EP2402467A1 - Gold alloy with improved hardness - Google Patents
Gold alloy with improved hardness Download PDFInfo
- 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
- Authority
- 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
Links
Images
Classifications
-
- 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 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.
Landscapes
- 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
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
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
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.
- 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 lafigure 1 en comparaison d'un or 18 carats obtenu de manière standard.
- 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
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
Un second domaine appelé B sur la
Le troisième domaine appelé C sur la
Le diagramme de la
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
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.
- 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)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10167859.7A EP2402467B1 (en) | 2010-06-30 | 2010-06-30 | Gold alloy with improved hardness |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2402467A1 true EP2402467A1 (en) | 2012-01-04 |
EP2402467B1 EP2402467B1 (en) | 2015-06-17 |
Family
ID=43037800
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10167859.7A Active EP2402467B1 (en) | 2010-06-30 | 2010-06-30 | Gold alloy with improved hardness |
EP11725466.4A Active EP2588635B1 (en) | 2010-06-30 | 2011-06-16 | Gold alloy with improved hardness |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11725466.4A Active EP2588635B1 (en) | 2010-06-30 | 2011-06-16 | Gold alloy with improved hardness |
Country Status (7)
Country | Link |
---|---|
US (1) | US20130153097A1 (en) |
EP (2) | EP2402467B1 (en) |
JP (1) | JP2013531736A (en) |
CN (1) | CN103038377B (en) |
CH (1) | CH705500B1 (en) |
HK (1) | HK1184198A1 (en) |
WO (1) | WO2012000803A2 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN112708797A (en) * | 2020-11-25 | 2021-04-27 | 西安汇创贵金属新材料研究院有限公司 | Purple gold alloy and preparation method thereof |
US11268174B1 (en) * | 2021-06-10 | 2022-03-08 | Chow Sang Sang Jewellery Company Limited | Jewelry alloy |
WO2023110997A1 (en) * | 2021-12-15 | 2023-06-22 | Rolex Sa | Metal matrix composite material for horological part |
CN115612887B (en) * | 2022-08-12 | 2024-04-12 | 深圳市沃尔弗斯珠宝实业股份有限公司 | High-strength k gold jewelry and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2024071A1 (en) * | 1970-05-16 | 1971-11-25 | Eugen Duerrwachter Doduco Fa D | Casting filigree type jewellry by addition of film forming - elements to noble metals for stripping mould material from casting |
EP0284699A1 (en) | 1987-03-10 | 1988-10-05 | Samuel Prof.Dr.Sc.Nat. Steinemann | Intermetallic compound and its use |
US5338378A (en) | 1992-09-29 | 1994-08-16 | Kyushu University | Dental gold alloy with age-hardenability at intraoral temperature |
JPH0813060A (en) * | 1994-06-26 | 1996-01-16 | Pilot Corp:The | Age hardening gold alloy |
EP0978572A1 (en) | 1998-08-01 | 2000-02-09 | C. HAFNER GmbH & Co. | Gold base alloy for jewellery |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5993872A (en) * | 1982-11-18 | 1984-05-30 | Mitsubishi Metal Corp | Au alloy member for decoration having surface hardened layer |
JPS6466097A (en) * | 1987-09-08 | 1989-03-13 | Seiko Instr & Electronics | Brazing filler metal |
JPH0678577B2 (en) * | 1989-06-13 | 1994-10-05 | 株式会社日本興業銀行 | Shape memory alloy |
JPH0474836A (en) * | 1990-07-13 | 1992-03-10 | Pilot Corp:The | Gold alloy fine wire and its manufacture |
JP2001049364A (en) * | 2000-07-03 | 2001-02-20 | Kazuo Ogasa | Hard noble metal alloy member and its production |
CN101565783B (en) * | 2009-05-27 | 2011-01-19 | 上海交通大学 | Gold alloy with 18k span effect and preparation method thereof |
-
2010
- 2010-06-30 EP EP10167859.7A patent/EP2402467B1/en active Active
-
2011
- 2011-06-16 US US13/805,230 patent/US20130153097A1/en not_active Abandoned
- 2011-06-16 EP EP11725466.4A patent/EP2588635B1/en active Active
- 2011-06-16 WO PCT/EP2011/060041 patent/WO2012000803A2/en active Application Filing
- 2011-06-16 CN CN201180032311.0A patent/CN103038377B/en not_active Expired - Fee Related
- 2011-06-16 CH CH03002/12A patent/CH705500B1/en unknown
- 2011-06-16 JP JP2013517158A patent/JP2013531736A/en active Pending
-
2013
- 2013-10-10 HK HK13111451.4A patent/HK1184198A1/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2024071A1 (en) * | 1970-05-16 | 1971-11-25 | Eugen Duerrwachter Doduco Fa D | Casting filigree type jewellry by addition of film forming - elements to noble metals for stripping mould material from casting |
EP0284699A1 (en) | 1987-03-10 | 1988-10-05 | Samuel Prof.Dr.Sc.Nat. Steinemann | Intermetallic compound and its use |
US5338378A (en) | 1992-09-29 | 1994-08-16 | Kyushu University | Dental gold alloy with age-hardenability at intraoral temperature |
JPH0813060A (en) * | 1994-06-26 | 1996-01-16 | Pilot Corp:The | Age hardening gold alloy |
EP0978572A1 (en) | 1998-08-01 | 2000-02-09 | C. HAFNER GmbH & Co. | Gold base alloy for jewellery |
Non-Patent Citations (2)
Title |
---|
C. CORTI; R. HOLLIDAY: "GOLD - Science and Applications", 20 May 2010, CRC PRESS, Florida, USA, ISBN: 978-1-4200-6523-7, article JÖRG FISCHER-BÜHNER: "7. Metallurgy of Gold", pages: 123 - 159, XP002609226 * |
SUSS, RAINER ET AL: "18 carat yellow gold alloys with increased hardness", GOLD BULLETIN (LONDON, UNITED KINGDOM) , 37(3-4), 196-207 CODEN: GOBUFW; ISSN: 1027-8591, 2004, XP009141051 * |
Also Published As
Publication number | Publication date |
---|---|
CN103038377A (en) | 2013-04-10 |
HK1184198A1 (en) | 2014-01-17 |
EP2588635A2 (en) | 2013-05-08 |
CH705500B1 (en) | 2015-12-31 |
CN103038377B (en) | 2016-04-27 |
JP2013531736A (en) | 2013-08-08 |
EP2588635B1 (en) | 2016-04-06 |
US20130153097A1 (en) | 2013-06-20 |
WO2012000803A3 (en) | 2012-09-20 |
EP2402467B1 (en) | 2015-06-17 |
WO2012000803A2 (en) | 2012-01-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2402467B1 (en) | Gold alloy with improved hardness | |
EP2393951B1 (en) | Method for producing a piece made from a superalloy based on nickel and corresponding piece | |
CH711398A2 (en) | Solid amorphous alloy based on nickel free zirconium. | |
EP2954079B1 (en) | Pink-gold alloy for timepiece | |
EP0863219B1 (en) | Titanium aluminide usable at elevated temperatures | |
EP3128035B1 (en) | Bulk amorphous alloy made of nickel-free zirconium | |
EP3241078A1 (en) | Timepiece or jewellery item made from lightweight precious alloy comprising titanium | |
EP2546371A1 (en) | 18-carat grey gold | |
CH703379B1 (en) | improved hardness of gold alloy. | |
EP1051533B1 (en) | Manufacturing process of titanium alloy watch parts | |
EP3656245B1 (en) | Gold based alloy comprising at least 990 per mille gold by weight, item of jewellery or watch comprising gold based alloy comprising at least 990 per mille gold by weight, and method of manufacturing said alloy | |
WO2009092920A2 (en) | Piece of jewellery or timepiece made of solid gold alloy having a white colour, the entirety of which is shining | |
EP3249060A1 (en) | Method for thermal treatment of austenitic steels and austenitic steels thus obtained | |
EP3527678B1 (en) | Alloy of gold and copper, method for preparing same and use thereof | |
FR2815044A1 (en) | GRAY GOLD ALLOY 18 CARATS FOR JEWELRY, WITHOUT NICKEL AND WITHOUT PALLADIUM | |
EP1584697B1 (en) | Titanium-aluminium alloy having high-temperature ductility | |
EP1297192B1 (en) | Steel compositions, method for obtaining same and parts made from same | |
WO2022136552A1 (en) | Non-magnetic timepiece parts and thermo-mechanical treatment method for obtaining said parts | |
FR3096690A1 (en) | Corrosion protection process | |
WO1997014819A1 (en) | Method for heat treating a nickel alloy strip material, and resulting product | |
CH710562A2 (en) | Cladding component for timepiece or jewelry piece in a light titanium-based precious alloy. | |
WO2006111178A1 (en) | Precious metal alloy | |
BE451105A (en) | Manufacturing process of metallic objects with hardened surface layer of precious metal | |
BE389823A (en) | ||
CH190479A (en) | Process for the heat treatment of gold-glucinium alloys. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
17P | Request for examination filed |
Effective date: 20110412 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME RS |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17Q | First examination report despatched |
Effective date: 20141110 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20150413 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: ICB INGENIEURS CONSEILS EN BREVETS SA, CH Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 731987 Country of ref document: AT Kind code of ref document: T Effective date: 20150715 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602010025238 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150917 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 731987 Country of ref document: AT Kind code of ref document: T Effective date: 20150617 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D Ref country code: NL Ref legal event code: MP Effective date: 20150617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150918 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150917 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151019 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151017 Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150617 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602010025238 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150630 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
26N | No opposition filed |
Effective date: 20160318 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150917 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150917 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20100630 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150630 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150617 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20200519 Year of fee payment: 11 Ref country code: FR Payment date: 20200520 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602010025238 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210630 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230615 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20230702 Year of fee payment: 14 |