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  • 权利要求
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    • 专利摘要:
    A method of manufacturing a material comprising between 12 and 23 carats of an adjustable solid noble metal formed of a noble metal-containing nanoparticle assembly in a matrix of an inorganic material, the material comprising at least 50% by weight of the noble metal; the process comprising the steps of providing in a reactor a mixture comprising a noble metal precursor, for example a gold salt, a precursor of the inorganic material, and a solvent including water, an alcoholic solvent, and an aprotic solvent polar; and heating said mixture to a first temperature so as to reduce the noble metal precursor. The mixture comprises between 5 and 20% vol of water; between 40 and 60% by volume of the polar aprotic solvent, between 25 and 50% vol of the alcoholic solvent; and between 50 and 100 g of the noble metal precursor. The material thus manufactured finds its application in fields as varied as watchmaking, jewelery, cosmetics or the medical field, among others.
    公开号:CH711352A1
    申请号:CH01080/15
    申请日:2015-07-24
    公开日:2017-01-31
    发明作者:Germain Vincent
    申请人:Cartier Int Ag；Neollia Sas；
    IPC主号:
    专利说明:

    Technical area
    The present invention relates to a method of manufacturing a material comprising between 12 and 23 carats of a solid noble metal adjustable color and the material obtained by the process.
    State of the art
    [0002] Precious metals such as gold, silver or one of their alloys are widely used in the manufacture of luxury products such as watchmaking products, jewelery or writing instruments. Precious metals can be used in the form of a thin or thick decorative layer but also in massive form.
    The use of such precious metals makes it possible to obtain products in a certain range of colors. For example, in the case of gold, 18-carat gold can be used, as well as golds commonly referred to as "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 silver alloys) aluminum) "yellow gold", or "rose" (alloys of gold, silver and copper), etc. The color palette obtained by these different alloys, however, remains limited mainly to shades on the original color of gold.
    It is impossible to obtain an extensive range of colors and colors by the use of precious metals or alloys of precious metals. In particular, it is difficult, if not impossible, to obtain until now certain ranges or varieties of colors such as red that are frank, bright and stable over time.
    The coating of the precious metal or alloy part with a coating to add a surface color is not satisfactory since the colored layer may leave to wear and the part will discolor partially or completely with time.
    The use of metal nanoparticles for coloring is known in the case of coloring glasses and ceramics. For example, in EP 1 887 052, ceramics have been pigmented with coated nanoparticles, especially silica-coated nanoparticles, have been used to manufacture a mass-pigmented ceramic material, for example of saturated red color.
    However, none of the known methods allows to color in the mass to obtain metals or alloys of precious metals in these shades of colors.
    [0008] EP 2 369 022 discloses a solid noble metal material of adjustable color formed of an assembly of nanoparticles, the nanoparticles containing a noble metal and being coated with an inorganic matrix (or dielectric). In particular, the noble metal nanoparticles are coated with an inorganic matrix which makes it possible to obtain a specific coloration in the solid state. Indeed, the inorganic matrix is likely to influence the wavelength of the plasmon resonance band and thus the perceived color. The inorganic matrix may comprise an oxide such as silica, zirconia or alumina or their derivatives. The nanoparticles are shaped so as to obtain an unconsolidated compact, the compact is sintered to obtain a colored noble metal material. The colored noble metal material comprises at least 50% by weight of the noble metal, its color being determined by the composition and the chemical environment, the shape and size of the nanoparticles.
    Nanoparticles of noble metal of controlled size and geometry (spheres, cubes, rods, etc.) can be synthesized by reducing a metal precursor (for example a metal salt) in solution to produce fine colloidal particles of the noble metal. A layer of an inorganic material, such as an oxide, is produced, for example, by adding an Si or Al precursor to a suspension of colloids in a preferably aqueous or alcoholic solvent (in particular methanol, ethanol, propanol, or isopropanol) and in the presence of a mineralizing agent, hydrolysis and or catalysis such as ammonia.
    However, the concentrations of the metal precursor that can be used in the synthesis solution remain low, that is to say typically less than one tenth of a gram of the metal precursor per liter of synthesis solution. The production yields of the solid material of synthesized noble metal therefore remain relatively low. In addition, the synthesis reaction must be done in several steps. For example, it is necessary to carry out the reduction of the metal precursor before formation of the inorganic matrix. For this purpose, the precursor of the inorganic material must be added to the synthesis solution after the reduction of the metal precursor.
    Brief summary of the invention
    The present invention relates to a method of manufacturing an adjustable color solid noble metal material formed of a noble metal-containing nanoparticle assembly in a matrix of an inorganic material, free from the limitations of known methods.
    More particularly, the present invention relates to a process for manufacturing a material comprising between 12 and 23 carats of a solid noble metal of adjustable color formed of a noble metal-containing nanoparticle assembly in a matrix of a inorganic material, the material comprising at least 50% by weight of the noble metal; the method comprising the steps of:providing in a reactor a synthesis mixture comprising a noble metal precursor, a precursor of the inorganic material, and a solvent including water, an alcoholic solvent, and a polar aprotic solvent; andheating said mixture to a first temperature so as to reduce the noble metal precursor;said mixture comprising between 5 and 20% vol of water; between 40 and 60% by volume of the polar aprotic solvent, between 25 and 50% vol of the alcoholic solvent; and between 50 and 100 g of the noble metal precursor.
    An advantage of the manufacturing method described herein is that the synthesis mixture can comprise up to 1 to 2 g / L of the noble metal precursor, that is to say about 40 to 80 times the allowable concentration. in known methods. The production yields of the solid material of synthesized noble metal are therefore relatively higher. In addition, the reduction of the metal precursor can be achieved with the formation of the inorganic matrix, making it possible to synthesize the noble material in a single step.
    Brief description of the figures
    Examples of implementation of the invention are indicated in the description illustrated by the appended figures in which:<tb> Fig. 1 <SEP> illustrates a sequence for adding to a reactor the different components of a synthesis mixture, according to a first embodiment; and<tb> fig. 2 <SEP> illustrates a sequence for adding to a reactor the different components of a synthesis mixture, according to a second embodiment.
    Example (s) of embodiment of the invention
    According to one embodiment, a method of manufacturing an adjustable color composite material comprising a noble metal and an inorganic matrix, the method comprising steps of:supplying to a reactor a mixture comprising a noble metal precursor, a precursor of the inorganic material, and a solvent including water, an alcoholic solvent, and a polar aprotic solvent; andheating said mixture to a first temperature T1 so as to reduce the noble metal precursor and form the inorganic matrix.
    Preferably, the mixture comprises between 8 and 14% vol of water; between 47 and 53 vol% of the aprotic polar solvent, and between 33 and 38 vol% of the alcoholic solvent.
    The reduction of the noble metal precursor in the mixture allows a higher concentration of the noble metal precursor in the mixture than in known manufacturing processes. Preferably, the mixture may comprise between 1 and 2 g / l of the noble metal precursor. The mixture therefore makes it possible to have higher production yields.
    Such a concentration of the noble metal precursor makes it possible to manufacture the solid noble metal material with a concentration of the noble metal of between 12 and 23 carats, that is to say between about 50% and 95% by weight.
    In the present process, the noble metal precursor and the precursor of the inorganic material are provided together in the reactor, before heating the mixture to the first temperature T1. Heating the T1 mixture enables the noble metal precursor to be reduced and the precursor of the inorganic material to be reacted to form the inorganic matrix. The addition of a chemical reductant to the mixture may be necessary to reduce the noble metal and to react the precursor of the inorganic material during the heating step. This is the case for the reduction of a gold precursor in the presence of a silica precursor, as described below. The reduction of the noble metal precursor and the reaction of the precursor of the inorganic material are therefore carried out in a single step, unlike known processes where the reduction of the noble metal precursor is carried out before the reaction of the precursor of the inorganic material. The heating step makes it possible to obtain a suspension (colloidal dispersion) formed by the noble metal in its inorganic matrix.
    Alternatively, a chelating agent is added to the mixture to reduce the reaction rate of the inorganic precursor.
    According to one embodiment, the alcoholic solvent is isopropanol. Preferably, the polar aprotic solvent is N, N-dimethylformamide (or DMF).
    [0022] Still according to one embodiment, the noble metal comprises a gold salt. The precursor of the inorganic material comprises a zirconium precursor, for example zirconium propoxide or a silica precursor, for example a tetraethylorthosilicate (TEOS).
    According to one embodiment, the method comprises a step of cooling the mixture to a second temperature T2 lower than the first temperature. The second temperature T 2 can be about 30 ° C. The method may also include a step of filtering the suspension, for example on a membrane. After passing the solution on the filter, a powder is recovered.
    The method may also include a step of passing the powder in an oven, for example at a temperature of about 80 ° C for about 12 hours. The method may also include a step of grinding and sieving the powder to obtain a fine and homogeneous powder. In particular, the grinding and sieving step makes it possible to control the particle size of the powder. The process may also include heat treatment of the powder at 450 to 900 ° C in air or in a neutral atmosphere. The heat treatment allows pre-consolidation of the inorganic material. The method may also include a sieving post treatment of the thermally treated powder.
    The method comprises a step of compacting the powder by a sintering process. The sintering process is preferably a flash sintering process (or SPS sintering).
    According to one embodiment, an inorganic adjuvant such as mica is added to the mixture provided in the reactor, before the step of heating the mixture to the first temperature T1. The inorganic adjuvant is intended to modify the optical and colorimetric properties of the solid noble metal material, for example gloss. The amount of inorganic adjuvant added is controlled according to the synthesis reaction so as to retain the valuable nature of the material. Alternatively, the inorganic adjuvant is added and mixed with the powder obtained after the filtration step, but before the compaction step.
    According to one embodiment, the solvent introduced into the reactor comprises between 4 to 6 L, but preferably 5.5 L, of water, between 20 to 25 L, but preferably 23.5 L, of DMF and between 12 and 17 L. but preferably 15.75 L, isopropanol and the noble metal precursor comprises between 50 and 100 g of gold salt in between 300 and 320 mL, but preferably 310 mL of water. The addition of the DMF creates an exothermic reaction resulting in a low rise in temperature of the mixture of water and DMF.
    According to a first embodiment, the precursor of the inorganic material comprises between 200 and 300 mL, but preferably 250 mL of isopropanol, about thirty mL of zirconium propoxide (precursor, polymer) and between 1 and 2 mL, but preferably 1.43 mL, of acetylacetone as a chelating agent.
    According to the first embodiment illustrated in FIG. 1, the various components of the mixture are added to the reactor in the following order:water (S1);the polar aprotic solvent (S2);the noble metal precursor, with stirring (S3); andthe precursor of the inorganic material (S4).
    According to a second embodiment, the precursor of the inorganic material comprises a first solution containing between 200 and 400 ml of isopropanol but preferably 250 ml of isopropanol, between 20 and 60 ml of silica precursor but preferably 45 ml. precursor silica, such as TEOS. A second solution contains between 300 and 400 g of sodium citrate in 1 L of H2O.
    According to the second embodiment illustrated in FIG. 2, the various components of the mixture can be added to the reactor in the following order:water (S1);the polar aprotic solvent (S2);the noble metal precursor, with stirring (S3);the first solution (S4);the second solution (S5); andthe step of heating the mixture at the first temperature T1 is carried out between the addition of the first solution and the addition of the second solution.
    The first temperature T1 at which the mixture is heated reduces the noble metal precursor between 90 and 130 ° C. The mixture is heated to the first temperature for about three hours from the time the mixture is refluxed. A first temperature of 130 ° C allows the mixture to reach about 95 ° C.
    Example 1
    This example relates to the manufacture of a material comprising a gold content of between 50 and 95% minimum by mass of gold, which corresponds respectively to objects between 12 K and 23 K minimum, in a matrix of silica.
    A mixture comprises 77.28 g of HAuCl4, 5.81 L of ultrapure water, between 20 to 25 L, but preferably 23.5 L, of N, N dimethylformamide, between 12 and 17 L, but preferably 15.4 L, of isopropanol. The amount of silica precursor (tetraethyl orthosilicate or TEOS) may be between 25.5 and 400 mL. In this example, the mixture comprises 80 mL of TEOS. The mixture is initially of yellow color, characteristic of the salt of gold.
    The mixture is supplied in a 60 L reactor and is then refluxed at a first temperature T1 of about 130 ° C. Once the reflux is reached, between 300 and 500 g, but preferably 391 g, sodium citrate pre-dissolved dissolved in between 300 and 900 ml of ultrapure water, but preferably 500 ml of ultra-pure water are added to the mixture (reaction medium). The mixture fades and becomes transparent. About ten minutes after the addition of sodium citrate, between 150 and 250 mL, but preferably 200 mL, of ammonia are added to the mixture. The particles of Au-silica are formed and the medium becomes dark blue. Once the particles are formed, the medium is left at the temperature T 2 for about two hours in order to obtain a suspension before going back to a second temperature T 2 corresponding to the ambient temperature.
    The suspension is then filtered through a 0.22 μm nylon membrane. The precipitate of powder is then rinsed by soaking in ultrapure water. About 45 g of powder are harvested at the end of the reaction. The Au-silica powder thus obtained is titrated at 91% by weight of gold.
    The powder is precooked between 400 and 900 ° C for 1 to 5 hours, in an oven to work under air, under nitrogen and under argon. The powder is preferably precooked under an inert atmosphere, preferably under argon and preferentially at 700 ° C. for two hours. The powder is then milled and sieved to obtain a fine particle size, preferably below 50 microns.
    The shaping is done by flash sintering. To this end, the powder is introduced into a graphite mold or tungsten carbide, preferably tungsten carbide, whose inner chamber is protected by a graphite sheet. The pressure is applied cold or hot, preferably cold. The pressure range is between 2 and 400 MPa. The rise in temperature occurs before or after the nominal pressure is applied, preferably after. The shaping temperature is between 500 and 900 ° C, preferably at 700 ° C. The working atmosphere for sintering can be nitrogen, argon or vacuum but is preferably argon. The sintering lasts between 7 and 19 minutes, preferably 12 minutes. The compactness of the pellets obtained is between 87 and 100%.
    For example, an Au-silica powder dosed at 94% by weight of gold, precooked at 450 ° C., with shaping under argon, pressure of 32 MPa applied cold and then raised to 700 ° C. for 7 minutes resulted in the formation of a pellet having a density of 14.4 g.cm <-> <3> and a compactness of 95%.
    Example 2
    This example relates to the manufacture of a material comprising a gold content of between 50 and 95% minimum by mass of gold, which respectively corresponds to objects between 12 K and 23 K minimum, in a matrix of zirconium.
    A mixture comprises between 50 and 100 g of HAuC4 but preferably 77.28 g of HAuCl4, between 3.5 and 8 L of ultra-pure water but preferably 5.81 L of ultrapure water, between 20 and 25 L of N, N dimethylformamide but preferably 23.5 L of N, N dimethylformamide, between 14 and 20 L of isopropanol but preferably 15.75 L of isopropanol. The amount of zirconia precursor can be between 6 and 55 ml of zirconium isopropoxide and the amount of chelating agent (acetylacetone) can be between 1.4 and 12 ml. In this example, the mixture comprises 6.58 ml of zirconium isopropoxide (Zr (OiPr) 4) and 1.43 ml of acetylacetone (a chelating agent). The mixture is initially of yellow color, characteristic of the salt of gold.
    The mixture is supplied in a 60 L reactor and is then refluxed at a first temperature T1 of 130 ° C. One hour after the reflux is reached, the mixture (reaction medium) fades and becomes transparent, and then recolor in brown. The reaction in the mixture is left under reflux for two hours, then the mixture is allowed to fall back to a second temperature T2 corresponding to the ambient temperature, so as to obtain a suspension.
    The suspension obtained is then filtered through a 0.22 μm nylon membrane. About 45 g of powder product are harvested at the end of the reaction. The Au-zirconia powder thus obtained, titrated at 94% by weight of gold,
    The powder is precooked between 400 and 900 ° C for 1 to 5 hours, in an oven for working under air, under nitrogen and under argon. The powder is preferably precooked under an inert atmosphere, preferably under argon and preferentially at 450 ° C. for two hours. The powder is then milled and sieved to obtain a fine particle size, preferably below 50 microns.
    The shaping is done by flash sintering. To this end, the powder is introduced into a graphite mold or tungsten carbide, preferably tungsten carbide, whose inner chamber is protected by a graphite sheet. The pressure is applied cold or hot, preferably cold. The pressure range is between 2 and 400 MPa. The rise in temperature occurs before or after the nominal pressure is applied, preferably after. The shaping temperature is between 500 and 900 ° C, preferably at 700 ° C. The working atmosphere for sintering can be nitrogen, argon or vacuum but is preferably argon. The sintering lasts between 9 and 20 minutes, preferably 11 minutes. The compactness of the pellets obtained are between 95 and 100%.
    For example, an Au-zirconia powder dosed at 73.4% by weight of gold, precooked at 450 ° C., with shaping under argon, a pressure of 300 MPa applied cold and then raised to 700 ° C. all for 19 minutes leads to the formation of a pellet having a density of 12.99 g.cm <-> <3> and a compactness of 98%.
    Example 3
    Starting from an Au-zirconia powder produced by the method described above, its gold content is measured by cupellation at 84% gold. A total of the inorganic adjuvant such as mica with a mass of 8% of the total mass of the powder is added to the powder. The whole is then finely mixed and ground to control the particle size. The mixture obtained is then shaped under argon, with a pressure of 300 MPa applied cold and then raised to 700 ° C, all for 19 minutes, so as to form a pellet having a density of 12.3 g.cm <-> <3> and a compactness of 98%.
    权利要求:
    Claims (21)
    [1]
    A process for producing a material comprising between 12 and 23 carats of an adjustable color solid noble metal formed of a noble metal-containing nanoparticle assembly in a matrix of an inorganic material, the material comprising at least 50 % by weight of the noble metal; the method comprising the steps of:supplying to a reactor a mixture comprising a noble metal precursor, a precursor of the inorganic material, and a solvent including water, an alcoholic solvent, and a polar aprotic solvent; andheating said mixture to a first temperature (T1) so as to reduce the noble metal precursor;characterized in that said mixture comprises between 5 and 20% vol of water; between 40 and 60% vol of the polar aprotic solvent, and between 25 and 50% vol of the alcoholic solvent;and in that said mixture comprises between 50 and 100 g of the noble metal precursor.
    [2]
    The process of claim 1, wherein the noble metal precursor comprises a gold salt.
    [3]
    3. The process according to claim 1 or 2, wherein the material comprises between 50% and 95% by weight of the noble metal.
    [4]
    4. The process according to one of claims 1 to 3, wherein the alcoholic solvent is isopropanol.
    [5]
    5. The process according to one of claims 1 to 4, wherein the polar aprotic solvent is N, N-dimethylformamide.
    [6]
    The process according to one of claims 1 to 5, wherein the inorganic material comprises a zirconia precursor,
    [7]
    7. The process of claim 6, wherein the precursor of is a zirconium propoxide.
    [8]
    The process of claim 6 or 7, wherein the mixture comprises a chelating agent.
    [9]
    The process according to one of claims 1 to 5, wherein the inorganic material comprises a silica precursor.
    [10]
    The process of claim 9, wherein the silica precursor is a tetraethyl orthosilicate.
    [11]
    The process of claim 9 or 10, wherein the mixture further comprises an aqueous solution of sodium citrate.
    [12]
    The process according to one of claims 1 to 11, wherein the first temperature is about 130 ° C.
    [13]
    13. The method according to one of claims 1 to 12, further comprising a step of cooling the mixture to a second temperature (T2) lower than the first temperature (T1) so as to obtain a suspension.
    [14]
    The method of claim 13, further comprising a step of filtering the slurry, and a step of grinding and sieving the filtered slurry to obtain a powder.
    [15]
    The method of claim 14, further comprising a step of compacting the powder by a sintering process.
    [16]
    The process of claim 15, wherein the sintering process comprises a flash sintering process.
    [17]
    17. The method according to one of claims 1 to 14 and claim 15, wherein an inorganic adjuvant is added to the mixture provided in the reactor, before the step of heating the mixture to the first temperature (T1), or added and mixed with the powder obtained after the filtration step, but before the compaction step.
    [18]
    18. The material comprises between 12 and 23 carats of an adjustable solid color noble metal formed by the process according to one of claims 1 to 17.
    [19]
    19. The material of claim 18, used to manufacture all or part of parts or components for applications in the field of luxury or cosmetics.
    [20]
    20. The material of claim 18, used to manufacture all or part of parts or components in the field of watchmaking, jewelery, jewelery, leather goods or writing instruments.
    [21]
    21. The material of claim 18, used to manufacture all or part of parts or components in the dental, medical or biomedical field.
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    同族专利:
    公开号 | 公开日
    CH711352B1|2019-09-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1887052A1|2006-07-31|2008-02-13|Rolex Sa|Pigmented ceramic element|
    EP2369022A1|2010-03-11|2011-09-28|Neollia SAS|Coloured solid precious material made up of an assembly of nanoparticles of noble metals|
    法律状态:
    2017-11-30| PK| Correction|Free format text: RECTIFICATION INVENTEUR |
    2017-11-30| PUEA| Assignment of the share|Owner name: CARTIER INTERNATIONAL AG, CH Free format text: FORMER OWNER: NEOLLIA SAS, CH |
    优先权:
    申请号 | 申请日 | 专利标题
    CH01080/15A|CH711352B1|2015-07-24|2015-07-24|Process for manufacturing a material of a colored solid noble metal|CH01080/15A| CH711352B1|2015-07-24|2015-07-24|Process for manufacturing a material of a colored solid noble metal|
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