EP2369022B1 - Buntes, massives Edelmaterial, das durch das Zusammenfügen von Nanopartikeln von Edelmetallen zustande kommt - Google Patents

Buntes, massives Edelmaterial, das durch das Zusammenfügen von Nanopartikeln von Edelmetallen zustande kommt Download PDF

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Publication number
EP2369022B1
EP2369022B1 EP11157346.5A EP11157346A EP2369022B1 EP 2369022 B1 EP2369022 B1 EP 2369022B1 EP 11157346 A EP11157346 A EP 11157346A EP 2369022 B1 EP2369022 B1 EP 2369022B1
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Prior art keywords
nanoparticles
noble metal
process according
gold
coated
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EP11157346.5A
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English (en)
French (fr)
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EP2369022A1 (de
Inventor
Mikhael Bechelany
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Cartier International AG
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Cartier International AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • 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
    • C22C5/06—Alloys based on silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • B22F2003/1054—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by microwave
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a solid, mass-colored precious material of adjustable color.
  • Precious metals such as gold, silver or one of their alloys are widely used in the manufacture of luxury goods such as watchmaking products, jewelry or writing instruments.
  • Precious metals can be used in the form of a thin or thick decorative layer but also in the solid form.
  • metallic nanoparticles for coloring is known in the case of the coloring of glasses and ceramics.
  • ceramics pigmented with coated nanoparticles in particular nanoparticles coated with silica, were used to manufacture a pigmented ceramic material in the mass, for example of saturated red color.
  • An object of the present invention is to provide a material free from known limitations.
  • the object of the invention aims precisely to overcome these handicaps, by proposing a noble metal material of adjustable color colored in the mass and which can be advantageously used in fields relating to the luxury industry such as watchmaking, jewelry and writing instruments, but also in areas where aesthetic aspects are important such as cosmetics, dental, medical, or biomedical.
  • these aims are achieved in particular by means of a process for manufacturing a solid material of noble metal of adjustable color formed from an assembly of nanoparticles, the nanoparticles containing a noble metal and being coated with a layer dielectric, the nanoparticles being able to be shaped so as to obtain an unconsolidated compact; the method comprising: providing the nanoparticles of noble metal with a size between 1 nm and 200 nm and coated with a dielectric layer; shaping the assembly said nanoparticles for producing the noble metal compact comprising the nanoparticles and having a defined geometry; said material being obtained by sintering carried out simultaneously with compacting by a flash sintering method; the colored noble metal material obtained being of adjustable color between blue and red and comprising at least 50% by weight of the noble metal, the color being determined by the composition and the chemical environment, the shape and size of the nanoparticles.
  • the noble metal is gold or an alloy of gold at least 12 carats.
  • the noble metal is a metal of class 10 or 11 of the periodic table.
  • the dielectric layer is an oxide or polymer layer.
  • the proposed solution has the particular advantage over the prior art of offering a greater palette of colors for parts made of a noble metal or alloy of noble metals.
  • the nanoparticles are made with a metal of class 11 of the periodic table, such as gold and silver, or even with a metal of class 10 of the periodic table, such as palladium or platinum.
  • Nanoparticles can also be made from alloys of one or more of these metals, for example, 12-carat gold (grading 50%) up to 18 carats (grading 75%), as well as gold commonly called in goldsmithery “white gold” (gold and nickel alloys), “red gold” (gold and copper alloys), “green gold” (gold and silver alloys), “gray gold” (gold and iron alloys), “purple gold” (gold and aluminum alloys) “yellow gold", or “rose” (gold, silver and copper alloys), etc.
  • non-ble metal to designate indifferently a metal of classes 10 and 11 of the periodic table proper, or of an alloy formed from at least one of these metals.
  • the nanoparticle can be a solid noble metal or in the form of a core, for example consisting of a common metal or a mineral, coated with a layer of the noble metal.
  • Nanoparticles formed of a noble metal, and more particularly nanoparticles formed of a metal of class 11 of the periodic table which have a free electron on their outermost electronic layer, can induce surface plasmon resonance effects which absorbs strongly light at certain wavelengths in the visible spectrum, creating colors, especially colors between blue and red.
  • the colors generated can be adjusted in the spectral range mentioned according to the size, the geometry (spherical, cylindrical and pyramidal), the composition and the chemical environment of the nanoparticles considered.
  • the noble metal nanoparticles are coated with a dielectric layer.
  • This dielectric layer makes it possible, among other things, to protect the noble metal nanoparticle, in particular during the shaping and / or sintering treatments which will be seen below, and to obtain a specific coloring in the solid state. .
  • the dielectric layer is capable of influencing the wavelength of the plasmon resonance band and therefore of the perceived color.
  • the dielectric layer can also influence the physical properties (mechanical, thermal, electrical and magnetic) of the metallic nanoparticle coated with the layer. In the literature, we commonly speak of "core” or "nucleus” to describe the metallic nanoparticle, and "shell” to describe the dielectric layer.
  • the noble metal nanoparticles are coated with an inorganic monophasic layer, such as a oxide layer.
  • the inorganic layer is a layer of an oxide such as silica, zirconia or alumina or their derivatives.
  • the noble metal nanoparticles of controlled size and geometry can be synthesized by reduction of a metal precursor in solution to produce fine colloidal particles of the noble metal.
  • the oxide layer is produced, for example, by adding a source of Si or Al to a suspension of colloids in a preferably aqueous or alcoholic solvent (especially methanol, ethanol, propanol, or isopropanol) and in the presence of a mineralization, hydrolysis and / or catalysis agent such as, for example, ammonia.
  • the source of Si is an alkylorthosilicate whose transformation in the presence of water added to the reaction mixture will produce silica which is deposited on the metal nanoparticles (sol- gel). Colored metal nanoparticles coated with a layer of amorphous silica are thus obtained.
  • the oxide layer can also be produced using a Ti or Zr oxide or a mixture of at least two of these oxides.
  • the synthesized noble metal nanoparticles have dimensions between 1 nm and 200 nm, but preferably between 5 nm and 50 nm.
  • the thickness of the oxide layer is not critical as long as it is sufficient. It seems that a value of 2 nm is a minimum and 100 nm is a practical maximum which will obviously be reached only for diameters of nanoparticles, of the order of 100 nm to 200 nm. This thickness has relatively little effect on color, unlike the size of the nanoparticles themselves.
  • noble metal nanoparticles can also be synthesized using a so-called organometallic method based on the decomposition of a metal complex used as a source of atoms, under the action of a reactive gas (CO, H2, H2O), in the presence of a stabilizing agent such as a polymer or a ligand.
  • a reactive gas CO, H2, H2O
  • This route can also be applied to the synthesis of nanoparticles on a porous inorganic support (silica, alumina, organized mesoporous, etc.) or on a silicon substrate of given size and geometry (sphere, cube, stick, disc, etc.) .
  • the noble metal nanoparticles are coated with a layer consisting of an organic compound.
  • the organic compound is a macromolecular compound, such as a polymer, for example, a polyelectrolyte allowing in particular the dispersion of the nanoparticles in aqueous phase.
  • the organic layer can be coated in situ, during the synthesis of the nanoparticles, or ex situ, after the synthesis of the nanoparticles. More particularly, the organic layer can be coated on the noble metal nanoparticle by the so-called “grafting from” method, which consists in synthesizing the polymer chain monomer by monomer from an initiator grafted on the surface.
  • the polymer thus formed has a perfectly controlled architecture and size. More particularly, an initiator can be grafted to the surface of the nanoparticle, and a macromolecule can be generated from this initiator using a technique of controlled radical polymerization or of radical polymerization by atom transfer.
  • a “grafting on” method can be used where the organic layer is coated on the metallic nanoparticle by dispersion of the nanoparticles in a solution of organic material.
  • the nature of the organic material can be adjusted according to the properties of use envisaged for the part and / or the shaping methods used (see below).
  • the organic material can be a thermoplastic or thermosetting polymer or even capable of photochemical crosslinking.
  • the organic layer can be linked by strong (covalent) bonds to the surface of the nanoparticle, with or without an oxide layer, or linked by weak interactions (electrostatic, Van der Waals).
  • the nanoparticles are coated with a multilayer comprising, for example, the oxide layer coated on the metal particle, and the organic layer, coated on the oxide layer.
  • the multilayer can be formed of several layers, each of the layers having, for example, a chemical composition and / or a crystallographic structure different from the other layers.
  • the coated noble metal nanoparticles are shaped so as to obtain an unconsolidated compact.
  • shaping is meant any industrial shaping process similar to the processes used for shaping polymer (plastics), ceramic or metallic parts.
  • the shaping can be carried out by a cold compaction method of casting, injection molding, tape casting. Cold compaction methods such as pressing, injection or extrusion pressing, or prototyping are also possible.
  • the coated nanoparticles can be in a solid mixture or in a liquid solution, for example, a slip preparation or suspension of the coated nanoparticles.
  • the shaping process makes it possible to produce a compact in a desired geometry such as a solid piece, for example, a pellet, a coating, fibers, or even powders.
  • the shaping of the compact can be facilitated by additives such as binders and / or plasticizers added to the nanoparticles.
  • additives such as binders and / or plasticizers added to the nanoparticles.
  • These additives can be removed (debinding) during a heat treatment (see below), possibly assisted by overpressure or reduced pressure or microwaves, or by capillary migration, or by sublimation under vacuum.
  • the compact is sintered under a controlled atmosphere, for example, in air or under a gas such as O 2 , N 2 , Ar, H 2 , NH 3 , to consolidate the nanoparticles shaped, densify the material and give mechanical strength to the colored noble metal material.
  • Sintering can be facilitated by additives which accelerate densification and / or form a glassy or liquid phase at high temperature, or which form a new inorganic phase during sintering (reactive sintering).
  • the sintering of the compact is carried out by a microwave heating source producing radiation in a range of frequencies which are preferably absorbed by the layer.
  • a microwave heating source producing radiation in a range of frequencies which are preferably absorbed by the layer.
  • Such a source of radiation makes it possible to consolidate this compact and form the colored noble metal material by bringing the layer into a temperature range compatible with its consolidation and / or densification.
  • the temperature of the oxide and / or organic layers rises, thereby producing the consolidation and densification of the compact.
  • the specific coloration of the nanoparticles of noble metal is therefore not altered.
  • the frequency range is between 900 MHz and 1000 MHz or 2.45 GHz.
  • the microwave heating source is assisted by another conventional thermal heating source, for example, a radiant, convective, induction, or other thermal heating source.
  • another conventional thermal heating source for example, a radiant, convective, induction, or other thermal heating source.
  • the sintering of the compact form can be carried out only using the conventional thermal heating source.
  • the sintering is carried out in a conventional manner by heating at high temperature.
  • sintering is carried out simultaneously with compacting, for example, by a hot pressing method, flash sintering (Spark Plasma Sintering, SPS), or by sintering laser, for example when designing a part by rapid prototyping.
  • a hot pressing method for example, by a hot pressing method, flash sintering (Spark Plasma Sintering, SPS), or by sintering laser, for example when designing a part by rapid prototyping.
  • the solid material of noble metal thus obtained can be machined and / or receive a surface treatment, such as polishing.
  • a surface treatment such as polishing.
  • Such a machining and / or surface treatment step makes it possible to obtain a product which can be used commercially and industrially.
  • TEOS tetraethyl orthosilicate
  • Aldrich 27% ammonia solution
  • the gold nanoparticles coated with silica are then collected by ultracentrifugation (20,000 g for 15 minutes).
  • a mass of 150 mg of gold nanoparticles covered with silica is formed using a pelletizer by pressing at room temperature. The densification of the pellet is carried out by heating to 600 ° C. coupled with microwave irradiation at 2.45 GHz.
  • the tablet obtained is black in color.
  • the synthesis of gold nanoparticles is identical to that described above. Then added 0. 803 ml of tetraethyl orthosilicate (TEOS) and 10 ml of a 27% ammonia solution and then the solution is left to stir for 1 hour. The solution takes on a hue dark red.
  • the gold nanoparticles coated with silica are then collected by ultracentrifugation (20,000 g for 15 minutes). A mass of 150 mg of gold nanoparticles covered with silica is formed using a pelletizer by pressing at room temperature. Densification of the pellet is carried out by heating to 750 ° C. in air. The lozenge obtained is dark red in color.
  • a preliminary step 5 ml of a 0.2 M CTAB solution (cetrimonium bromide, Aldrich) is added to 5.0 ml of a 0.5 mM HAuCl 4 solution (Aldrich). 0.6 ml of a NaBH 4 solution (0.01 M) (Aldrich) cooled to 0 ° C. is added to the preceding mixture with stirring. The solution becomes brown and is stirred for 5 minutes at room temperature. This first step makes it possible to obtain a solution of germs of gold.
  • 5 ml of a 0.15 M solution of BDAC (benzyl dimethyl hexadecyl ammonium chloride, Aldrich) is added to 0.145 g of CTAB.
  • the mixture is dissolved by sonication for 20 minutes at 40 ° C.
  • 0.2 ml of a 4 mM solution of silver nitrate (Aldrich) is then added to the mixture.
  • 5 ml of a 1 mM solution of HauCl 4 are then added .
  • 0.07 ml of a solution of ascorbic acid (0.8 mM) (Aldrich) is added.
  • 0.015 ml of the previously prepared seed solution is added and the mixture is left stirring for 24 hours.
  • the gold particles are collected by ultracentrifugation.
  • the colored noble metal material can be shaped so as to produce solid parts or coatings.
  • the noble metal material consists essentially of a solid noble metal material.
  • the colored noble metal material can be advantageously used for the manufacture of all or part of parts or components where the decorative aspect is important, for example, in the fields of the luxury industry, such as for example in the fields of the watchmaking, jewelry, jewelry, writing instruments, leather goods, eyewear, tableware, etc.
  • the colored noble metal material can also advantageously be used in fields such as dental, medical and biomedical, where aesthetic aspects are important.
  • the colored noble metal material is produced in the form of colored particles which can be used for pigmentation in various applications such as food or cosmetics.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)

Claims (13)

  1. Verfahren zur Herstellung eines massiven Edelmetallmaterials mit anpassbarer Farbe, das aus einer Anordnung von Nanopartikeln gebildet ist, wobei die Nanopartikel ein Edelmetall enthalten und mit einer dielektrischen Schicht überzogen sind,
    wobei die Nanopartikel geeignet sind, so geformt zu werden, dass ein nicht verfestigter Pressling erhalten wird, wobei das Verfahren umfasst:
    die Bereitstellung von Edelmetall-Nanopartikeln mit einer Größe zwischen 1 nm und 200 nm, die mit einer dielektrischen Schicht überzogen sind;
    das Formen der Anordnung aus den Nanopartikeln, um den festen Edelmetall-Pressling zu erhalten, der die Nanopartikel beinhaltet und eine definierte Geometrie hat;
    dadurch gekennzeichnet, dass das Material durch Sintern erhalten wird, das mithilfe einer Strahlungsquelle mit einer von der dielektrischen Schicht bevorzugt absorbierten Frequenz ausgeführt wird;
    wobei das erhaltene Edelmetall eine anpassbare Farbe in der Masse hat und mindestens 50 Gew.-% des Edelmetalls umfasst, wobei die Farbe durch die Zusammensetzung und die chemische Umgebung, die Form und die Größe der Nanopartikel bestimmt wird.
  2. Verfahren nach Anspruch 1, bei dem das Edelmetall Gold oder eine Goldlegierung mit mindestens 12 Karat ist.
  3. Verfahren nach Anspruch 1, bei dem das Edelmetall ein Metall der Klasse 10 oder 11 des Periodensystems ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem die dielektrische Schicht eine Oxidschicht oder eine Polymerschicht ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem die Größe der Edelmetall-Nanopartikel zwischen 1 nm und 200 nm, bevorzugt aber zwischen 5 nm und 50 nm beträgt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem das Sintern unter kontrollierter Atmosphäre ausgeführt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem die Strahlungsquelle eine Mikrowellenstrahlung ist.
  8. Verfahren nach Anspruch 7, bei dem die Mikrowellenstrahlung eine Frequenz zwischen 900 und 1000 MHz hat.
  9. Verfahren nach Anspruch 7, bei dem die Mikrowellenstrahlung eine Frequenz von 2,45 GHz hat.
  10. Material, das mit dem Verfahren nach einem der Ansprüche 1 bis 9 erhalten wird.
  11. Verwendung des Materials nach Anspruch 10 zur vollständigen oder teilweisen Herstellung von Teilen oder Komponenten für Anwendungen im Luxus- oder Kosmetikbereich.
  12. Verwendung des Materials nach Anspruch 10 oder 11 zur vollständigen oder teilweisen Herstellung von Teilen und Komponenten im Uhren-, Schmuck-, Juwelier-, Lederwaren oder Schreibgerätebereich.
  13. Verwendung des Materials nach Anspruch 10 bis 12 zur vollständigen oder teilweisen Herstellung von Teilen oder Komponenten im Dental-, Medizin- oder Biomedizinbereich.
EP11157346.5A 2010-03-11 2011-03-08 Buntes, massives Edelmaterial, das durch das Zusammenfügen von Nanopartikeln von Edelmetallen zustande kommt Active EP2369022B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH00343/10A CH702835A2 (fr) 2010-03-11 2010-03-11 Matériau précieux massif coloré constitué par l'assemblage de nanoparticules de métaux nobles.

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Publication Number Publication Date
EP2369022A1 EP2369022A1 (de) 2011-09-28
EP2369022B1 true EP2369022B1 (de) 2020-06-17

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH711352B1 (fr) * 2015-07-24 2019-09-30 Cartier Int Ag Procédé de fabrication d'un matériau d'un métal noble massif coloré.
CH714326A1 (fr) * 2017-11-14 2019-05-15 Cartier Int Ag Procédé de fabrication d'un matériau de couleur noire ou anthracite comprenant au moins 18 carats d'or.
FR3078966A1 (fr) * 2018-03-16 2019-09-20 Luxeram Matrice ceramique transparente comportant une inclusion visible
ES2941332B2 (es) * 2021-11-18 2023-11-06 Univ Jaume I Procedimiento de obtención in situ de un pigmento cerámico molturado
EP4257265A1 (de) 2022-04-06 2023-10-11 Patek Philippe SA Genève Verfahren zur herstellung einer uhren- oder schmuckkomponente und diese uhren- oder schmuckkomponente
CN121970002A (zh) 2023-10-03 2026-05-01 百达翡丽日内瓦公司 钟表部件或珠宝部件及制造该钟表部件或珠宝部件的方法
WO2025224296A1 (fr) 2024-04-26 2025-10-30 Patek Philippe Sa Geneve Procede de fabrication d'un composant horloger ou de bijouterie
WO2025224295A1 (fr) 2024-04-26 2025-10-30 Patek Philippe Sa Geneve Composant horloger ou de bijouterie et procede de fabrication d'un tel composant horloger ou de bijouterie
WO2026087788A1 (fr) * 2024-10-25 2026-04-30 Patek Philippe Sa Geneve Procede de fabrication d'un article en materiau composite

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5782439A (en) * 1980-11-13 1982-05-22 Tanaka Kikinzoku Kogyo Kk Manufacture of material for decoration
DE3820970C1 (de) * 1988-06-22 1989-11-09 Degussa Ag, 6000 Frankfurt, De
ZA938045B (en) * 1992-09-23 1994-06-20 Mintek Gold or yellow coloured noble metal compositions and their production
US6136061A (en) * 1995-12-01 2000-10-24 Gibson; Charles P. Nanostructured metal compacts, and method of making same
JP2000219902A (ja) * 1999-01-28 2000-08-08 Citizen Watch Co Ltd 射出成形による粉末焼結体およびその製造方法
KR100620615B1 (ko) * 2005-05-23 2006-09-06 한국생명공학연구원 가시광선 영역의 색을 갖는 금속 나노입자 혼합물이 코팅된 다색 콜로이드 입자 및 그 제조방법
DE602006009921D1 (de) 2006-07-31 2009-12-03 Rolex Sa Pigmentierter keramischer Körper

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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CH702835A2 (fr) 2011-09-15
EP2369022A1 (de) 2011-09-28

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