EP2402467A1 - Gold alloy with improved hardness - Google Patents

Gold alloy with improved hardness Download PDF

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Publication number
EP2402467A1
EP2402467A1 EP20100167859 EP10167859A EP2402467A1 EP 2402467 A1 EP2402467 A1 EP 2402467A1 EP 20100167859 EP20100167859 EP 20100167859 EP 10167859 A EP10167859 A EP 10167859A EP 2402467 A1 EP2402467 A1 EP 2402467A1
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EP
European Patent Office
Prior art keywords
metal
gold
precipitate
addition
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.)
Granted
Application number
EP20100167859
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German (de)
French (fr)
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EP2402467B1 (en
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/en
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to PCT/EP2011/060041 priority patent/WO2012000803A2/en
Priority to JP2013517158A priority patent/JP2013531736A/en
Priority to CN201180032311.0A priority patent/CN103038377B/en
Priority to US13/805,230 priority patent/US20130153097A1/en
Priority to CH03002/12A priority patent/CH705500B1/en
Priority to EP11725466.4A priority patent/EP2588635B1/en
Publication of EP2402467A1 publication Critical patent/EP2402467A1/en
Priority to HK13111451.4A priority patent/HK1184198A1/en
Application granted granted Critical
Publication of EP2402467B1 publication Critical patent/EP2402467B1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14Changing 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
    • AHUMAN NECESSITIES
    • A44HABERDASHERY; JEWELLERY
    • A44CPERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00Making jewellery or other personal adornments
    • A44C27/001Materials for manufacturing jewellery
    • A44C27/002Metallic materials
    • A44C27/003Metallic alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C5/00Alloys based on noble metals
    • C22C5/02Alloys based on gold

Definitions

  • the invention relates to a gold-based alloy having improved hardness.
  • the invention also relates to a process for obtaining a gold-based alloy with improved hardness.
  • 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.
  • the invention relates to a gold-based alloy, characterized in that it consists of a mixture comprising in mass at least 75% of gold, from 0.1% to 2.1% of a second metal chosen for its ability to form intermetallics 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 gold on the other hand, said mixture further comprising at least one said precipitate of said second metal with the selected gold to obtain a hardness greater than 250 HV.
  • said second metal is aluminum and said selected precipitate is the aluminum and gold Al 2 Au 5 precipitate.
  • said addition metal is silver.
  • said addition metal is silver and is supplemented by another addition metal of concentration lower than that of silver.
  • said other addition metal is copper.
  • the selection of said at least one selected precipitate is restricted to a single precipitate.
  • said structuring income is made at least 24 hours after said sudden cooling.
  • aluminum is chosen for said second metal, and the precipitate of aluminum and gold Al 2 Au 5 is chosen for the said selected precipitate.
  • silver is chosen for said addition metal.
  • silver is chosen for said addition metal, and another addition metal of concentration lower than that of silver is added thereto.
  • copper is chosen for the said other additive metal.
  • the invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of such an alloy.
  • 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.
  • 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 D domain 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.
  • the structuring tempering temperature is greater than 200 ° C to facilitate this growth of the precipitates, and also limit the duration of the 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 18 K gold alloy, or 18 K, 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 must have this additive metal, namely the ability to promote a stable FCC structure on the one hand, and the ability to increase the solubility of 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 for example selected from chromium, copper, iron, hafnium, manganese, niobium, palladium, platinum, vanadium, this list not being exhaustive, it is necessary to pay attention to the fact that the aluminum could form precipitates with some of these metals of addition, but that one wishes to form preferentially precipitates Al 2 Au 5 . So, in addition to silver and aluminum, it is preferable to use 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 beach of aluminum concentrations to respect to obtain precipitates Al 2 Au 5 , 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 precipitates with gold, and a complement consisting of at least one addition metal chosen for its ability to favor a stable face-centered cubic FCC structure on the one hand, and for its ability to increase the solubility of said second metal in gold on the other hand, this mixture further 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 especially 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)
  • Powder Metallurgy (AREA)
  • Display Devices Of Pinball Game Machines (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Gold-based alloy (I) comprises a mixture comprising gold (at least 75 wt.%), a second metal (0.1-2.1 wt.%) selected for its ability to form precipitates with gold, and at least one filler metal (balance) selected for its ability to sustain a stable face-centered cubic structure and for its ability to increase the solubility of the second metal in gold, where the mixture further comprises at least one precipitate of the second metal with gold selected to obtain a hardness of greater than 250 HV. An independent claim is included for preparing (I) comprising: selecting the second metal; selecting the filler metal; creating the insertion condition in a face-centered cubic structure resulting of the dissolution of a mixture of gold, the second metal, and the filler metal and precipitates of the second metal with gold; preparing the mixture; placing the mixture at 400-700[deg] C; rapid cooling; after rapid cooling, treating obtained material at 200-400[deg] C for producing the selected precipitate of the second metal with gold; increasing the selected precipitate to obtained material for a sufficient time to obtain the required hardness; and cooling the material in room temperature.

Description

L'invention concerne un alliage à base d'or présentant une dureté améliorée.The invention relates to a gold-based alloy having improved hardness.

L'invention concerne encore un procédé d'obtention d'un alliage à base d'or, à dureté améliorée.The invention also relates to a process for obtaining a gold-based alloy with improved hardness.

L'invention concerne encore une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé en un tel alliage.The invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of such an alloy.

L'invention a pour but la réalisation d'un alliage à base d'or, qui possède des qualités de dureté améliorées par rapport, non seulement à l'or pur, mais aussi par rapport aux alliages à base d'or connus.It is an object of the invention to provide a gold-based alloy which has improved hardness qualities compared not only to pure gold, but also to known gold-based alloys.

Les applications principales sont l'horlogerie, la bijouterie, la joaillerie, et la dentisterie.The main applications are watchmaking, jewelery, jewelery, and dentistry.

Le durcissement de l'or est un problème ancien, qui, depuis l'antiquité, à conduit à l'utilisation d'alliages afin d'obtenir des caractéristiques mécaniques suffisantes pour assurer au moins la tenue des objets fabriqués. En effet, le procédé d'écrouissage par déformation plastique du matériau, qui s'applique bien à certains métaux, s'applique mal à l'or puisque celui-ci ne présente que très peu de consolidation lors de la déformation, et, de plus, recristallise à des températures relativement basses. Le procédé d'affinement de la taille des grains, permettant théoriquement d'élever la limite élastique du matériau, n'est pas approprié non plus pour l'or, qui a une structure cubique faces centrées, dite ci-après FCC, puisqu'il y a suffisamment de systèmes de glissement actifs pour le libre passage des dislocations d'un grain à un autre.The hardening of gold is an ancient problem, which, since antiquity, has led to the use of alloys in order to obtain mechanical characteristics sufficient to ensure at least the holding of artifacts. Indeed, the process of hardening by plastic deformation of the material, which applies well to certain metals, applies poorly to gold since it has only very little consolidation during deformation, and more, recrystallizes at relatively low temperatures. The method of refining the grain size, theoretically allowing to raise the elastic limit of the material, is not suitable either for the gold, which has a face-centered cubic structure, hereinafter referred to as FCC, since there are enough active sliding systems for the free passage of dislocations from one grain to another.

La mise en solution d'éléments d'alliage est le procédé le plus couramment employé, souvent de façon empirique, et ne procure que des duretés médiocres, de l'ordre de 150 à 155 HV sur l'échelle Vickers dans le meilleur des cas.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 .

Différentes tentatives ont été faites, par exemple pour affiner la taille de grain comme dans le document de brevet EP 0 284 699 au nom de Steinemann avec un alliage binaire contenant de l'or et un autre métal choisi parmi l'aluminium, le gallium ou le silicium, ou encore avec un alliage pseudo-binaire similaire comportant encore du cuivre, pour au plus 15% de la concentration en or. Un tel composé donne une structure cubique centrée et une taille de grain inférieure à 50 microns, ce qui permet d'obtenir une certaine ductilité, ce qui n'est pas la qualité recherchée ici.Various attempts have been made, for example to refine the grain size as in the patent document EP 0 284 699 in the name of Steinemann with a binary alloy containing gold and another metal selected from aluminum, gallium or silicon, or with a similar pseudo-binary alloy still containing copper, for at most 15% of the gold concentration. Such a compound gives a centered cubic structure and a grain size less than 50 microns, which allows to obtain a certain ductility, which is not the quality sought here.

On connaît encore la préparation d'alliages dentaires présentant une dureté croissante dans le temps et à la température du corps, par le document de brevet US 5 338 378 au nom de Université de Kyushu, qui met en oeuvre un alliage avec 67% à 82 % d'or, 18% à 33% de cuivre, et 2% à 8% d'au moins un autre métal pris parmi le gallium, l'aluminium et le zinc, cet alliage subit une opération de trempe après une chauffe entre 650 et 700°C, avant son utilisation. De façon similaire un brevet EP 0 978 572 au nom de Hafner GmbH décrit un alliage composé de 70% à 80% d'or, de 15% à 25% de cuivre, de 0% à 15% d'argent, et de 0,1 % à 5% de gallium, qui, de façon inexpliquée, s'oxyde peu lors d'un second traitement à 400°C qui suit un premier traitement à 800°C, et acquiert une dureté qui croît avec le temps à température ambiante.The preparation of dental alloys with increasing hardness in time and at body temperature is still known from the patent document US 5,338,378 in the name of Kyushu University, which uses an alloy with 67% to 82% gold, 18% to 33% copper, and 2% to 8% of at least one other metal taken from gallium, aluminum and zinc, this alloy undergoes a quenching operation after heating to 650-700 ° C, prior to use. Similarly 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.

En somme, les procédés connus sont empiriques, peu maîtrisés, et donnent souvent naissance à des alliages qui, d'une part n'ont qu'une dureté moyenne, et d'autre part ont une coloration très particulière et très différente de celle de l'or pur.In short, the known processes are empirical, poorly controlled, and often give rise to alloys which, on the one hand have a moderate hardness, and on the other hand have a very particular coloring and very different from that of pure gold.

Il s'agit, dans le cadre de l'invention, de mettre au point un alliage qui possède des propriétés de bonne dureté superficielle, supérieure à 250 HV sur l'échelle Vickers, ainsi que des propriétés de dureté équivalentes à coeur, en comparaison avec les duretés de l'ordre de 155 HV couramment obtenus par mise en solution d'éléments d'alliage métalliques.In the context of the invention, it is a question of developing an alloy which has properties of good surface hardness, greater than 250 HV on the Vickers scale, as well as hardness properties equivalent to core, in comparison with the hardnesses of the order of 155 HV commonly obtained by dissolving metal alloy elements.

Il est, encore, important de pouvoir conserver l'aspect de l'or, ainsi que son éclat.It is still important to be able to maintain the appearance of gold, as well as its brilliance.

A cet effet l'invention concerne un alliage à base d'or, caractérisé en ce qu'il est constitué d'un mélange comportant en masse au moins 75% d'or, de 0,1 % à 2,1% d'un second métal choisi pour son aptitude à constituer des intermétalliques avec l'or, et un complément constitué d'au moins un métal d'addition choisi pour son aptitude à favoriser une structure cubique faces centrées FCC stable d'une part, et pour son aptitude à augmenter la solubilité dudit second métal dans l'or d'autre part, ledit mélange comportant encore au moins un dit précipité dudit second métal avec l'or sélectionné pour obtenir une dureté supérieure à 250 HV.For this purpose, the invention relates to a gold-based alloy, characterized in that it consists of a mixture comprising in mass at least 75% of gold, from 0.1% to 2.1% of a second metal chosen for its ability to form intermetallics 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 gold on the other hand, said mixture further comprising at least one said precipitate of said second metal with the selected gold to obtain a hardness greater than 250 HV.

Selon une caractéristique de l'invention, ledit second métal est l'aluminium et ledit précipité sélectionné est le précipité d'aluminium et d'or Al2Au5.According to one characteristic of the invention, said second metal is aluminum and said selected precipitate is the aluminum and gold Al 2 Au 5 precipitate.

Selon une autre caractéristique de l'invention, ledit métal d'addition est l'argent.According to another characteristic of the invention, said addition metal is silver.

Selon une autre caractéristique encore de l'invention, ledit métal d'addition est l'argent et est complété par un autre métal d'addition de concentration inférieure à celle de l'argent.According to yet another feature of the invention, said addition metal is silver and is supplemented by another addition metal of concentration lower than that of silver.

Selon une caractéristique particulière de l'invention, ledit autre métal d'addition est le cuivre.According to a particular characteristic of the invention, said other addition metal is copper.

L'invention concerne encore un procédé d'obtention d'un alliage à base d'or, à dureté améliorée, caractérisé en ce que :

  • on choisit un second métal pour son aptitude à constituer des précipités avec l'or ;
  • on choisit au moins un métal d'addition pour son aptitude à favoriser une structure cubique faces centrées FCC stable d'une part, et pour son aptitude à augmenter la solubilité à haute température dudit second métal dans l'or d'autre part ;
  • on crée les conditions d'insertion, dans une structure cubique faces centrées FCC résultant de la mise en solution d'un mélange d'or, dudit second métal, et dudit au moins un métal d'addition, de précipités dudit second métal avec l'or ;
  • on prépare un mélange comportant en masse au moins 75% d'or, de 0,1% à 2,1% dudit second métal, et un complément constitué dudit au moins un métal d'addition, ledit second métal et ledit métal d'addition étant choisis pour obtenir au moins un précipité sélectionné dudit second métal avec l'or d'une dureté supérieure à 250 HV ;
  • on met en solution ledit mélange par une mise en température entre 400°C et 700°C ;
  • on effectue un refroidissement brusque après ladite mise en solution ;
  • on effectue après ledit refroidissement brusque un traitement de revenu structurant à une température comprise entre 200°C et 400°C pour donner naissance audit au moins un précipité sélectionné dudit second métal avec l'or ;
  • on fait croître de façon contrôlée ledit au moins un précipité sélectionné en maintenant ledit revenu structurant pendant une durée suffisante pour obtenir la dureté requise ;
  • on effectue un refroidissement à l'ambiante.
The invention also relates to a process for obtaining a gold-based alloy, with improved hardness, characterized in that:
  • a second metal is chosen for its ability to form precipitates with gold;
  • at least one addition metal is chosen for its ability to favor a stable cubic face-centered FCC structure on the one hand, and for its ability to increase the high temperature solubility of said second metal in gold on the other hand;
  • the insertion conditions are created in a cubic face-centered FCC structure resulting from the dissolution of a mixture of gold, of said second metal, and of said at least one addition metal, of precipitates of said second metal with 'gold ;
  • a mixture comprising at least 75% gold, from 0.1% to 2.1% of said second metal, and a complement consisting of said at least one additive metal, said second metal and said metal are prepared addition being selected to obtain at least one selected precipitate of said second metal with gold of hardness greater than 250 HV;
  • said mixture is brought into solution by bringing the temperature between 400 ° C and 700 ° C;
  • an abrupt cooling is effected after said dissolution;
  • after said quenching is carried out a structuring income treatment at a temperature between 200 ° C and 400 ° C to give rise to said at least one selected precipitate of said second metal with gold;
  • said at least one selected precipitate is controlledly grown by maintaining said structuring income for a time sufficient to obtain the required hardness;
  • cooling is carried out at room temperature.

Selon une caractéristique de l'invention, on restreint la sélection dudit au moins un précipité sélectionné à un seul précipité.According to one characteristic of the invention, the selection of said at least one selected precipitate is restricted to a single precipitate.

Selon une autre caractéristique de l'invention, on effectue ledit revenu structurant au moins 24 heures après ledit refroidissement brusque.According to another characteristic of the invention, said structuring income is made at least 24 hours after said sudden cooling.

Selon une caractéristique particulière de l'invention, on choisit pour ledit second métal l'aluminium, et on choisit pour ledit précipité sélectionné le précipité d'aluminium et d'or Al2Au5.According to a particular characteristic of the invention, aluminum is chosen for said second metal, and the precipitate of aluminum and gold Al 2 Au 5 is chosen for the said selected precipitate.

Selon une autre caractéristique de l'invention, on choisit pour ledit métal d'addition l'argent.According to another characteristic of the invention, silver is chosen for said addition metal.

Selon une autre caractéristique de l'invention, on choisit pour ledit métal d'addition l'argent et on y ajoute un autre métal d'addition de concentration inférieure à celle de l'argent.According to another characteristic of the invention, silver is chosen for said addition metal, and another addition metal of concentration lower than that of silver is added thereto.

De façon particulière, on choisit pour ledit autre métal d'addition le cuivre.In a particular way, copper is chosen for the said other additive metal.

L'invention concerne encore une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé en un tel alliage.The invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of such an alloy.

Dans le mode de réalisation préférentiel de la description, concernant un alliage 18 carats, l'alliage conserve l'aspect spécifique à l'or pur. Cet alliage obtenu, par sa dureté améliorée, est résistant aux rayures, et est tout à fait approprié pour des pièces d'horlogerie, de bijouterie ou de joaillerie, et en particulier pour leurs composants visibles tels que lunettes et carrures de montres, et structures de bijoux, bracelets, fermoirs, boucles, et autres articles.In the preferred embodiment of the description, concerning an 18-carat alloy, 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.

L'invention procure un procédé de mise en oeuvre simple, reproductible, permettant d'obtenir avec certitude un alliage d'or avec une dureté requise, supérieure à 250 HV, avec une durée de traitement faible. L'alliage obtenu est directement utilisable, sans nécessiter de vieillissement supplémentaire.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.

D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description qui va suivre, en référence aux dessins annexés, où :

  • la figure 1 est un diagramme de phases d'un alliage pseudo-binaire Au-Ag-Al selon l'invention, dans un exemple d'alliage à 18 carats, et qui représente les différentes phases, en fonction, d'une part en abscisse de la concentration d'aluminium, c'est-à-dire du rapport entre la masse d'aluminium et la masse totale de l'alliage, et d'autre part en ordonnée de la température, ici représentée en degrés Celsius ;
  • la figure 2 est un diagramme de dureté Vickers en ordonnée, en fonction du temps en abscisse, d'un alliage selon l'invention réalisé dans un domaine préférentiel A du diagramme de la figure 1 en comparaison d'un or 18 carats obtenu de manière standard.
Other features and advantages of the invention will appear on reading the description which follows, with reference to the appended drawings, in which:
  • the figure 1 is a phase diagram of an Au-Ag-Al pseudo-binary alloy according to the invention, in an 18-carat alloy example, and which represents the different phases, depending, on the one hand, on the abscissa of the aluminum concentration, that is to say the ratio between the mass of aluminum and the total mass of the alloy, and secondly the ordinate of the temperature, here represented in degrees Celsius;
  • the figure 2 is a Vickers hardness chart on the ordinate, as a function of time on the abscissa, of an alloy according to the invention produced in a preferred domain A of the diagram of FIG. figure 1 compared to a standard 18-carat gold.

L'invention a pour but la réalisation d'un alliage à base d'or, qui possède des qualités de dureté améliorées par rapport, non seulement à l'or pur, mais aussi par rapport aux alliages à base d'or connus.It is an object of the invention to provide a gold-based alloy which has improved hardness qualities compared not only to pure gold, but also to known gold-based alloys.

L'invention met en oeuvre un procédé de durcissement structural, par la sélection d'éléments particuliers, qui sont ici choisis pour former des précipités particuliers. Parmi les différents précipités que peut former l'or avec d'autres métaux, dans des conditions physico-chimiques bien particulières, il s'agit de choisir ceux dont on peut contrôler, par la mise en oeuvre d'un traitement approprié, la germination et la croissance, pour optimiser les caractéristiques mécaniques, et en particulier ici pour améliorer la dureté.The invention uses a method of structural hardening, by the selection of particular elements, which are here chosen to form particular precipitates. Among the 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.

En particulier, la caractéristique mécanique que la présente invention permet d'améliorer, par la création d'un procédé particulier, est la dureté, qui concerne aussi bien la dureté à coeur de l'alliage, que la dureté superficielle qui est très importante en horlogerie, bijouterie, joaillerie pour résister aux rayures ou du moins pour en minimiser les effets.In particular, 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.

On est donc dans un cas de figure très différent de la plupart des alliages d'or, utilisés en bijouterie, qui sont élaborés le plus souvent de façon à comporter le titre d'or minimal garantissant un aspect proche de celui de l'or, et avec la recherche d'une grande formabilité, de façon à permettre le laminage, ou encore l'étirement, en corps creux ou en feuilles, faciles à mettre en forme, et faciles à souder.We are thus in a situation very different from most gold alloys, used in jewelery, which are most often elaborated so as to include the minimal gold title guaranteeing an appearance close to that of gold, and with the search for great formability, so as to allow rolling or stretching, hollow bodies or sheets, easy to form, and easy to weld.

La démarche inventive de l'invention a consisté à rechercher la possibilité d'insertion, dans une structure cubique faces centrées ou FCC, de précipités, et de les y faire croître de manière contrôlée, de façon à obtenir une dureté supérieure à la dureté usuelle.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. .

L'invention concerne plus particulièrement le domaine des alliages d'or à haute teneur en or, et tout particulièrement les alliages 18 carats, comportant au moins 75% de leur poids d'or.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.

La sélection de l'aluminium est propre à l'invention, en raison de l'aptitude de ce métal à former avec l'or différents précipités : Al2Au5, AlAu2, AlAu. Ces trois précipités permettent d'obtenir des alliages avec une dureté améliorée.The selection of aluminum is peculiar to the invention, because of the ability of this metal to form with gold different precipitates: Al 2 Au 5 , AlAu 2 , AlAu. These three precipitates make it possible to obtain alloys with improved hardness.

On préfère conduire le procédé de façon à obtenir le précipité Al2Au5, qui procure, incorporé dans un alliage, une tenue normale au cours d'opérations d'usinage ou de transformation. Il s'agit donc d'obtenir la création de ce précipité Al2Au5, et, de préférence, d'obtenir la création de ce précipité Al2Au5 seul, car il possède de meilleures propriétés que les deux autres précipités AlAu2 et AlAu.It is preferred to conduct the process 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.

La création de ce précipité Al2Au5 doit être obtenue au sein d'une structure FCC. Un alliage binaire composé uniquement d'or et d'aluminium est malcommode à élaborer, et est très fragile, ce qui le rend inapte à la plupart des emplois en bijouterie ou joaillerie. Il est donc nécessaire de stabiliser la phase FCC par l'incorporation d'au moins un autre élément d'alliage permettant d'assurer la solubilité intermétallique à haute température, et aussi d'assurer une phase FCC la plus longue possible, c'est-à-dire pour une plage de teneur d'aluminium la plus large possible.The creation of 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.

Différents essais d'alliages pseudo-binaires ont été testés.Various tests of pseudo-binary alloys were tested.

Le second métal peut être choisi parmi l'argent, le chrome, le cuivre, le fer, le hafnium, le manganèse, le niobium, le palladium, le platine, le vanadium, cette liste n'étant pas exhaustive.The second metal may be selected from silver, chromium, copper, iron, hafnium, manganese, niobium, palladium, platinum, vanadium, this list is not exhaustive.

L'expérimentation démontre que le choix de l'argent est le plus particulièrement favorable à la solubilité intermétallique à haute température, et à l'obtention d'une phase FCC longue, car la miscibilité argent-or est complète, et car l'argent peut dissoudre également de l'aluminium.Experimentation shows that the choice of silver is most particularly favorable to the intermetallic solubility at high temperature, and to obtaining a long FCC phase, because the miscibility silver-gold is complete, and because the silver can also dissolve aluminum.

De façon innovante, l'invention s'est attachée à créer le diagramme de phases de l'alliage pseudo-binaire Au-Ag-Al, tel que visible sur la figure 1. Ce diagramme représente de façon classique les différentes phases, en fonction, d'une part en abscisse de la concentration d'aluminium, c'est-à-dire du rapport entre la masse d'aluminium et la masse totale de l'alliage, et d'autre part en ordonnée de la température, ici représentée en degrés Celsius. Le diagramme de la figure 1 représente le cas préféré d'une concentration en masse d'or de 75%, soit le cas préféré d'un alliage 18 carats.In an innovative way, 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.

C'est un diagramme à miscibilité partielle, et l'on observe des limites de solubilité, sensiblement verticales sur le diagramme, qui séparent des phases chacune de composition définie et différente de la voisine. Dans chacune de ces phases, les atomes se réorganisent localement pour former des précipités, qui sont des composés définis de composition fixe.It is a partially miscible diagram, and there are solubility limits, substantially vertical in the diagram, which separate phases each of defined composition and different from the neighbor. In each of these phases, the atoms reorganize locally to form precipitates, which are defined compounds of fixed composition.

Afin d'obtenir le précipité Al2Au5 souhaité, et lui seul, il convient de se restreindre à un premier domaine appelé A sur la figure 1, dans lequel ne coexistent, que les éléments de l'alliage sous forme FCC d'une part, et les précipités de Al2Au5 d'autre part. La concentration en aluminium, pour rester dans ce domaine, doit rester inférieure à 2,1%. La plage de concentrations à respecter est 0,1% à 2,1% d'aluminium afin d'être certain de ne développer que du Al2Au5.To obtain the precipitated Al 2 In 5 hoped, and he alone, it should be restricted to 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 .

Un second domaine appelé B sur la figure 1 correspond à une phase où coexistent, avec les éléments de l'alliage sous forme FCC, les précipités de Al2Au5 et de AlAu2.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.

Le troisième domaine appelé C sur la figure 1 correspond à une phase où coexistent, avec les éléments de l'alliage sous forme FCC, seulement les précipités de AlAu2.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.

Le diagramme de la figure 1 montre que, pour obtenir un alliage dans une composition optimale dans le domaine A, un mode d'obtention consiste à opérer une mise en température de tous les éléments de l'alliage, puis de se trouver dans le domaine D de la figure 1, correspondant à une mise en solution de l'aluminium. Un traitement thermique de dilution, à une température entre le solidus et le liquidus délimitant le domaine D, permet une mise en solution homogène : l'or est en structure FCC, grâce à l'élément ou aux éléments d'addition choisis, notamment l'argent, et la structure FCC est stable. On observe une grande solubilité de l'aluminium dans la phase FCC_A1, à haute température, en particulier aux températures comprises entre 400°C et 700°C. Ce ou ces éléments d'addition facilitent aussi la solubilité de l'aluminium dans l'or.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 D domain 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.

L'alliage est ensuite rendu métastable. La montée en température, effectuée par exemple entre environ 400°C et 700°C pour la partie extrême du domaine A, idéalement aux environs de 650°C, est suivie d'un refroidissement rapide, tel qu'une trempe à l'eau, ou similaire. Ainsi, les atomes d'aluminium n'ont pas le temps de se réorganiser. Après une durée variable, mais de préférence voisine de 24 heures, l'alliage est soumis à un traitement de revenu structurant, dans la gamme de températures définie par le solvus du domaine A pour la concentration en aluminium considérée. En tout état de cause, ce revenu structurant ne dépasse pas la température de 400°C. Pendant ce revenu, les précipités de Al2Au5 se développent et croissent. De préférence, la température de revenu structurant est supérieure à 200°C pour faciliter cette croissance des précipités, et aussi limiter la durée du traitement thermique.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. Thus, aluminum atoms do not have time to reorganize. After a variable duration, but preferably close to 24 hours, 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. During this income, Al 2 Au 5 precipitates develop and grow. Preferably, the structuring tempering temperature is greater than 200 ° C to facilitate this growth of the precipitates, and also limit the duration of the heat treatment.

La figure 2 est un diagramme de dureté Vickers en ordonnée en fonction du temps en abscisse. On voit, sur l'exemple de la figure 2 d'un revenu structurant à 200°C, qu'une dureté supérieure à 250 HV est obtenue très vite, après environ 2 heures. Cette dureté va encore croître si l'on prolonge le traitement de revenu structurant, mais de façon asymptotique, et il n'est guère utile, même si on recherche la dureté maximale, de prolonger le traitement au-delà d'une dizaine d'heures, où l'on atteint une dureté de l'ordre de 280 HV. La figure 2 montre, à titre de comparaison, le niveau de dureté de 150 HV obtenu avec un alliage d'or 18 K, ou 18 carats, conventionnel.The figure 2 is a Vickers hardness chart in ordinate as a function of time on the abscissa. We see, on the example of figure 2 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 18 K gold alloy, or 18 K, conventional.

Si l'on effectue le revenu structurant à une température plus basse, par exemple 100°C, une dureté supérieure à 200 HV ne sera obtenue qu'après 10 à 15 heures, et le traitement doit encore être prolongé pour atteindre un niveau de l'ordre de 250 HV.If 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.

Le précipité Al2Au5 obtenu est plus dur que l'or.The precipitate Al 2 Au 5 obtained is harder than gold.

Il est essentiel, selon l'invention, de favoriser la présence du précipité Al2Au5, et, de préférence, de restreindre la formation de précipités constitués uniquement d'or et d'aluminium à ce seul précipité Al2Au5 qui possède les meilleures caractéristiques, pour permettre de résoudre le problème technique du durcissement de l'alliage.It is essential, according to the invention, to promote the presence of the Al 2 Au 5 precipitate, and preferably to restrict the formation of precipitates composed solely of gold and aluminum to this single precipitate Al 2 Au 5 which has the best features, to help solve the technical problem of hardening of the alloy.

De préférence, afin de permettre le développement optimal des précipités Al2Au5, l'alliage ne comporte pas d'autre métal que de l'or, de l'aluminium, et un métal d'addition, de préférence l'argent, choisi pour augmenter la solubilité intermétallique et pour allonger au maximum la phase D, en termes d'amplitude de plage de concentrations d'aluminium.Preferably, in order to allow the optimal development of Al 2 Au 5 precipitates, 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.

En somme, l'invention se distingue de l'art antérieur en ce qu'elle crée les conditions de développement de précipités Al2Au5, au sein d'un alliage de composition adéquate comportant de l'or, de l'aluminium, et au moins un métal d'addition choisi pour son aptitude à favoriser une structure FCC stable d'une part, et à augmenter la solubilité de l'aluminium dans l'or d'autre part, ce métal d'addition étant de préférence l'argent.In sum, 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.

La composition optimale en masse est de 0,1% à 2,1% d'aluminium, au moins 75% d'or afin de respecter l'aloi légal en bijouterie et joaillerie, et le complément constitué par le métal d'addition.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.

Le métal d'addition peut aussi être du cuivre. Il est, encore, possible de cumuler plusieurs métaux ayant chacun les propriétés que doit avoir ce métal d'addition, à savoir l'aptitude à favoriser une structure FCC stable d'une part, et l'aptitude à augmenter la solubilité de l'aluminium dans l'or d'autre part.The addition metal can also be copper. It is also possible to combine several metals each having the properties that must have this additive metal, namely the ability to promote a stable FCC structure on the one hand, and the ability to increase the solubility of aluminum in gold on the other hand.

L'argent est le meilleur élément, et les autres éléments métalliques de la liste énoncée plus haut peuvent être ajoutés pour ajuster la teinte de l'alliage. Cette liste des éléments a été dressée de sorte à ce que les éléments y figurant satisfont la condition d'augmenter la solubilité de l'aluminium dans la structure FCC à haute température.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.

Notamment le cuivre se montre moins favorable que l'argent pour remplir ces fonctions particulières en présence d'or et d'aluminium. L'emploi du cuivre reste possible pour des raisons de coût, mais est nettement moins favorable que l'argent, et devrait toujours, en cas d'emploi, être combiné à de l'argent, en prêtant attention que la concentration d'argent soit toujours supérieure à la concentration de cuivre dans l'alliage.In particular, 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.

Lors de l'emploi d'autres métaux d'addition que l'argent, par exemple choisis parmi le chrome, le cuivre, le fer, le hafnium, le manganèse, le niobium, le palladium, le platine, le vanadium, cette liste n'étant pas exhaustive, il convient de prêter attention au fait que l'aluminium pourrait former des précipités avec certains de ces métaux d'addition, mais qu'on souhaite former préférentiellement des précipités Al2Au5. Donc, en plus de l'argent et l'aluminium, il faut utiliser préférentiellement ces seuls éléments : le chrome, le cuivre, le fer, le hafnium, le manganèse, le niobium, le palladium, le platine, le vanadiumWhen using other addition metals than silver, for example selected from chromium, copper, iron, hafnium, manganese, niobium, palladium, platinum, vanadium, this list not being exhaustive, it is necessary to pay attention to the fact that the aluminum could form precipitates with some of these metals of addition, but that one wishes to form preferentially precipitates Al 2 Au 5 . So, in addition to silver and aluminum, it is preferable to use these elements alone: chromium, copper, iron, hafnium, manganese, niobium, palladium, platinum, vanadium

De plus, chaque nouvelle composition avec différents métaux d'addition nécessite de mener une expérimentation complète afin de définir les diagrammes de phase correspondants, inexistants dans la littérature, d'analyser les précipités et autres intermétalliques créés au sein de chacune des phases, de vérifier que ces composés n'altèrent pas les propriétés mécaniques de l'alliage à base d'or. Ces études et expérimentations sont longues et coûteuses et ne peuvent être menées au hasard. Elles ont encore pour but de déterminer, au cas par cas, la plage de concentrations d'aluminium à respecter pour obtenir des précipités Al2Au5, et de préférence seulement celui-ci.In addition, 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 beach of aluminum concentrations to respect to obtain precipitates Al 2 Au 5 , and preferably only this one.

En résumé, l'invention permet l'obtention d'un alliage à base d'or à dureté améliorée, qui est constitué d'un mélange comportant en masse au moins 75% d'or, de 0,1% à 2,1% d'un second métal choisi pour son aptitude à constituer des précipités avec l'or, et un complément constitué d'au moins un métal d'addition choisi pour son aptitude à favoriser une structure cubique faces centrées FCC stable d'une part, et pour son aptitude à augmenter la solubilité dudit second métal dans l'or d'autre part, ce mélange comportant encore au moins un tel précipité du second métal avec l'or sélectionné pour obtenir une dureté supérieure à 250 HV.In summary, 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 precipitates with gold, and a complement consisting of at least one addition metal chosen for its ability to favor a stable face-centered cubic FCC structure on the one hand, and for its ability to increase the solubility of said second metal in gold on the other hand, this mixture further comprising at least one such precipitate of the second metal with the gold selected to obtain a hardness greater than 250 HV.

De façon avantageuse, le second métal est l'aluminium et le précipité sélectionné est le précipité d'aluminium et d'or Al2Au5, qui permet d'obtenir un alliage avec de très bonnes caractéristiques de dureté, qui est supérieure à 250 HV, et notamment au voisinage de 280 HV. Ce précipité Al2Au5 procure également à l'alliage une bonne tenue lors de sa transformation ou de son usinage, car il ne rend pas l'alliage cassant.Advantageously, 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 especially 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.

Préférentiellement, le métal d'addition est l'argent, qui assure une bonne mise en solution de l'ensemble du mélange.Preferably, the addition metal is silver, which ensures good dissolution of the entire mixture.

Dans une réalisation particulière, le métal d'addition est l'argent et il est complété par un autre métal d'addition pour ajuster la teinte de l'alliage.In a particular embodiment, the addition metal is silver and is supplemented with another addition metal to adjust the color of the alloy.

Le procédé d'obtention d'un tel alliage à base d'or, à dureté améliorée, selon l'invention, comporte les étapes selon lesquelles:

  • on choisit un second métal pour son aptitude à constituer des précipités avec l'or ;
  • on choisit au moins un métal d'addition pour son aptitude à favoriser une structure cubique faces centrées FCC stable d'une part, et pour son aptitude à augmenter la solubilité dudit second métal dans l'or d'autre part ;
  • on crée les conditions d'insertion, dans une structure cubique faces centrées FCC résultant de la mise en solution d'un mélange d'or, de ce second métal, et de ce métal d'addition ou de ces métaux d'addition, de précipités du second métal avec l'or ;
  • on prépare un mélange comportant en masse au moins 75% d'or, de 0,1% à 2,1% du second métal, et un complément constitué du au moins un métal d'addition, ce second métal et ce métal d'addition étant choisis pour obtenir au moins un précipité sélectionné du second métal avec l'or d'une dureté supérieure à 250 HV ;
  • on met en solution ce mélange par une mise en température entre 400°C et 700 °C;
  • on effectue un refroidissement brusque après la mise en solution;
  • on effectue après ce refroidissement brusque un traitement de revenu structurant à une température comprise entre 200°C et 400°C pour donner naissance à au moins un précipité sélectionné du second métal avec l'or ;
  • on fait croître de façon contrôlée ce précipité sélectionné ou ces précipités sélectionnés en maintenant le revenu structurant pendant une durée suffisante pour obtenir la dureté requise ;
  • on effectue un refroidissement à l'ambiante.
The process for obtaining such a gold-based alloy, with improved hardness, according to the invention comprises the steps according to which:
  • a second metal is chosen for its ability to form precipitates with gold;
  • at least one addition metal is chosen for its ability to promote a stable FCC face-centered cubic structure on the one hand, and for its ability to increase the solubility of said second metal in gold on the other hand;
  • the insertion conditions are created in a cubic face-centered FCC structure resulting from the dissolving of a mixture of gold, of this second metal, and of this additive metal or of these addition metals, precipitated from the second metal with gold;
  • a mixture comprising, by mass, at least 75% gold, from 0.1% to 2.1% of the second metal, and a complement consisting of at least one addition metal, this second metal and said metal of addition being selected to obtain at least one selected precipitate of the second metal with gold of hardness greater than 250 HV;
  • this mixture is brought into solution by bringing the temperature to between 400 ° C. and 700 ° C .;
  • an abrupt cooling is carried out after the dissolution;
  • after this quenching, a structuring income treatment is carried out at a temperature of between 200 ° C. and 400 ° C. to give rise to at least one selected precipitate of the second metal with gold;
  • the selected precipitate or selected precipitates are controlled grown by maintaining the structuring income for a time sufficient to obtain the required hardness;
  • cooling is carried out at room temperature.

De façon préférée, on restreint la sélection de précipités sélectionnés à un seul précipité.Preferably, the selection of selected precipitates is restricted to a single precipitate.

Avantageusement, on effectue le revenu structurant au moins 24 heures après le refroidissement brusque.Advantageously, the structuring income is made at least 24 hours after the quenching.

De préférence, on choisit pour le second métal l'aluminium, et on choisit pour précipité sélectionné le précipité d'aluminium et d'or Al2Au5.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.

De façon avantageuse, on choisit comme métal d'addition l'argent.Advantageously, the addition metal is silver.

Dans une variante de réalisation, on choisit comme métal d'addition l'argent et on y ajoute un autre métal d'addition ayant des caractéristiques similaires à l'argent, pour ajuster la teinte de l'alliage.In an alternative embodiment, silver is used as the addition metal and another addition metal with silver-like characteristics is added to adjust the color of the alloy.

L'invention concerne encore une pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé en un tel alliage.The invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of such an alloy.

Claims (14)

Alliage à base d'or, caractérisé en ce qu'il est constitué d'un mélange comportant en masse au moins 75% d'or, de 0,1% à 2,1% d'un second métal choisi pour son aptitude à constituer des précipités avec l'or, et un complément constitué d'au moins un métal d'addition choisi pour son aptitude à favoriser une structure cubique faces centrées FCC stable d'une part, et pour son aptitude à augmenter la solubilité dudit second métal dans l'or d'autre part, ledit mélange comportant encore au moins au moins un dit précipité dudit second métal avec l'or sélectionné pour obtenir une dureté supérieure à 250 HV.Gold-based alloy, characterized in that it consists of a mixture comprising in mass at least 75% of gold, from 0.1% to 2.1% of a second metal chosen for its suitability for forming precipitates 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 gold on the other hand, said mixture further comprising at least one said precipitate of said second metal with the selected gold to obtain a hardness greater than 250 HV. Alliage à base d'or selon la revendication 1, caractérisé en ce que ledit second métal est l'aluminium et ledit précipité sélectionné est le précipité d'aluminium et d'or Al2Au5.A gold-based alloy according to claim 1, characterized in that said second metal is aluminum and said selected precipitate is Al 2 Au 5 aluminum and gold precipitate. Alliage à base d'or selon l'une des revendications 1 ou 2, caractérisé en ce que ledit métal d'addition est l'argent.Gold-based alloy according to one of claims 1 or 2, characterized in that said addition metal is silver. Alliage à base d'or selon l'une des revendications 1 à 3, caractérisé en ce que ledit métal d'addition est l'argent et est complété par un autre métal d'addition de concentration inférieure à celle de l'argent.Gold-based alloy according to one of Claims 1 to 3, characterized in that the said addition metal is silver and is supplemented by another addition metal of concentration lower than that of silver. Alliage à base d'or selon la revendication 4, caractérisé en ce que ledit autre métal d'addition est le cuivre.Gold-based alloy according to claim 4, characterized in that said other addition metal is copper. Procédé d'obtention d'un alliage à base d'or, à dureté améliorée, caractérisé en ce que : - on choisit un second métal pour son aptitude à constituer des précipités avec l'or ; - on choisit au moins un métal d'addition pour son aptitude à favoriser une structure cubique faces centrées FCC stable d'une part, et pour son aptitude à augmenter la solubilité à haute température dudit second métal dans l'or d'autre part ; - on crée les conditions d'insertion, dans une structure cubique faces centrées FCC résultant de la mise en solution d'un mélange d'or, dudit second métal, et dudit au moins un métal d'addition, de précipités dudit second métal avec l'or ; - on prépare un mélange comportant en masse au moins 75% d'or, de 0,1 % à 2,1 % dudit second métal, et un complément constitué dudit au moins un métal d'addition, ledit second métal et ledit métal d'addition étant choisis pour obtenir au moins un précipité sélectionné dudit second métal avec l'or d'une dureté supérieure à 250 HV ; - on met en solution ledit mélange par une mise en température entre 400°C et 700°C; - on effectue un refroidissement brusque après ladite mise en solution ; - on effectue après ledit refroidissement brusque un traitement de revenu structurant à une température comprise entre 200°C et 400°C pour donner naissance audit au moins un précipité sélectionné dudit second métal avec l'or ; - on fait croître de façon contrôlée ledit au moins un précipité sélectionné en maintenant ledit revenu structurant pendant une durée suffisante pour obtenir la dureté requise ; - on effectue un refroidissement à l'ambiante. Process for obtaining a gold-based alloy with improved hardness, characterized in that : a second metal is chosen for its ability to form precipitates with gold; at least one addition metal is chosen for its ability to favor a stable face-centered cubic FCC structure on the one hand, and for its ability to increase the high temperature solubility of said second metal in gold on the other hand; the conditions of insertion are created in a cubic face-centered FCC structure resulting from the dissolving of a mixture of gold, of said second metal, and of said at least one addition metal, of precipitates of said second metal with gold; a mixture comprising, by mass, at least 75% gold, from 0.1% to 2.1% of said second metal, and a complement consisting of said at least one additive metal, said second metal and said metal; addition being selected to obtain at least one selected precipitate of said second metal with gold of a hardness greater than 250 HV; said mixture is brought into solution by bringing the temperature to between 400 ° C. and 700 ° C .; an abrupt cooling is effected after said dissolution; after said quenching, a structuring income treatment is carried out at a temperature of between 200 ° C. and 400 ° C. to give rise to said at least one selected precipitate of said second metal with gold; the at least one selected precipitate is controlledly grown by maintaining said structuring income for a time sufficient to obtain the required hardness; - Cooling is carried out at ambient temperature. Procédé selon la revendication 6, caractérisé en ce qu'on effectue ledit refroidissement brusque par une trempe à l'eau.Process according to claim 6, characterized in that said quenching is carried out by quenching with water. Procédé selon la revendication 6 ou 7, caractérisé en ce qu'on restreint la sélection dudit au moins un précipité sélectionné à un seul précipité.Process according to Claim 6 or 7, characterized in that the selection of the said at least one selected precipitate is restricted to a single precipitate. Procédé selon l'une des revendications 6 à 8, caractérisé en ce qu'on effectue ledit revenu structurant au moins 24 heures après ledit refroidissement brusque.Process according to one of Claims 6 to 8, characterized in that said structuring income is carried out at least 24 hours after said sudden cooling. Procédé selon l'une des revendications 6 à 9, caractérisé en ce qu'on choisit pour ledit second métal l'aluminium, et on choisit pour ledit précipité sélectionné le précipité d'aluminium et d'or Al2Au5.Process according to one of Claims 6 to 9, characterized in that aluminum is chosen for the said second metal, and the precipitate of Al 2 Au 5 aluminum and gold is chosen for the said selected precipitate. Procédé selon l'une des revendications 6 à 10, caractérisé en ce qu'on choisit pour ledit métal d'addition l'argent.Process according to one of Claims 6 to 10, characterized in that silver is chosen for the said addition metal. Procédé selon l'une des revendications 6 à 11, caractérisé en ce qu'on choisit pour ledit métal d'addition l'argent et on y ajoute un autre métal d'addition de concentration inférieure à celle de l'argent.Process according to one of Claims 6 to 11, characterized in that the silver is selected for the said addition metal and a lower concentration addition metal is added to that of the silver. Procédé selon la revendication 12, caractérisé en ce qu'on choisit pour ledit autre métal d'addition le cuivre.Process according to Claim 12, characterized in that copper is chosen for the said other additive metal. Pièce d'horlogerie, de bijouterie ou de joaillerie comportant au moins un composant réalisé en un alliage d'or à dureté améliorée selon l'une des revendications 1 à 5 ou/et obtenu par un procédé selon une des revendications 7 à 13.Timepiece, jewelery or jewelery comprising at least one component made of a gold alloy with improved hardness according to one of claims 1 to 5 and / or obtained by a method according to one of claims 7 to 13.
EP10167859.7A 2010-06-30 2010-06-30 Gold alloy with improved hardness Active EP2402467B1 (en)

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EP10167859.7A EP2402467B1 (en) 2010-06-30 2010-06-30 Gold alloy with improved hardness
JP2013517158A JP2013531736A (en) 2010-06-30 2011-06-16 Gold alloy with improved hardness
CN201180032311.0A CN103038377B (en) 2010-06-30 2011-06-16 There is the au-alloy of the hardness of raising
US13/805,230 US20130153097A1 (en) 2010-06-30 2011-06-16 Gold alloy with improved hardness
PCT/EP2011/060041 WO2012000803A2 (en) 2010-06-30 2011-06-16 Gold alloy with improved hardness
CH03002/12A CH705500B1 (en) 2010-06-30 2011-06-16 gold alloy.
EP11725466.4A EP2588635B1 (en) 2010-06-30 2011-06-16 Gold alloy with improved hardness
HK13111451.4A HK1184198A1 (en) 2010-06-30 2013-10-10 Gold alloy with improved hardness

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RU2665650C1 (en) * 2017-09-18 2018-09-03 Юлия Алексеевна Щепочкина Jewelry alloy
CN108677115A (en) * 2018-04-24 2018-10-19 王振涛 A kind of chill gold process of gold ultra-deep
EP3800511B1 (en) * 2019-10-02 2022-05-18 Nivarox-FAR S.A. Pivoting shaft for a regulating organ
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CN103038377B (en) 2016-04-27
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US20130153097A1 (en) 2013-06-20
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EP2402467B1 (en) 2015-06-17
WO2012000803A2 (en) 2012-01-05

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