18-carat gold alloy.
  • the invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of such an alloy.
  • the main applications are watchmaking, jewelery, jewelery, and dentistry.
  • the dissolution of alloying elements is the most commonly used method, often empirically, and provides only poor hardness, of the order of 150 to 155 HV on the Vickers scale in the best case .
  • a patent EP 0 978 572 in the name of Hafner GmbH describes an alloy consisting of 70% to 80% gold, 15% to 25% copper, 0% to 15% silver, and 0.1% to 5% gallium, which, unexplained, oxidizes little during a second treatment at 400 ° C following a first treatment at 800 ° C, and acquires a hardness that increases with time at room temperature.
  • EP 0 978 572 A1 in the name of HAFNER describes an alloy with 70 to 80% gold and 15 to 25% copper, to which is added 0.1 to 5% gallium. According to certain variants it could still contain: 0.1 to 3% of zinc, and / or 0.5 to 5% of silver, and / or 0.1 to 0.5% of silicon, and / or of 0 , 1 to 2% iron and / or 0.1 to 0.3% indium, and / or 0.1 to 0.5% aluminum and / or 0.1 to 3% tin.
  • said Al 2 Au 5 aluminum and gold precipitate constitutes an intermetallic imparting to said alloy a hardness greater than 250 HV, to improve the structural hardening of said alloy.
  • said addition metal is silver.
  • one said additive metal is silver, and is completed by another addition metal of concentration lower than that of silver. More particularly, said other addition metal is copper.
  • said quenching is carried out by quenching with water.
  • said structuring income is carried out at least 24 hours after said sudden cooling.
  • the invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of an 18K gold alloy with improved hardness comprising a selected precipitate of aluminum and gold Al 2 Au 5 thus used and inserted into a CFC-faced cubic structure resulting from dissolving a mixture of gold, aluminum, said at least one adduct, and said selected aluminum and gold precipitate Al 2 At 5 , said component comprising at least 75% of gold, from 1.0% to 2.1% of aluminum, and the complement at 100%, of between 22.4% and 24.0%, of minus a chosen addition metal and further characterized in that said addition metal is selected from the following elements: silver, chromium, copper, iron, hafnium, manganese, niobium, palladium, platinum, vanadium.
  • the alloy retains the specific appearance of pure gold.
  • This alloy obtained, by its improved hardness, is resistant to scratches, and is entirely appropriate for timepieces, jewelery or jewelery, and in particular for their visible components such as glasses and watch frames, and structures jewelry, bracelets, clasps, buckles, and other items.
  • the invention provides a simple, reproducible method of implementation, making it possible to obtain with certainty a gold alloy with a required hardness, greater than 250 HV, with a short treatment time.
  • the alloy obtained is directly usable without requiring additional aging.
  • the invention uses a method of structural hardening, by the selection of particular elements, which are here chosen to form particular precipitates.
  • particular elements which are here chosen to form particular precipitates.
  • various precipitates that can form gold with other metals under very specific physico-chemical conditions, it is a question of choosing those which can be controlled, by the implementation of an appropriate treatment, the germination and growth, to optimize the mechanical characteristics, and in particular here to improve the hardness.
  • the mechanical characteristic that the present invention makes it possible to improve, by the creation of a particular process is the hardness, which concerns both the core hardness of the alloy, and the surface hardness which is very important in watches, jewelery, jewelery to resist scratches or at least to minimize the effects.
  • the inventive step of the invention was to search for the possibility of insertion, in a cubic face-centered or FCC structure, of precipitates, and to grow them in a controlled manner, so as to obtain a hardness greater than the usual hardness. .
  • the invention relates more particularly to the field of gold alloys with a high gold content, and particularly 18-carat alloys, comprising at least 75% of their weight of gold.
  • the process is carried out so as to obtain the Al 2 Au 5 precipitate, which provides, embedded in an alloy, a normal behavior during machining or processing operations. It is therefore necessary to obtain the creation of this precipitate Al 2 Au 5 , and preferably to obtain the creation of this precipitate Al 2 Au 5 alone, because it has better properties than the other two precipitates AlAu 2 and AlAu.
  • This precipitate Al 2 Au 5 must be obtained within an FCC structure.
  • a binary alloy composed solely of gold and aluminum is inconvenient to develop, and is very fragile, making it unsuitable for most jewelery and jewelery jobs. It is therefore necessary to stabilize the FCC phase by the incorporation of at least one other alloying element making it possible to ensure the intermetallic solubility at high temperature, and also to ensure the longest possible FCC phase; for a range of aluminum content as wide as possible.
  • the second metal may be selected from silver, chromium, copper, iron, hafnium, manganese, niobium, palladium, platinum, vanadium, this list is not exhaustive.
  • the invention has sought to create the phase diagram of the pseudo-binary alloy Au-Ag-Al, as visible on the figure 1 .
  • This diagram represents, in a conventional way, the different phases, as a function, on the one hand, of the abscissa of the aluminum concentration, that is to say on the ratio between the aluminum mass and the total mass of the alloy, and on the other hand on the ordinate of the temperature, here represented in degrees Celsius.
  • the diagram of the figure 1 represents the preferred case of a gold mass concentration of 75%, the preferred case of an 18-carat alloy.
  • a on figure 1 a first field called A on figure 1 , in which only the elements of the alloy in FCC form coexist on the one hand, and the precipitates of Al 2 Au 5 on the other hand.
  • the concentration of aluminum, to remain in this area, must remain below 2.1%.
  • the range of concentrations to be respected is 0.1% to 2.1% of aluminum in order to be certain to develop only Al 2 Au 5 .
  • a second domain called B on the figure 1 corresponds to a phase where the precipitates of Al 2 Au 5 and AlAu 2 coexist with the elements of the alloy in FCC form.
  • the third domain called C on the figure 1 corresponds to a phase where only the precipitates of AlAu 2 coexist with the elements of the alloy in FCC form.
  • the diagram of the figure 1 shows that, to obtain an alloy in an optimal composition in the domain A, a method of obtaining is to heat up all the elements of the alloy, then to be in the domain D of the figure 1 , corresponding to a dissolution of aluminum.
  • a dilution heat treatment at a temperature between the solidus and the liquidus delimiting the D domain, allows a homogeneous solution solution: the gold is in FCC structure, thanks to the chosen element or elements of addition, in particular the silver, and the FCC structure is stable.
  • High solubility of aluminum in the FCC_A1 phase is observed at high temperature, in particular at temperatures between 400 ° C. and 700 ° C. This or these addition elements also facilitate the solubility of aluminum in gold.
  • the alloy is then made metastable.
  • the rise in temperature carried out for example between about 400 ° C. and 700 ° C. for the end portion of area A, ideally around 650 ° C., is followed by rapid cooling, such as water quenching. , or similar.
  • rapid cooling such as water quenching. , or similar.
  • aluminum atoms do not have time to reorganize.
  • the alloy is subjected to structuring income treatment, in the temperature range defined by the solvus of the A domain for the aluminum concentration considered. In any case, this structuring income does not exceed the temperature of 400 ° C.
  • Al 2 Au 5 precipitates develop and grow.
  • the temperature of structuring income is greater than 200 ° C to facilitate this growth of precipitates, and also limit the duration of heat treatment.
  • the figure 2 is a Vickers hardness chart in ordinate as a function of time on the abscissa.
  • a structuring income at 200 ° C a hardness greater than 250 HV is obtained very quickly, after about 2 hours. This hardness will still increase if the structuring income treatment is prolonged, but asymptotically, and it is hardly useful, even if the maximum hardness is sought, to prolong the treatment beyond ten or so years. hours, where one reaches a hardness of the order of 280 HV.
  • the figure 2 shows, for comparison, the hardness level of 150 HV obtained with an 18 K gold alloy, or 18 karat gold, conventional.
  • the structuring income is made at a lower temperature, for example 100 ° C, a hardness greater than 200 HV will be obtained after 10 to 15 hours, and the treatment must be further extended to reach a level of order of 250 HV.
  • the precipitate Al 2 Au 5 obtained is harder than gold.
  • the alloy contains no other metal than gold, aluminum, and an addition metal, preferably silver, chosen to increase intermetallic solubility and to maximize phase D, in terms of range amplitude of aluminum concentrations.
  • the invention differs from the prior art in that it creates the conditions for the development of Al 2 Au 5 precipitates, in an alloy of suitable composition comprising gold, aluminum, and at least one addition metal chosen for its ability to promote a stable FCC structure on the one hand, and to increase the solubility of aluminum in gold on the other hand, this addition metal being preferably 'money.
  • the optimum composition by weight is from 0.1% to 2.1% of aluminum, at least 75% of gold in order to respect the legal requirement in jewelery and jewelry, and the complement constituted by the metal of addition.
  • the addition metal can also be copper. It is also possible to combine several metals each having the properties that this adduct must have, namely the ability to promote a stable FCC structure on the one hand, and the ability to increase the solubility of the aluminum in gold on the other hand.
  • Silver is the best element, and the other metallic elements listed above can be added to adjust the tint of the alloy. This list of elements has been drawn up so that the elements contained therein satisfy the condition of increasing the solubility of aluminum in the FCC structure at high temperature.
  • copper is less favorable than silver for fulfilling these particular functions in the presence of gold and aluminum.
  • the use of copper is still possible for reasons of cost, but is much less favorable than silver, and should always, in case of employment, be combined with money, paying attention that the concentration of money always be greater than the concentration of copper in the alloy.
  • addition metals than silver for example selected from chromium, copper, iron, hafnium, manganese, niobium, palladium, platinum, vanadium
  • these elements alone: chromium, copper, iron, hafnium, manganese, niobium, palladium, platinum, vanadium
  • each new composition with different addition metals requires a complete experiment in order to define the corresponding phase diagrams, nonexistent in the literature, to analyze the precipitates and other intermetallics created within each of the phases, to verify that these compounds do not alter the mechanical properties of the gold-based alloy.
  • These studies and experiments are long and expensive and can not be conducted at random. They are also intended to determine, on a case by case basis, the range of aluminum concentrations to be observed in order to obtain Al 2 Au 5 precipitates, and preferably only this one.
  • the invention makes it possible to obtain a gold-based alloy with improved hardness, which consists of a mixture comprising in mass at least 75% gold, from 0.1% to 2.1%. % of a second metal chosen for its ability to form precipitated with gold, and a complement consisting of at least one addition metal chosen for its ability to promote a stable face-centered cubic FCC structure on the one hand, and for its ability to increase the solubility of said second metal in the or on the other hand, this mixture also comprising at least one such precipitate of the second metal with the gold selected to obtain a hardness greater than 250 HV.
  • the second metal is aluminum and the precipitate selected is the Al 2 Au 5 aluminum and gold precipitate, which makes it possible to obtain an alloy with very good hardness characteristics, which is greater than 250 HV, and in particular in the vicinity of 280 HV.
  • This Al 2 Au 5 precipitate also provides the alloy with good resistance during its transformation or its machining, because it does not make the alloy brittle.
  • the addition metal is silver, which ensures good dissolution of the entire mixture.
  • the addition metal is silver and is supplemented with another addition metal to adjust the color of the alloy.
  • the selection of selected precipitates is restricted to a single precipitate.
  • the structuring income is made at least 24 hours after the quenching.
  • Aluminum is preferably chosen for the second metal, and the precipitate of Al 2 Au 5 aluminum and gold is selected as the selected precipitate.
  • the addition metal is silver.
  • silver is used as the addition metal and another addition metal with silver-like characteristics is added to adjust the color of the alloy.
  • the invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of such an alloy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adornments (AREA)
  • Dental Preparations (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Display Devices Of Pinball Game Machines (AREA)
  • Powder Metallurgy (AREA)

Claims (8)

  1. Verwendung eines Niederschlags zum Härten einer Goldlegierung mit 18 Karat, dadurch gekennzeichnet, dass
    der Niederschlag ein Niederschlag aus Aluminium und Gold, Al2Au5, ist, um eine Goldlegierung zu härten, die wenigstens enthält: 75 % Gold, 0,1 % bis 2,1 % Aluminium und für den Rest auf 100 % wenigstens ein additives Metall im Bereich von 22,4 % bis 24,0 %, das einerseits wegen seiner Eignung, eine stabile FCC kubisch-flächenzentrierte Struktur, zu begünstigen, und andererseits wegen seiner Eignung, die Löslichkeit von Aluminium in Gold gewählt ist, enthält, wobei die Verwendung aus dem Einbringen des Niederschlags aus Aluminium und Gold, Al2Au5 in eine FCC kubisch-flächenzentrierte Struktur resultiert, die aus dem Bringen in Lösung des Gemisches, das aus Gold, Aluminium, dem wenigstens einen zusätzlichen Metall und Niederschlägen von Aluminium mit Gold gebildet ist, resultiert,
    dass das Einbringen durch ein Verfahren zum Erhalten einer Legierung mit 18 Karat auf Goldbasis mit verbesserter Härte ausgeführt wird, gemäß dem:
    - ein zweites Metall, das Aluminium ist, wegen seiner Eignung, Niederschläge mit Gold zu bilden, gewählt wird;
    - wenigstens ein zusätzliches Metall wegen seiner Eignung, einerseits eine stabile FCC kubisch-flächenzentrierte Struktur zu begünstigen, und andererseits wegen seiner Eignung, die Löslichkeit bei hoher Temperatur von Aluminium im Gold zu erhöhen, gewählt wird;
    - Bedingungen zum Einbringen der Niederschläge aus Aluminium mit Gold in eine FCC kubisch-flächenzentrierte Struktur, die aus dem Bringen in Lösung eines Gemisches aus Gold, Aluminium und dem wenigstens einen zusätzlichen Metall resultiert, erzeugt werden;
    - ein Gemisch vorbereitet wird, das wenigstens 75 Gew.-% Gold, 0,5 Gew.-% bis 2,1 Gew.-% Aluminium und einen Rest, der aus dem wenigstens einen zusätzlichen Metall gebildet ist, enthält, wobei Aluminium und das zusätzliche Metall gewählt werden, um wenigstens einen ausgewählten Niederschlag aus Aluminium mit Gold zu erhalten, um ein Intermetall zu bilden, das der Legierung eine Härte von mehr als 250 HV verleiht;
    - die Auswahl des wenigstens einen ausgewählten Niederschlags auf den einzigen ausgewählten Niederschlag aus Aluminium und Gold, Al2Au5, eingeschränkt wird,
    - das Gemisch durch Erwärmen auf eine Temperatur im Bereich von 650 °C bis 700 °C in Lösung gebracht wird;
    - eine plötzliche Abkühlung nach dem Einbringen in eine Lösung in Form eines Abschreckens erfolgt;
    - nach dem plötzlichen Abkühlen eine strukturierende Anlassverarbeitung bei einer Temperatur im Bereich von 200 °C bis 250 °C ausgeführt wird, um den ausgewählten Niederschlag aus Aluminium und Gold, Al2Au5, entstehen zu lassen,
    - bewirkt wird, dass der ausgewählte Niederschlag aus Aluminium und Gold, Al2Au5, kontrolliert aufwächst; wobei das strukturierende Anlassen während einer Dauer, die ausreicht, um die erforderliche Härte zu erhalten, beibehalten wird;
    - eine Abkühlung im Raumtemperatur ausgeführt wird,
    und außerdem dadurch gekennzeichnet, dass das zusätzliche Metall unter den folgenden Elementen gewählt ist: Silber, Chrom, Kupfer, Eisen, Hafnium, Mangan, Niob, Palladium, Platin, Vanadium.
  2. Verwendung eines Niederschlags nach Anspruch 1, dadurch gekennzeichnet, dass der Niederschlag aus Aluminium und Gold, Al2Au5, ein Intermetall bildet, das der Legierung eine Härte von mehr als 250 HV verleiht, um die strukturelle Aushärtung der Legierung zu verbessern.
  3. Verwendung eines Niederschlags nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das zusätzliche Metall Silber ist.
  4. Verwendung eines Niederschlags nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das zusätzliche Metall Silber ist und durch ein anderes zusätzliches Metall mit einer Konzentration, die kleiner als jene von Silber ist, vervollständigt wird.
  5. Verwendung eines Niederschlags nach Anspruch 4, dadurch gekennzeichnet, dass das andere zusätzliche Metall Kupfer ist.
  6. Verwendung eines Niederschlags nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das plötzliche Abkühlen durch ein Abschrecken mit Wasser erfolgt.
  7. Verwendung eines Niederschlags nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das strukturierende Anlassen wenigstens 24 Stunden nach dem plötzlichen Abkühlen ausgeführt wird.
  8. Zeitmessgerät, Schmuck- oder Juweliererstück, das wenigstens eine Komponente enthält, die aus einer Goldlegierung mit 18 Karat mit verbesserter Härte verwirklicht ist, die einen ausgewählten Niederschlag aus Aluminium und Gold, Al2Au5, enthält, der gemäß einem der vorhergehenden Ansprüche verwendet wird und in eine FCC kubisch-flächenzentrierte Struktur eingebracht wird, die aus dem Bringen in Lösung eines Gemisches resultiert, das aus Gold, Aluminium, dem wenigstens einen zusätzlichen Metall und dem ausgewählten Niederschlag aus Aluminium und Gold, Al2Au5, gebildet ist, wobei die Komponente wenigstens 75 % Gold, 0,1 % bis 2,1 % Aluminium und für den Rest auf 100 % wenigstens ein zusätzliches Metall im Bereich von 22,4 % bis 24,0 % enthält, das so gewählt ist und dadurch gekennzeichnet ist, dass das zusätzliche Metall gewählt ist unter den folgenden Elementen: Silber, Chrom, Kupfer, Eisen, Hafnium, Mangan, Niob, Palladium, Platin, Vanadium.
EP10167859.7A 2010-06-30 2010-06-30 Goldlegierung mit verbesserter Härte Active EP2402467B1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP10167859.7A EP2402467B1 (de) 2010-06-30 2010-06-30 Goldlegierung mit verbesserter Härte
PCT/EP2011/060041 WO2012000803A2 (fr) 2010-06-30 2011-06-16 Alliage d'or à dureté améliorée
JP2013517158A JP2013531736A (ja) 2010-06-30 2011-06-16 硬度が向上した金合金
CN201180032311.0A CN103038377B (zh) 2010-06-30 2011-06-16 具有提高的硬度的金合金
EP11725466.4A EP2588635B1 (de) 2010-06-30 2011-06-16 Goldlegierungen mit verbesserten härte
CH03002/12A CH705500B1 (fr) 2010-06-30 2011-06-16 Alliage d'or.
US13/805,230 US20130153097A1 (en) 2010-06-30 2011-06-16 Gold alloy with improved hardness
HK13111451.4A HK1184198A1 (zh) 2010-06-30 2013-10-10 具有提高的硬度的金合金

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP10167859.7A EP2402467B1 (de) 2010-06-30 2010-06-30 Goldlegierung mit verbesserter Härte

Publications (2)

Publication Number Publication Date
EP2402467A1 EP2402467A1 (de) 2012-01-04
EP2402467B1 true EP2402467B1 (de) 2015-06-17

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US (1) US20130153097A1 (de)
EP (2) EP2402467B1 (de)
JP (1) JP2013531736A (de)
CN (1) CN103038377B (de)
CH (1) CH705500B1 (de)
HK (1) HK1184198A1 (de)
WO (1) WO2012000803A2 (de)

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RU2665650C1 (ru) * 2017-09-18 2018-09-03 Юлия Алексеевна Щепочкина Ювелирный сплав
CN108677115A (zh) * 2018-04-24 2018-10-19 王振涛 一种黄金超深冷硬金工艺
EP3800511B1 (de) * 2019-10-02 2022-05-18 Nivarox-FAR S.A. Schwenkachse eines regulierorgans
CN112708797A (zh) * 2020-11-25 2021-04-27 西安汇创贵金属新材料研究院有限公司 一种紫色金合金及其制备方法
US11268174B1 (en) * 2021-06-10 2022-03-08 Chow Sang Sang Jewellery Company Limited Jewelry alloy
WO2023110997A1 (fr) * 2021-12-15 2023-06-22 Rolex Sa Matériau composite à matrice métallique pour pièce d'horlogerie
CN115612887B (zh) * 2022-08-12 2024-04-12 深圳市沃尔弗斯珠宝实业股份有限公司 一种高强度k金首饰及其制备方法

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CN101565783B (zh) * 2009-05-27 2011-01-19 上海交通大学 具有18k斯斑效应金合金及其制备方法

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Publication number Publication date
EP2588635B1 (de) 2016-04-06
EP2402467A1 (de) 2012-01-04
WO2012000803A3 (fr) 2012-09-20
CN103038377A (zh) 2013-04-10
CH705500B1 (fr) 2015-12-31
WO2012000803A2 (fr) 2012-01-05
HK1184198A1 (zh) 2014-01-17
EP2588635A2 (de) 2013-05-08
CN103038377B (zh) 2016-04-27
JP2013531736A (ja) 2013-08-08
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