• 专利附录
  • 专利说明
  • 权利要求
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  • 优先权
    • 专利摘要:
    The present invention relates to a method of manufacturing a part by alloying a precious metal with boron, this method comprising the steps consisting in: - providing with an amount of precious metal reduced to the powder state; - provide themselves with a quantity of nano-structured micrometric boron powder; - mix the precious metal powder with the nano-structured micrometric boron powder and compact this powder mixture by applying a uni-axial pressure; - subjecting the mixture of precious metal powder and nano-structured micrometric boron powder to a spark plasma sintering treatment under a pressure between 0.5 GPa and 10 GPa, or to a hot isostatic pressing (HIP) compression treatment at a pressure between 80 bars and 2200 bars, the treatment being carried out at a temperature between 400 ° C and 2100 ° C in order to obtain at least one ingot of an alloy of precious metal and boron, and - machining the ingot of alloy of precious metal and boron in order to obtain the desired part, or else - reducing the ingot of alloy of precious metal and boron to l powder state by a micronization treatment, and obtain the desired part by treatment of the powder resulting from the micronization treatment. The invention also relates to an alloy of gold and boron.
    公开号:CH715619A2
    申请号:CH01514/18
    申请日:2018-12-07
    公开日:2020-06-15
    发明作者:Miko Csilla；Bazin Jean-Luc；Grosjean Rémi
    申请人:Swatch Group Res & Dev Ltd；
    IPC主号:
    专利说明:

    Technical field of the invention
    The present invention relates to a process for the manufacture of precious metal alloys. The present invention also relates to such precious alloys. In particular, the present invention relates to a process for manufacturing light alloys of precious metals obtained from gold, silver, platinum, palladium, ruthenium or iridium. The light alloys of precious metals in question here are titratable, that is to say that they are alloys whose ratio between the mass of the precious metal which enters into the composition of the alloy and the total mass of this alloy is determined by law.
    Technological background of the invention
    A metal alloy results from the combination by fusion of a first metallic element with at least one second metallic element. The advantage of metal alloys lies in the fact that the properties, in particular mechanical, of such alloys are superior to the mechanical properties of the metallic elements considered individually which enter into their composition.
    The mechanical properties of a metal can in particular be improved by deformation, in particular by work hardening; these mechanical properties can also be improved chemically, by adding one or more alloying elements to the base metal. These additions also often improve chemical properties such as the corrosion resistance of the base metal.
    The technique of metal alloys is particularly interesting in the case of precious metals such as gold. Indeed, gold is known to easily deform when cold, which is why it was used from the end of the Neolithic to make jewelry and adornments as well as coins from Antiquity. However, the ease with which gold can be deformed is also a drawback since a simple mechanical impact is enough to deform the jewel produced using this noble metal. This is why we sought very early to improve the mechanical properties of gold by combining it with other metallic elements; silver and copper are the two main metals used in alloy with gold and are known to improve the rigidity of gold.
    The alloying of gold with other metallic elements such as silver or copper leads to metallic alloys whose hardness is greater than that of gold. However, these gold alloys have the disadvantage of having a high density. This is why it has been attempted to combine gold with metallic elements of lower density.
    Tests have already been carried out to try to combine gold (Au) which is a heavy metal, that is to say a metal whose density is high (about 19.3 g.cm <-3 >), with boron (B) which is a very light metal, that is to say one with a low density (about 2.3 g.cm <-3>). However, attempts to date to try to combine gold and boron using conventional metallurgical techniques have all failed or, at best, resulted in dissolution rates very weak boron, not allowing to envisage an industrial production. The materials resulting from the combination of gold and boron have indeed proved to be unstable and it has proved impossible to produce solid titratable components such as 18 carat gold using this combination. These problems are explained in particular by the fact that during melting, it is not possible to mix gold and boron; in fact, because of its high density, gold tends to sediment at the bottom of the crucible, while boron, whose density is lower, floats.
    The recent marketing of boron powders obtained by nanostructuring techniques has revived interest in gold and boron alloys and, more generally, for any type of alloy between a precious metal (gold (Au), silver (Ag), platinum (Pt), palladium (Pd), ruthenium (Rh) or iridium (Ir)) and boron (B).
    The processes for manufacturing metal alloys by powder metallurgy technology make it possible to obtain materials which would be impossible to manufacture using traditional metallurgy techniques. This is particularly interesting in the case where the metal which goes into the composition of such a metal alloy is a titratable precious metal such as gold (Au), silver (Ag), platinum (Pt), palladium (Pd), ruthenium (Rh) or iridium (Ir). In addition, the metal alloys obtained by powder technology are both lighter and harder than the metal alloys obtained by conventional metallurgy.
    Nano-structured boron is in the form of a gray / black powder formed of particles whose dimensions are between 5 nm and 12 nm and which are formed of a core consisting of HfB2, NiB , CoB, YB4 or YB6 and whose structure is crystalline, and an amorphous boron layer whose thickness is a few nanometers and in which the core of these particles is coated. These particles are agglomerated together to form three-dimensional structures whose dimensions lie in the micrometric range and whose specific surface is of the order of 700 m 2 for 1 g of powder.
    Summary of the invention
    The present invention aims to provide a method of manufacturing light alloys of precious metals allowing in particular to obtain light alloys stable from a physicochemical point of view using which it is possible to produce components massive. The present invention also relates to such precious light alloys.
    To this end, the present invention relates to a process for manufacturing a part by alloying a precious metal with boron, this process comprising the steps consisting in:<tb> - <SEP> have at least a quantity of precious metal reduced to a powder state;<tb> - <SEP> take a quantity of a nano-structured micrometric boron powder;<tb> - <SEP> mix the precious metal powder with the nano-structured micrometric boron powder and compact this mixture of powders by applying a uni-axial pressure;<tb> - <SEP> subject the mixture of precious metal powder and nano-structured micrometric boron powder to a spark plasma sintering treatment under a pressure of between 0.5 GPa and 10 GPa, or else a hot isostatic pressing (HIP) compression treatment at a pressure between 80 bars and 2200 bars, the treatment being carried out at a temperature between 400 ° C and 2100 ° C in order to '' obtain at least one ingot of a precious metal and boron alloy, and<tb> - <SEP> to machine the ingot of alloy of precious metal and boron in order to obtain the desired part, or else<tb> - <SEP> reduce the ingot of precious metal and boron alloy to the powder state by a micronization treatment, and obtain the desired part by treatment of the powder resulting from the micronization treatment.
    Thanks to these characteristics, the method according to the invention makes it possible to obtain alloys of precious metal and of boron which have both excellent mechanical properties and whose density is low. To the knowledge of the Applicant, the method according to the invention offers, for the first time, the possibility of combining, on an industrial scale, a very low density component, in this case boron, with a precious metal , in particular but not exclusively gold, whose density is high. Thanks to the process of the invention, it is possible to obtain alloys of precious metal and of boron which are stable from a physicochemical point of view, having excellent mechanical properties, and whose density is low. Remarkably, in the process according to the invention, the selected precious metal and the boron particles are intimately combined, without at any time a phenomenon of segregation between the two materials being observed.
    According to special embodiments of the invention:<tb> - <SEP> in order to obtain the desired part, the powder resulting from the micronization treatment is introduced into a mold and subjected to a uni-axial or isostatic pressure;<tb> - <SEP> in order to obtain the required part, the powder resulting from the micronization treatment is subjected to a three-dimensional additive manufacturing treatment;<tb> - <SEP> the three-dimensional additive manufacturing process is of the direct printing type;<tb> - <SEP> the treatment by direct printing is chosen from the group formed by laser sintering (Selective Laser Melting or SLM) and sintering by electron bombardment (E-beam melting);<tb> - <SEP> the three-dimensional additive manufacturing process is of the indirect printing type;<tb> - <SEP> indirect printing processing is chosen from the group formed by Inkjetting, nanoparticle jetting (NPJ) and Digital Light Projecting (DLP).
    According to another special embodiment of the invention, the manufacturing process further comprises the steps of:<tb> - <SEP> mix the powder resulting from the micronization treatment of the ingot of precious metal and boron alloy with a binder in order to obtain a feedstock;<tb> - <SEP> produce a green body (green body) by subjecting the feedstock to an injection or micro-injection of additive manufacturing;<tb><tb> - <SEP> obtain a brown body by subjecting the green part to a step of removing the polymeric binder called debinding step during which the green part is chemically treated then heat in an oven to burn the residual polymeric binder, this debinding step typically taking place in the gas phase in an atmosphere of nitric acid or oxalic acid and at a temperature between 100 ° C and 140 ° C;<tb> - <SEP> subject the brown part to a sintering treatment in a protected atmosphere and at a temperature between 700 ° C and 1800 ° C in order to obtain the desired part.
    According to another special embodiment of the invention, the manufacturing process also comprises the steps consisting in:<tb> - <SEP> mix the powder resulting from the micronization treatment of the ingot of precious metal and boron alloy with a binder in order to obtain a feedstock;<tb> <SEP> produce a green body (green body) whose shape corresponds to the profile of the sought-after part using an indirect additive manufacturing technique;<tb> - <SEP> obtain a brown body by subjecting the green part to a step of removing the polymeric binder called debinding step during which the green part is chemically treated then heat in an oven to burn the residual polymeric binder, this debinding step typically taking place in the gas phase in an atmosphere of nitric acid or oxalic acid and at a temperature between 100 ° C and 140 ° C;<tb> - <SEP> subject the brown part to a sintering treatment in a protected atmosphere and at a temperature between 700 ° C and 1800 ° C in order to obtain the desired part.
    According to other special embodiments of the invention:<tb> - <SEP> the additive manufacturing technique is chosen from the group formed by Binder jetting, Solvent on Granulate jetting, FDM or micro-extrusion;<tb> - <SEP> after the sintering treatment, the part resulting from the sintering step is subjected to a post-treatment step by hot isostatic pressing (HIP) under a pressure of between 500 bars and 2200 bars, and at a temperature between 600 ° C and 2100 ° C;<tb> - <SEP> the binder is chosen from the group formed by polyethylene glycol (PEG), cellulose acetate butyrate (CAB), nano-cellulose, corn starch, sugar, polylactic acid ( Polylactic Acid or PLA), polyethylene, polypropylene, synthetic or natural wax and stearic acid;<tb> - <SEP> the precious metal is chosen from the group formed by gold (Au), silver (Ag), platinum (Pt), palladium (Pd), ruthenium (Rh) and l iridium (Ir), and the nanostructured micrometric boron is chosen from the group formed by NiB, CoB, YB4 and YB6;<tb> - <SEP> 25% by weight of nano-structured micrometric boron are mixed with 75% by weight of gold;<tb> - <SEP> the nanostructured boron is in the form of a powder formed of particles whose dimensions are between 5 nm and 12 nm and which are formed of a core consisting of HfB2 whose structure is crystalline , and a layer of amorphous boron whose thickness is a few nanometers and in which the core of these particles is coated, these particles being agglomerated together to form three-dimensional structures whose dimensions lie in the micrometric range;<tb> - <SEP> the specific surface of the nanostructured boron particles is of the order of 700 m <2> for 1g of powder;<tb> - <SEP> Nano-structured micrometric boron is obtained by synthesis in molten salt, a technique better known by its Anglo-Saxon name Synthesis by Molten Knows or SMS, this synthesis being carried out dry, wet or under an argon atmosphere;<tb> - <SEP> the alloy of gold and boron in accordance with the process of the invention makes it possible to obtain an 18 carat gold with a density between 6.6 and 7 g / cm <3>.
    Detailed description of an embodiment of the invention
    The present invention proceeds from the general inventive idea which consists in providing an alloy of a titratable precious metal which is stable from a physicochemical point of view and which has excellent mechanical properties.
    To this end, the present invention relates to a process for manufacturing a part by alloying a precious metal with boron, this process comprising the steps consisting in:<tb> - <SEP> have at least a quantity of precious metal reduced to a powder state;<tb> - <SEP> take a quantity of a nano-structured micrometric boron powder;<tb> - <SEP> mix the precious metal powder with the nano-structured micrometric boron powder and compact this mixture of powders by applying a uni-axial pressure;<tb> - <SEP> subject the mixture of precious metal powder and nano-structured micrometric boron powder to a spark plasma sintering treatment under a pressure of between 0.5 GPa and 10 GPa, or else a hot isostatic pressing (HIP) compression treatment at a pressure between 80 bars and 2200 bars, the treatment being carried out at a temperature between 400 ° C and 2100 ° C in order to '' obtain at least one ingot of a precious metal and boron alloy, and<tb> - <SEP> machining the ingot of precious metal and boron alloy in order to obtain the desired part, or<tb> - <SEP> reduce the ingot of precious metal and boron alloy to the powder state by a micronization treatment, and obtain the desired part by treatment of the powder resulting from the micronization treatment.
    Once the ingot of precious metal and boron alloy obtained by implementing the method according to the invention has been micronized, a first possibility for obtaining the desired solid piece consists in introducing the resulting powder. of the micronization treatment in a mold and subjecting this mold to a uni-axial or isostatic pressure.
    Once the ingot of precious metal and boron alloy obtained by the implementation of the method according to the invention has been micronized, a second possibility for obtaining the desired solid piece consists in subjecting the resulting powder from the micronization treatment to a three-dimensional additive manufacturing treatment.
    The three-dimensional additive manufacturing treatment can be of the direct printing type. The three-dimensional additive manufacturing techniques of the direct type available are laser sintering, also known by its Anglo-Saxon name Selective Laser Melting or SLM and electron bombardment sintering also known by its Anglo-Saxon name E-beam melting.
    The three-dimensional additive manufacturing treatment can be of the indirect printing type. The three-dimensional additive manufacturing techniques of the indirect type available are:<tb> - <SEP> inkjet printing: the powder resulting from the micronization treatment of the ingot of precious metal and boron alloy is dispersed in the ink. The ink is printed layer after layer, each layer being hardened by exposure to radiation from a light source, for example UV light, before deposition of the next layer.<tb> - <SEP> nanoparticle jetting (NPJ): this technique, notably developed by the company XJet, is similar to printing by liquid ink jet, with the difference that the ink is composed of nanoparticles in suspension resulting from the micronization treatment. The suspension is then sprayed, then dried layer by layer.<tb> - <SEP> Digital Light Projecting (DLP): this technique consists in projecting the image of the part you wish to structure by reflection onto a mirror onto a powder bed containing the powder particles resulting from the processing of micronization dispersed in a photopolymer.
    According to another special embodiment of the invention, after mixing the powder resulting from the micronization treatment of the ingot of precious metal and boron alloy with a binder in order to obtain a feedstock ( feedstock), a green body is produced, the shape of which corresponds to the profile of the part sought by subjecting the feedstock either to an injection or micro-injection, or to an additive manufacturing technique.
    Among the indirect additive manufacturing techniques available, there may be mentioned:<tb> - <SEP> Binder jetting: this technique consists in spraying an ink jet containing a solvent and a binder on a powder bed in which the powder particles are dispersed resulting from the dispersed micronization treatment.<tb> - <SEP> Solvent on Granulate jetting: this technique consists in spraying a solvent on a bed of aggregates, each of these aggregates being formed from a plurality of powder particles resulting from the micronization treatment agglomerated together by means of 'a binder. The dimensions of these aggregates are of the order of 10 μm to 50 μm. The required part is printed layer by layer, the aggregates agglomerating thanks to the binder. Once the desired part has been printed, it is subjected to a debinding operation in order to remove the solvent, then it is sintered.<tb> - <SEP> FFD (Fused Filament Deposition): filaments whose dimensions are in the millimeter range are made by agglomerating the powder particles resulting from the micronization treatment by means of a binder. These filaments are then heated and the material of which they are made escape from a nozzle whose diameter is of the order of 40 μm and make it possible to print the desired part in three dimensions.<tb> - <SEP> micro-extrusion.
    As for the binder, it is chosen from the group formed by polyethylene glycol (PEG), cellulose acetate butyrate (CAB), nano-cellulose (nanometric cellulose derivative), corn starch, sugar, polylactic acid (Polylactic Acid or PLA), polyethylene, polypropylene, synthetic or natural wax and stearic acid.
    A brown body is obtained by subjecting the green part to a step of removing the polymeric binder called debinding step during which the green part is chemically treated then heat in an oven to burn the polymeric binder residual, this debinding step typically taking place in the gas phase in an atmosphere of nitric acid or oxalic acid and at a temperature between 100 ° C. and 140 ° C.
    Finally, the brown part is subjected to a sintering treatment in a protected atmosphere and at a temperature between 700 ° C and 1800 ° C in order to obtain the desired part.
    It will be noted that it is possible, after the sintering treatment, to subject the part resulting from the sintering step to a post-treatment step by hot isostatic pressing (HIP) under pressure. between 500 bars and 2200 bars, and at a temperature between 600 ° C and 2100 ° C.
    According to particular embodiments of the invention, the precious metal is chosen from the group formed by gold (Au), silver (Ag), platinum (Pt), palladium (Pd ), ruthenium (Rh) and iridium (Ir). As for the nanostructured micrometric boron, it is NiB, CoB, YB4 or YB6. This nanostructured boron is in the form of a powder formed of particles whose dimensions are between 5 nm and 12 nm and which are formed of a core consisting of boron whose structure is crystalline, and of a layer of amorphous boron the thickness of which is a few nanometers and in which the core of these particles is coated, these particles being agglomerated together to form three-dimensional structures whose dimensions lie in the micrometric range. The specific surface of the nanostructured boron particles is of the order of 700 m 2 for 1 g of powder. To obtain the desired material, a ratio which gives good results for the mixture of gold and boron is 25% by weight of nano-structured micrometric boron and 75% by weight of gold.
    In particular, the present invention relates to a process for manufacturing light alloys of precious metals obtained from gold, silver, platinum, palladium, ruthenium or iridium. The light alloys of precious metals in question here are titratable, that is to say that they are alloys whose ratio between the mass of the precious metal which enters into the composition of the alloy and the total mass of this alloy is determined by law. A remarkable precious metal alloy obtained by the process of the invention is an alloy of 18 carat gold and boron with a density between 6.6 and 7 g / cm <3>.
    It goes without saying that the present invention is not limited to the embodiment which has just been described and that various modifications and simple variants can be envisaged by those skilled in the art without departing from the scope of the invention as defined by the appended claims.
    It will be noted in particular that it has been decided to qualify the boron powder in question here as "micrometric" and "nanostructured" insofar as the aggregates of boron particles which constitute this powder have dimensions in the micrometer range, these aggregates themselves being made up of particles which have a crystal structure in the nanometer range.
    It will also be noted that, although the present description is essentially concerned with a binary precious metal alloy formed from gold and boron, the present invention is not limited to such an example and also covers alloys of precious metals, for example ternary or quaternary. By way of example, in accordance with the invention, it is possible to mix particles of nano-structured micrometric boron powder with gold in weight percentages of 75% and 23% respectively, the balance being constituted by micronized nickel.
    It will also be noted that the gold used in the context of the present invention is 24-carat bright Y2 yellow gold and that the dimensions of the particles obtained by threshing this gold and which form the gold powder used in the framework of the present invention are less than 50 µm.
    It will also be noted that the nano-structured micrometric boron particles in question here are notably known from the thesis in the name of Remi Grosjean, entitled "Boron-based nanomaterials under extreme conditions", pages 70 et seq., Presented publicly October 19, 2018 at Pierre et Marie Curie University - Paris VI, 2016. This thesis is available on the Internet at the following address: https://tel.archives-ouvertes.fr/tel-01898865 (HAL Id : tel-01898865). These nano-structured micrometric boron particles are obtained by synthesis in molten salts, also known by its Anglo-Saxon name Synthesis in Molten Salts or SMS. This synthesis consists of bringing reactive substances of metal and boron into a mixture of salts. When the mixture is heated, the salts melt, thus acting like a liquid medium. The typical synthesis of nanostructured borides in molten salts uses a source of metal (usually a MClx chloride), and sodium hydroboride. Sodium hydroboride is used both as a source of boron and as a reducing agent, so as to obtain M <0> in the reactive medium. The use of such precursors and of lithium and potassium salts necessitates having to work under an inert atmosphere, due to the sensitivity of these chemicals to water and / or oxygen. Therefore, the precursors are handled and mixed in a laboratory glove box under an inert argon atmosphere. The actual synthesis is carried out under an argon atmosphere and not nitrogen, since argon is capable of reacting with certain species of boron and leading to the formation of boron nitride.
    The conditions required for the experimental implementation are therefore the following:<tb> - <SEP> ensure that the reactive medium remains under an argon atmosphere; this objective is achieved by using a quartz tube which is stable at working temperatures and which is connected to a Schlenk line.<tb> - <SEP> heat within a temperature range between 300 ° C and 1000 ° C. The zone of the quartz tube in which the temperature is homogeneous has an extent of approximately 8 cm, that is to say sufficiently large to allow a homogeneous heating of the reactive medium, and sufficiently limited to allow the condensation of the salt vapors to avoid loss of solvents during the reaction. The heating ramp is 10 ° C / min.<tb> - <SEP> avoid parasitic reactions between the reactive medium and the quartz tube. Vitreous carbon is chemically inert in an argon atmosphere and is therefore used as a crucible. The crucible is sufficiently large to allow the condensation of salt vapors in the low temperature zone of the oven.<tb> - <SEP> in some cases it is necessary to stir the reaction mixture. This is done using a rotating glassy carbon rod.
    After the reaction, the reactive medium is allowed to cool naturally. Metal borides are obtained in the form of nanoparticles dispersed in a volume of frozen salts. To remove the salts, washing / centrifugation cycles are carried out in a polar solvent such as water or methanol. Among the adjustable parameters, we note the synthesis temperature, the stopping time and the initial ratio between the metal and boron sources.
    The thesis mentioned above was particularly interested in two nanostructured metal borides: hafnium diboride and calcium hexaboride. CaB6 and HfB2 do not exhibit phase transition under high temperature and high pressure and are therefore well suited for studying the crystallization of the amorphous phase in which the boride particles are embedded.
    Two mixtures of eutectic salts, namely LiCI / KCI and Lil / KI, were used. The first synthesis of HfB2 was carried out in a LiCI / KCI eutectic mixture (45/55 in mass percentage) whose melting temperature is of the order of 350 ° C. HfCl4 and NaBH4 are used in a Hf: B molar ratio = 1: 4 and are mixed with the salt solution. After heating to 900 ° C. for 4 hours, cooling, washing with deionized water and drying under vacuum, a black powder is obtained. The X-ray diffraction grating of this powder shows that HfB2 is the only crystalline phase and has no reflection corresponding either to the solvent salts or to the sodium chloride which may appear as by-products of boride formation. Furthermore, the structure of HfB2 is typical of that of diborides with metal atoms interposed between sheets of boron which have a honeycomb structure.
    According to Scherrer's formula, the particle size is 7.5 nm. This is confirmed by a study by transmission electron microscopy which shows that the particle size is in the range 5-12 nm. Other images obtained by SAED, FFT and HRTEM confirm that HfB2 is the only crystalline phase in the material and that only the nanoparticles are crystalline.
    Transmission electron microscopy also shows that the particles are surrounded by an amorphous bark whose thickness is between 2 and 4 nm. The particles appear as inclusions in a three-dimensional amorphous matrix. The spaces between the particles are filled with an amorphous matrix whose thickness is between 2 and 4 nm. Therefore, the matrix is also nanostructured and the material can be described as a nanocomposite.
    权利要求:
    Claims (20)
    [1]
    1. A method of manufacturing a part by alloying a precious metal with boron, this method comprising the steps consisting in:- bring at least a quantity of precious metal reduced to a powder state;- provide themselves with a quantity of nano-structured micrometric boron powder;- mix the precious metal powder with the nano-structured micrometric boron powder and compact this powder mixture by applying a uni-axial pressure;- subjecting the mixture of precious metal powder and nano-structured micrometric boron powder to a spark plasma sintering treatment under a pressure between 0.5 GPa and 10 GPa, or a hot isostatic pressing (HIP) compression treatment at a pressure between 80 bars and 2200 bars, the treatment being carried out at a temperature between 400 ° C and 2100 ° C in order to obtain at least one ingot an alloy of precious metal and boron, and- machining the ingot of precious metal and boron alloy in order to obtain the desired part, or else- reduce the ingot of precious metal and boron alloy to the powder state by a micronization treatment, and obtain the desired part by treatment of the powder resulting from the micronization treatment.
    [2]
    2. Manufacturing method according to claim 1, characterized in that, in order to obtain the desired part, the powder resulting from the micronization treatment is introduced into a mold and subjected to a uni-axial or isostatic pressure.
    [3]
    3. The manufacturing method according to claim 1, characterized in that, in order to produce the desired part, the powder resulting from the micronization treatment is subjected to a three-dimensional additive manufacturing treatment.
    [4]
    4. The manufacturing method according to claim 3, characterized in that the three-dimensional additive manufacturing treatment is of the direct printing type.
    [5]
    5. Manufacturing method according to claim 4, characterized in that the treatment by direct printing is chosen from the group formed by laser sintering (Selective Laser Melting or SLM) and sintering by electron bombardment (E-beam melting) .
    [6]
    6. The manufacturing method according to claim 3, characterized in that the three-dimensional additive manufacturing treatment is of the indirect printing type.
    [7]
    7. The manufacturing method according to claim 6, characterized in that the treatment by indirect printing is chosen from the group formed by Inkjetting, nanoparticle jetting (NPJ) and Digital Light Projecting (DLP).
    [8]
    8. Manufacturing method according to claim 1, characterized in that it further comprises the steps of:- mix the powder resulting from the micronization treatment of the ingot of precious metal and boron alloy with a binder in order to obtain a feedstock;- produce a green part (green body) whose shape corresponds to the profile of the part sought by subjecting the feedstock either to an injection or micro-injection, or to an additive manufacturing technique;- Obtain a brown piece (brown body) by subjecting the green piece to a step of removing the polymeric binder called debinding step during which the green piece is chemically treated then heat in an oven to burn the residual polymeric binder, this debinding step taking place in the gas phase in an atmosphere of nitric acid or oxalic acid and at a temperature between 100 ° C and 140 ° C;- subject the brown part to a sintering treatment in a protected atmosphere and at a temperature between 700 ° C and 1800 ° C in order to obtain the desired part.
    [9]
    9. The manufacturing method according to claim 8, characterized in that the additive manufacturing technique is chosen from the group formed by Binder jetting, Solvent on Granulate jetting, FDM or micro-extrusion.
    [10]
    10. Manufacturing process according to one of claims 8 and 9, characterized in that, after the sintering treatment, the part resulting from the sintering step is subjected to a post-treatment step by hot isostatic compression ( Hot Isostatic Pressing or HIP) at a pressure between 500 bar and 2200 bar, and at a temperature between 600 ° C and 2100 ° C.
    [11]
    11. Manufacturing process according to one of claims 8 to 10, characterized in that the binder is chosen from the group formed by polyethylene glycol (PEG), cellulose acetate butyrate (CAB), nano-cellulose, corn starch, sugar, polylactic acid, polyethylene, polypropylene, synthetic or natural wax and stearic acid.
    [12]
    12. Manufacturing method according to one of claims 1 to 11, characterized in that the precious metal is chosen from the group formed by gold (Au), silver (Ag), platinum (Pt), palladium (Pd), ruthenium (Rh) and iridium (Ir), and in that the nanostructured micrometric boron is chosen from the group formed by NiB, CoB, YB4 and YB6.
    [13]
    13. The manufacturing method according to claim 12, characterized in that 25% by weight of nano-structured micrometric boron is mixed with 75% by weight of gold.
    [14]
    14. The manufacturing method according to one of claims 12 and 13, characterized in that the nanostructured boron is in the form of a powder formed of particles whose dimensions are between 5 nm and 12 nm and which are formed of a core consisting of HfB2, the structure of which is crystalline, and of an amorphous boron layer the thickness of which is a few nanometers and in which the core of these particles is coated, these particles being agglomerated together to form structures three-dimensional whose dimensions are in the micrometric range.
    [15]
    15. The manufacturing method according to claim 14, characterized in that the specific surface of the nanostructured boron particles is of the order of 700 m <2> for 1g of powder.
    [16]
    16. Manufacturing process according to one of claims 12 to 15, characterized in that the gold that is used is 1⁄2 bright yellow 24 carat gold and that the dimensions of the gold particles are smaller at 50 µm).
    [17]
    17. Alloy of gold and boron.
    [18]
    18. Alloy according to claim 17, characterized in that it is 18 carat gold.
    [19]
    19. Alloy according to one of claims 17 and 18, characterized in that it contains other alloyed elements.
    [20]
    20. Alloy according to one of claims 17 to 19, characterized in that it has a density between 6.6 and 7 g / cm <3>.
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    BE431573A|
    BE659600A|
    同族专利:
    公开号 | 公开日
    CH715619B1|2020-12-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    2020-07-15| PK| Correction|Free format text: RECTIFICATION INVENTEUR |
    优先权:
    申请号 | 申请日 | 专利标题
    CH01514/18A|CH715619B1|2018-12-07|2018-12-07|A method of manufacturing a part made of an alloy of a precious metal with boron, a method of manufacturing such an alloy and an alloy of 18 carat gold and boron.|CH01514/18A| CH715619B1|2018-12-07|2018-12-07|A method of manufacturing a part made of an alloy of a precious metal with boron, a method of manufacturing such an alloy and an alloy of 18 carat gold and boron.|
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