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    • 专利摘要:
    The invention relates to a process for the preparation of coated metal nanoparticles. According to the invention, each nanoparticle comprises a core consisting of at least one metal M and a layer consisting of at least one polymer, the layer coating the metal core, which process comprises the following steps: (a1) the preparation of a solution A comprising: said at least one metal M in the form of Mn + cations, n being an integer between 1 and 3, each metal M being a transition metal, a polyol, and a salt of a noble metal, (a2) preparing a solution B comprising at least one organic monomer of said at least one polymer, in an organic solvent, (b) mixing the solutions A and B, said mixture being brought to the temperature of boiling of the polyol, and (c) recovery of coated metal nanoparticles. The invention also relates to a method of manufacture and uses of a composite material comprising these coated metal nanoparticles as well as to a radiofrequency device comprising this composite material.
    公开号:FR3059661A1
    申请号:FR1661979
    申请日:2016-12-06
    公开日:2018-06-08
    发明作者:Mohammed Benwadih；Jacqueline Bablet；Olivier Poncelet；Jonathan SKRZYPSKI
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    Holder (s): COMMISSIONER OF ATOMIC ENERGY AND ALTERNATIVE ENERGIES Public establishment.
    Extension request (s)
    Agent (s): BREVALEX Limited liability company.
    FR 3 059 661 - A1
    104 / METHODS OF MANUFACTURING COATED METAL NANOPARTICLES AND A COMPOSITE MATERIAL COMPRISING THE SAME, USE OF SUCH A MATERIAL AND DEVICE COMPRISING THE SAME.
    ©) The invention relates to a site preparation process.
    coated metallic nanoparticles.
    According to the invention, each nanoparticle comprising a core made up of at least one metal M and a layer made up of at least one polymer, the layer covering the metallic core, which process comprises the following steps:
    (a ·,) the preparation of a solution A comprising: said at least one metal M in the form of cations M n + , n being an integer between 1 and 3, each metal
    M being a transition metal, a polyol, and a salt of a noble metal, (a 2 ) the preparation of a solution B comprising at least one organic monomer of said at least one polymer, in an organic solvent, (b) mixing solutions A and B, this mixture being brought to the boiling point of the polyol, and (c) recovering the coated metal nanoparticles.
    The invention also relates to a method of manufacturing and to the uses of a composite material comprising these coated metallic nanoparticles as well as to a radiofrequency device comprising this composite material.
    METHODS OF MAKING COATED METAL NANOPARTICLES AND COMPOSITE MATERIAL COMPRISING SAME, USE OF SUCH MATERIAL AND DEVICE COMPRISING SAME
    DESCRIPTION
    TECHNICAL AREA
    The invention relates to a process for the preparation of coated metallic nanoparticles, these nanoparticles having magnetic and dielectric properties.
    The invention also relates to a process for manufacturing a composite material obtained from a formulation comprising these coated metal nanoparticles dispersed in a polymer matrix.
    The invention also relates to the uses of the composite material as obtained by this manufacturing process as well as to a device, electronic or radiofrequency, comprising this composite material.
    PRIOR STATE OF THE ART
    Faced with miniaturization and the desire to integrate an ever-increasing number of new applications within the same wireless communication system, such as a mobile terminal, the reduction in the size of its constituent elements, in particular that of the antenna, becomes an important issue.
    The dimensions of such an antenna being inversely proportional to the product of the relative dielectric permittivity, noted ε Γ , and of the relative magnetic permeability, noted p r , the reduction of the size of the antenna generally passes through the use of materials purely dielectric with high permittivity.
    However, the use of such dielectric materials is to the detriment of some of the performances of the antenna, among which its bandwidth.
    To remedy the drop in bandwidth performance, it has been proposed to use materials associating magnetic permeability with dielectric permittivity and, in particular, materials called composite materials, magnetic and dielectric materials or magneto-dielectric materials. It is the expression of composite material (s) which will be used in the remainder of this description.
    These composite materials are conventionally obtained from a formulation comprising a polymer matrix and particles dispersed in the polymer matrix.
    Conventionally, the particles dispersed in the polymer matrix are inorganic nanoparticles, the term nanoparticles defining particles whose three dimensions are between 1 nm and 1000 nm.
    The properties of the composite material can thus be adjusted as required, in particular as a function of the nature of these nanoparticles dispersed in the polymer matrix.
    In particular, the use of nanoparticles of a transition metal of the 3d series, and / or its metal alloys, gives said composite material good magnetic permeability but low dielectric permittivity.
    Indeed, due to their magnetic properties, these metallic nanoparticles tend to agglomerate with one another. As such agglomerates of nanoparticles are particularly difficult to disperse in a solvent or in a polymer matrix, it becomes practically impossible to form layers of composite material having a homogeneous distribution of these nanoparticles. In addition, the presence of these agglomerates can promote the circulation of an electric current between the nanoparticles present in the composite material and, thus, cause short-circuits within the same layer of composite material, or even between the different layers. of the same multilayer structure.
    In addition, experience has shown that films of a composite material obtained from a formulation comprising such agglomerates of metallic nanoparticles in a polymer matrix are characterized by a lack of cohesion and mechanical strength.
    The object of the invention is, therefore, to overcome the drawbacks of composite materials of the prior art, and to propose a process for the preparation of nanoparticles which, once dispersed in a polymer matrix, form with this matrix a formulation allowing to obtain a composite material which has a magnetic permeability comparable to that of the composite materials of the prior art, typically at least 1, as well as mechanical properties and a dielectric permittivity which are both superior to those of these composite materials of the prior art, the dielectric permittivity being at least 2, this dielectric permittivity being advantageously at least 3 and, preferably, at least 4.
    Another object of the invention is therefore to propose a method for manufacturing such a composite material, this composite material having in particular to make it possible to produce antennas which have a space requirement which is as small as possible without their properties, and in particular their bandwidth, are not altered.
    STATEMENT OF THE INVENTION
    These and other aims are achieved, firstly, by a process for the preparation of coated metal nanoparticles, each nanoparticle comprising a core made up of at least one metal M and a layer made up of at least one polymer, the layer covering the metallic core.
    According to the invention, the method comprises the following steps:
    (ai) the preparation of a solution A comprising:
    said at least one metal M in the form of cations M n + , n being an integer between 1 and 3, each metal M being a transition metal, a polyol, and a salt of a noble metal, (a ) preparing a solution B comprising at least one organic monomer of said at least one polymer, in an organic solvent, (b) mixing solutions A and B, this mixture being brought to the boiling point of the polyol, whereby coated metallic nanoparticles are obtained, (c) recovering coated metallic nanoparticles.
    In the foregoing and in the following, the term “nanoparticles” means particles whose three dimensions are between 1 nm and 1000 nm.
    Likewise, the expression between ... and ... which has just been used to define an interval and which is used in the rest of the present application, should be understood as defining not only the values of l 'interval, but also the values of the limits of this interval.
    The coated metal nanoparticles as prepared by the process according to the invention concomitantly have magnetic properties, conferred by the metal or the metal alloy forming the core of these nanoparticles, and dielectric properties, conferred by the polymer or the polymer alloy forming the layer of said nanoparticles, it being specified that this polymeric layer coats the metallic core so as to be in contact with this core and to coat it.
    Thus, and as will be seen below, the composite material, which is prepared from a formulation comprising these coated metallic nanoparticles dispersed in a polymer matrix, concomitantly exhibits magnetic permeability and dielectric permittivity, as well as good properties mechanical.
    The process for preparing coated metal nanoparticles according to the invention comprises a step (ai) during which a preparation A is carried out comprising at least one metal M in the form of cations M n + , a polyol and a salt of a noble metal.
    This solution A can comprise only one metal M in cationic form, but it can also comprise several metals M in cationic form, that is to say comprise a mixture of two, three, or even more, metals Mi, M2 , M3 ... distinct, these metals all being in cationic form.
    Solution A prepared during step (ai) comprises said at least one metal M in the form of cations M n + , with n being an integer between 1 and 3.
    If it is more particularly envisaged that solution A comprises one or more metals M in only one of their cationic forms, nothing prevents us from considering that this solution A comprises this or these metals M in several of their cationic forms.
    In an advantageous variant of the invention, solution A comprises said at least metal M in the form of M 2+ cations, corresponding to the case where n = 2.
    Whether the solution A comprises a single metal M or several metals M, whether this or these metals M are in a single cationic form or in several of their cationic forms, each metal M is a transition metal.
    In an advantageous variant of the invention, each transition metal M has an atomic number between 21 and 30, thus corresponding to a transition metal of the 3d series.
    In a preferred variant of the invention, each transition metal M is chosen from the group consisting of Ni, Fe and Co.
    The metallic core of each nanoparticle can thus be constituted in particular by a single one of these metals, which can then be Ni, Fe or Co, by an alloy of two of these metals, this alloy then being able to be an alloy of Ni-Fe, Co -Ni or Fe-Co, or by an alloy of these three metals, that is to say an Ni-Fe-Co alloy.
    In a more preferred variant, the metallic core of each nanoparticle consists of a Co-Ni alloy.
    While it is of course conceivable to prepare nanoparticles whose metallic core can include any Co / Ni molar ratio, a Co / Ni molar ratio of between 50/50 and 90/10 is preferred to obtain nanoparticles whose morphology is close to that of sticks.
    This Co / Ni molar ratio is advantageously between 70/30 and 85/15 and is preferably around 80/20.
    In one embodiment of the invention, said at least one metal M in the form of cations M n + is a metal salt.
    In an advantageous variant of the invention, this metal salt comprises at least one element chosen from the group consisting of an acetate, an acetylacetonate, a hydroxide and an oxide of the transition metal M.
    In a preferred variant of the invention, this metal salt is an acetate of the transition metal M, such an acetate possibly being anhydrous or hydrated.
    As examples of acetates of the transition metal M, there may be mentioned in particular a nickel acetate Ni (CH3COO) 2, an iron acetate FefChbCOOh or also a cobalt acetate CofCHiCOOh.
    Mention may in particular be made, as examples of acetylacetonates of the transition metal M, of a nickel acetylacetonate, an iron acetylacetonate or also a cobalt acetylacetonate.
    In one embodiment of the invention, the molar concentration of cations M n + , denoted [M n + ], in solution A, is between 0.02 mol / L and 1 mol / L.
    In an advantageous variant of the invention, this molar concentration [M n + ] is between 0.04 mol / L and 0.5 mol / L and, preferably, between 0.06 mol / L and 0.1 mol / L .
    In addition to the metal (s) M in the form of cations M n + , the solution A used during step (ai) comprises a solvent, in this case a polyol, and a nucleating agent, in this case a noble metal salt.
    In the above, noble metal means one of the following eight metals: gold, silver, rhodium, osmium, palladium, ruthenium, iridium and platinum.
    In one embodiment of the invention, the noble metal is chosen from osmium, ruthenium and iridium.
    Polyols are polar protic solvents which make it possible to at least partially dissolve the metal salts and, in particular, the acetates of the transition metal M described above.
    In one embodiment of the invention, the polyol is a diol, advantageously an α-diol.
    As non-limiting examples of α-diols, mention may especially be made of ethane-1,2-diol, also known under the name of ethylene glycol, propane-1,2diol or even butane-l , 2-diol.
    The noble metal salt, the role of which is specified below, can in particular be chosen from osmium chloride, ruthenium chloride and iridium chloride.
    In one embodiment of the invention, the ratio between the molar concentration of noble metal and the molar concentration of cations M n + , denoted [noble metal] / [M n + ], is between 0.005 and 0.1.
    In an advantageous embodiment of the invention, this ratio of molar concentrations [noble metal] / [M n + ] is between 0.01 and 0.05 and, preferably, between 0.02 and 0.03.
    In one embodiment of the invention, solution A can also comprise sodium hydroxide, in a molar concentration [NaOH] of at most 0.5 mol / L.
    In an advantageous variant of the invention, this molar concentration [NaOH] is between 0.05 mol / L and 0.4 mol / L and, preferably, between 0.1 mol / L and 0.3 mol / L.
    In one embodiment of the invention, step (ai) of preparation of solution A is carried out at a temperature which is strictly lower than the boiling temperature of the polyol present in this solution A.
    In an advantageous variant, the temperature at which solution A is prepared is between 0 ° C and 30 ° C and, preferably, between 15 ° C and 25 ° C, the latter interval corresponding to ambient temperature.
    The process for preparing coated metal nanoparticles according to the invention also comprises a step (a ) During which a preparation B is carried out comprising at least one organic monomer of said at least one polymer, in an organic solvent .
    Solution B may comprise only one organic monomer, in which case, after polymerization, a homopolymer is obtained. However, nothing prevents us from considering that solution B comprises two, three, or even more, monomers, in which case a copolymer is obtained, after polymerization.
    In one embodiment of the invention, this or these organic monomers may in particular be chosen from the group consisting of styrene, an alkyl (meth) acrylate, a fluorocarbon monomer, norbornene and ethylene.
    By the expression (alkyl meth) acrylate, we mean both an alkyl acrylate and an alkyl methacrylate.
    The alkyl (meth) acrylate monomer can in particular be chosen from methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, octyl (meth) acrylate and 2ethylhexyl (meth) acrylate. This alkyl (meth) acrylate monomer is advantageously methyl methacrylate, denoted MMA.
    In an advantageous variant of the invention, solution B comprises only one monomer, this monomer possibly being in particular methyl methacrylate MMA, styrene, norbornene or ethylene which, after polymerization, lead respectively to poly ( methyl methacrylate) or PMMA, polystyrene, polynorbornene or polyethylene.
    Solution B also includes an organic solvent in which the organic monomer (s) are in solution.
    As examples, one can choose tetrahydrofuran (THF) or chloroform to dissolve the styrene.
    In one embodiment of the invention, step (a ) Of preparing solution B is carried out at ambient temperature, that is to say at a temperature typically between 15 ° C. and 25 ° C. .
    Steps (ai) and (a 2 ) of preparation of solutions A and B can be carried out one after the other or concomitantly.
    The process for preparing coated metallic nanoparticles according to the invention also comprises a step (b) during which the mixing of the solutions A and B prepared during steps (ai) and (a 2 ) is carried out.
    This step (b) of mixing solutions A and B is carried out at a temperature corresponding to the boiling point of the polyol present in solution A.
    During this step (b) of mixing solutions A and B occurs concomitantly:
    the total dissolution of the compound comprising the metal (s) M in the form of cations M n + ,
    reduction of the cations M n + into said at least one metal M at its oxidation state 0, denoted M °, according to the following reaction:
    M n + + ne -> M °, and in so doing, the formation of the metallic core of each of the nanoparticles
    - the growth of this metallic core,
    - The formation of the polymeric layer around this metal core by polymerization of the monomer (s) present in the mixture and, in so doing, obtaining coated metallic nanoparticles.
    The coated metal nanoparticles as obtained at the end of the mixing step (b) are in the form of solid nanoparticles in the solution.
    The use of an α-diol as a polyol has several advantages due to the polar and reducing nature of these α-diols and their high boiling point. It is thus possible to dissolve a large number of metal salts comprising the metal (s) M in cationic form and to reduce the corresponding cations at a temperature which is adjustable over a fairly wide temperature range.
    The reduction of cations M n + to metal or metals M ° is therefore carried out directly in solution.
    The noble metal, which is also found in cationic form in the noble metal salt present in solution A, is also reduced during step (b) of mixing and will thus form seeds which will serve as growth sites, or nucleation sites, for the metallic core. The size of the nanoparticles is controlled by the molar ratio [noble metal] / [M n + ],
    To promote this reduction reaction so as to make it as quantitative as possible, sodium hydroxide can be introduced into solution A.
    The layer of polymer (s) which forms around the nanoparticles is obtained by solution polymerization of the organic monomer (s) initially present in solution B, this polymerization being catalyzed by the noble metal salt initially present in solution A.
    It should be noted that the morphology of the coated metallic nanoparticles as obtained at the end of step (b) of mixing can be modulated as a function of the compounds present in solution A and of their molar concentration.
    In a particularly preferred embodiment of the invention, which makes it possible to obtain nanoparticles comprising a metallic core constituted by a Co-Ni alloy and having a rod morphology, solution A comprises cobalt acetate, an acetate of nickel, butane-1,2-diol, sodium hydroxide, and ruthenium trichloride, under the following conditions:
    - a Co / Ni molar ratio of between 50/50 and 90/10,
    - a molar concentration [Co + Ni] of between 0.02 mol / L and mol / L,
    a molar ratio [Ru] / [Co + Ni] of between 0.005 and 0.1, and
    - a molar concentration of NaOH [NaOH] between 0.05 mol / L and 0.5 mol / L.
    The process for preparing coated metallic nanoparticles according to the invention comprises, after step (b) of mixing solutions A and B, a step (c) during which the coated metallic nanoparticles are recovered, the latter can then be used later.
    This recovery step (c) can be carried out by any usual technique used for the separation of a solid and a liquid, such as filtration, centrifugation, etc.
    The invention relates, secondly, to a method of manufacturing a composite material.
    According to the invention, this manufacturing process comprises the following steps (1) to (4):
    (1) a preparation of coated metallic nanoparticles, each nanoparticle comprising a core made up of at least one metal M and a layer made up of at least one polymer, the layer covering the metallic core, by implementing the preparation process as defined above, (2) a mixture of the nanoparticles prepared in step (1) in a polymer matrix, whereby a formulation is obtained comprising the nanoparticles dispersed in the polymer matrix, (3) a deposit of the formulation obtained at the end of step (3), and (4) an application of energy to the formulation deposited in step (3), whereby the composite material is obtained.
    The characteristics described above in connection with the process for the preparation of coated metallic nanoparticles, in particular the composition of solutions A and B as well as the characteristics relating to coated metallic nanoparticles and to the polymers capable of being used in the polymer matrix, are of course applicable. to the present manufacturing process.
    The manufacturing process according to the invention is therefore particularly easy to implement, the nanoparticles prepared during step (1) being able to be directly incorporated and dispersed in the polymer matrix.
    Step (2) consists in obtaining, by mixing and / or kneading, a formulation characterized by a distribution of metallic nanoparticles coated in the polymer matrix which is as homogeneous as possible.
    According to a particular embodiment of the invention, the mass proportion of coated metallic nanoparticles, relative to the total mass of the formulation, is between 10% and 50%, advantageously between 15% and 45% and, preferably, between 20% and 40%.
    Many polymers can be envisaged for the polymer matrix of the formulation from which the composite material according to the invention is obtained.
    This polymer matrix can in particular comprise at least one polymer chosen from the group consisting of a thermosetting polymer, a thermoplastic polymer and an elastomer, this polymer possibly being alone or as a mixture in the form of an alloy.
    In an advantageous variant, the polymer matrix comprises at least one thermoplastic polymer, which can in particular be chosen from the group consisting of a polystyrene, a poly (methyl methacrylate), a fluorocarbon polymer, a polynorbornene and a polyethylene, this polymer being of preferably a polystyrene.
    In a preferred variant, the polymer forming the layer of each nanoparticle and the polymer of the polymer matrix are identical, so as to promote the properties of the composite material, in particular its cohesion and its mechanical strength.
    Step (3) of depositing the formulation can be carried out by any known technique and, inter alia, by spinning (in English, spin coating), screen printing, gravure printing, spraying, etc.
    Step (4) of applying energy is conventionally carried out by a heat treatment of the formulation deposited during step (3), possibly combined with ionizing radiation, in order to allow the polymerization of the polymer or polymers forming the formulation matrix.
    The invention relates, thirdly, to uses of the composite material as defined above, the advantageous characteristics of this composite material being able to be taken alone or in combination.
    The composite material according to the invention can in particular be used to form a film or else a magnetic and dielectric layer, this film or this layer being in particular intended for an electronic device or a radiofrequency device, such as an antenna.
    This radiofrequency device can in particular be adapted to high frequency, the high frequency being defined by a frequency between 10 MHz and 3 GHz.
    The invention relates, fourthly, to an electronic device or to a radio frequency device.
    According to the invention, this device, whether electronic or radiofrequency, comprises, as a dielectric material, a composite material as defined above, the advantageous characteristics of this composite material being able to be taken alone or in combination.
    The radiofrequency device can in particular be an antenna, in particular an antenna intended for a communicating object, such as a portable telephone.
    It is observed, in fact, that the presence of a composite material in such an antenna makes it possible to remedy the reduction in bandwidth that is observed with the composite materials used to date.
    Other characteristics and advantages of the invention will appear better on reading the additional description which follows and which relates to two examples of preparation of Co-Ni nanoparticles, one of which conforms to the invention.
    It is specified that this additional description, which refers in particular to Figures 1 and 2 as annexed, is given only by way of illustration of the subject of the invention and does not in any way constitute a limitation of this object.
    BRIEF DESCRIPTION OF THE DRAWINGS
    FIG. 1 corresponds to a photograph taken by means of a scanning electron microscope (SEM) of uncoated Co-Ni nanoparticles.
    FIG. 2 corresponds to a photograph taken by means of a scanning electron microscope (SEM) of Co-Ni nanoparticles coated with a layer of polystyrene, as obtained by the implementation of the method according to the invention.
    DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
    1. Preparation of uncoated Co-Ni nanoparticles
    The Co-Ni nanoparticles were prepared from cobalt acetate tetrahydrate, Co (CH3COO) 2, 4 H2O, and nickel acetate tetrahydrate Ni (CH3COO) 2, 4 H 2 O.
    1.59 g of cobalt acetate tetrahydrate and 0.398 g of nickel acetate tetrahydrate were dissolved in 100 ml of butane-1,4-diol, in a Co / Ni molar ratio of 80/20. To the mixture thus obtained are then successively added 600 mg of sodium hydroxide pellets NaOH, so as to reach a molar concentration of NaOH, in the solution, of 0.15 mol / L, and 52 mg of ruthenium trichloride RuCb . The resulting solution has the following characteristics:
    - a molar concentration of cobalt-nickel [CoNi] = 0.08 mol / L,
    - a molar ratio [Ru] / [Co + Ni] = 2.5%, and
    - a molar concentration of NaOH [NaOH] = 0.15 mol / L.
    The reaction mixture thus obtained is then heated to 170 ° C, with mechanical stirring, for 30 min, time after which a black solution is obtained.
    The Co-Ni nanoparticles are then collected and washed, three times, with ethanol by centrifugation for 5 min and at 8000 rpm, before being dried in an oven.
    With reference to FIG. 1, which corresponds to the SEM photograph of the nanoparticles thus prepared, it is observed that the nanoparticles obtained by implementing the preparation process described above are in the form of nanoparticles which are agglomerated to each other . These agglomerates have a size between 30 nm and 60 nm, it being noted that, by additional analysis, it has been determined that the nanoparticles themselves have a size of 2 nm to 3 nm.
    It is therefore easily understood that a composite material which would be obtained from a formulation comprising the nanoparticles prepared in accordance with the protocol which has just been described cannot have a homogeneous distribution of the nanoparticles within the polymer matrix. This has the consequence that an electric current is likely to be established, at least within this composite material, or even with other materials with which it comes to be in contact, thereby causing its dielectric properties to be lost. this composite material.
    2. Preparation of Co-Ni nanoparticles coated according to the process of the invention
    The Co-Ni nanoparticles were prepared from cobalt acetate tetrahydrate, Co (CH3COO) 2.4 H2O, and nickel acetate tetrahydrate Ni (CH3COO) 2.4 H2O.
    As in Example 1 above, 1.59 g of cobalt acetate tetrahydrate and 0.398 g of nickel acetate tetrahydrate were dissolved in 100 mL of butane-1,2-diol, in a Co / Ni molar ratio of 80/20. To the mixture thus obtained are then successively added 600 mg of sodium hydroxide pellets, so as to reach a molar concentration of NaOH, in the solution, of 0.15 mol / L, and 52 mg of ruthenium trichloride RuCb. The resulting solution has the following characteristics:
    - a molar concentration of cobalt-nickel [CoNi] = 0.08 mol / L,
    - a molar ratio [Ru] / [Co + Ni] = 2.5%, and
    - a molar concentration of NaOH [NaOH] = 0.15 mol / L.
    To this resulting solution are then added 5 mg of polystyrene with a molar mass 35,000 g / mol previously dissolved with a few drops of tetrahydrofuran THF.
    The reaction mixture thus obtained is then heated to 170 ° C, with mechanical stirring, for 30 min, time after which a black solution is obtained.
    The coated metal nanoparticles thus obtained are then collected and washed, three times, with ethanol by centrifugation for 5 min and at 8000 rpm, before being dried in an oven.
    With reference to FIG. 2, it can be seen that the SEM photograph shows that the coated metallic nanoparticles as obtained by the implementation of the preparation process according to the invention are in the form of individualized sticks, of average length of 200 nm.
    This length of the coated metal nanoparticles is directly related to the reaction time of the reaction mixture. Indeed, if a reaction time of 30 min makes it possible to obtain an average length of 200 nm, experience shows that a reaction time of 10 h allows to reach average lengths of coated metallic nanoparticles of 10 pm.
    It is therefore possible, without any difficulty, to adapt the reaction time to the average length of the coated metal nanoparticles which it is desired to obtain.
    The coated metal nanoparticles as obtained by the process according to the invention can then be introduced into a polymer matrix. The formulation thus obtained can be deposited on a surface in the form of a layer in which the nanoparticles are distributed in a regular manner and in the same direction. The polymeric coating of the nanoparticles makes it possible to ensure that no short-circuit is formed in the composite material obtained after heat treatment, even in the event that some of the nanoparticles come into contact with each other. The composite material therefore simultaneously exhibits magnetic and dielectric properties
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    1. Process for the preparation of coated metallic nanoparticles, each nanoparticle comprising a core made up of at least one metal M and a layer made up of at least one polymer, the layer covering the metallic core, which process comprises the following steps:
    (ai) the preparation of a solution A comprising:
    said at least one metal M in the form of cations M n + , n being an integer between 1 and 3 and, advantageously, equal to 2, each metal M being a transition metal, a polyol, and a salt of a noble metal, (a 2 ) the preparation of a solution B comprising at least one organic monomer of said at least one polymer, in an organic solvent, (b) the mixture of solutions A and B, this mixture being brought to temperature d boiling of the polyol, whereby coated metal nanoparticles are obtained, (c) recovering the coated metal nanoparticles.
    [2" id="c-fr-0002]
    2. The method of claim 1, wherein each transition metal M has an atomic number between 21 and 30 and is preferably chosen from the group consisting of Ni, Fe and Co.
    [3" id="c-fr-0003]
    3. Method according to claim 2, wherein the core consists of Ni, Fe, Co, Νί-Fe, Co-Ni, Fe-Co or Ni-Fe-Co.
    [4" id="c-fr-0004]
    4. Method according to claim 3, wherein, the core being constituted by a Co-Ni alloy, the Co / Ni molar ratio is between 50/50 and 90/10, advantageously between 70/30 and 85/15 and being , preferably, of 80/20.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1 to 4, wherein said at least one metal M in the form of cations M n + is a metal salt, this metal salt advantageously comprising at least one element chosen from the group consisting of a acetate, an acetylacetonate, a hydroxide and an oxide of the transition metal M, this metal salt preferably being an acetate of the transition metal M.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 5, in which the molar concentration of cations M n + [M n + ], in solution A, is between 0.02 mol / L and 1 mol / L, advantageously between 0.04 mol / L and 0.5 mol / L and, preferably, between 0.06 mol / L and 0.1 mol / L.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 6, wherein the polyol is a diol, advantageously an α-diol and, preferably, butane-1,2diol.
    [8" id="c-fr-0008]
    8. Method according to any one of claims 1 to 7, wherein the salt of a noble metal is chosen from osmium chloride, ruthenium chloride and iridium chloride.
    [9" id="c-fr-0009]
    9. Method according to any one of claims 1 to 8, in which the ratio of molar concentrations between the noble metal and the cations M n + , denoted [noble metal] / [M n + ], is between 0.005 and 0.1 , advantageously between 0.01 and 0.05 and, preferably, between 0.02 and 0.03.
    [10" id="c-fr-0010]
    10. Method according to any one of claims 1 to 9, in which solution A further comprises sodium hydroxide, in a molar concentration [NaOH] of at most 0.5 mol / L, advantageously between 0.05 mol / L and 0.4 mol / L and, preferably, between 0.1 mol / L and 0.3 mol / L.
    [11" id="c-fr-0011]
    11. Method according to any one of claims 1 to 10, wherein said at least one organic monomer is chosen from the group consisting of styrene, an alkyl (meth) acrylate, a fluorocarbon monomer, norbornene and ethylene.
    [12" id="c-fr-0012]
    12. A method of manufacturing a composite material, which method comprises the following steps:
    (1) a preparation of coated metallic nanoparticles, each nanoparticle comprising a core made up of at least one metal M and a layer made up of at least one polymer, the layer covering the metallic core, by implementing the preparation process according to any one of claims 1 to li, (2) a mixture of the nanoparticles prepared in step (1) in a polymer matrix, whereby a formulation is obtained comprising the nanoparticles dispersed in the polymer matrix, (3) a depositing the formulation obtained at the end of step (3), and (4) applying energy to the formulation deposited in step (3), whereby the composite material is obtained.
    [13" id="c-fr-0013]
    13. The method of claim 12, wherein the polymer matrix comprises at least one polymer chosen from the group consisting of a polystyrene, a poly (methyl methacrylate), a fluorocarbon polymer, a polynorbornene and a polyethylene, the polymer preferably being polystyrene.
    [14" id="c-fr-0014]
    14. The method of claim 12 or 13, wherein the polymer of the layer coating each nanoparticle and the polymer of the polymer matrix are identical.
    5
    [0015]
    15. Use of a composite material obtained by implementing the manufacturing method according to any one of claims 12 to 14 to form a film or a magnetic and dielectric layer, in particular intended for an electronic device or for a radio frequency device, such as an antenna.
    10
    [0016]
    16. Electronic or radiofrequency device, in particular antenna, comprising, as dielectric material, a composite material obtained by the implementation of the manufacturing process according to any one of claims 12 to 14.
    S.61251
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    同族专利:
    公开号 | 公开日
    US20180155508A1|2018-06-07|
    FR3059661B1|2021-06-04|
    US10899895B2|2021-01-26|
    EP3332893A1|2018-06-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2007106771A2|2006-03-10|2007-09-20|The Arizona Board Of Regents On Behalf Of The University Of Arizona|Multifunctional polymer coated magnetic nanocomposite materials|
    US8236284B1|2008-04-02|2012-08-07|University Of Central Florida Research Foundation, Inc.|Multimodal, multifunctional polymer coated nanoparticles|
    US20130063296A1|2011-08-11|2013-03-14|Basf Se|Microwave absorbing composition|FR3074576B1|2017-12-04|2020-01-03|Commissariat A L'energie Atomique Et Aux Energies Alternatives|THERMAL PATTERN SENSOR WITH PYROELECTRIC CAPACITY COMPRISING A SOL-GEL MATRIX AND METAL OXIDE PARTICLES|
    FR3074574B1|2017-12-04|2020-01-03|Commissariat A L'energie Atomique Et Aux Energies Alternatives|THERMAL PATTERN SENSOR WITH PYROELECTRIC CAPACITY|
    FR3074575B1|2017-12-04|2020-10-16|Commissariat Energie Atomique|PYROELECTRIC CAPACITY THERMAL PATTERN SENSOR|
    FR3074577B1|2017-12-04|2020-10-23|Commissariat Energie Atomique|THERMAL PATTERN SENSOR WITH PYROELECTRIC CAPACITY AND HARD PROTECTIVE LAYER|
    CN111230140A|2020-02-13|2020-06-05|合肥工业大学|Preparation method of dielectric adjustable three-dimensional grading nanocapsule wave-absorbing material|
    法律状态:
    2018-01-02| PLFP| Fee payment|Year of fee payment: 2 |
    2018-06-08| PLSC| Publication of the preliminary search report|Effective date: 20180608 |
    2019-12-31| PLFP| Fee payment|Year of fee payment: 4 |
    2020-12-28| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1661979A|FR3059661B1|2016-12-06|2016-12-06|METHODS OF MANUFACTURING COATED METAL NANOPARTICLES AND A COMPOSITE MATERIAL CONTAINING THEM, USE OF SUCH MATERIAL AND DEVICE CONTAINING IT|
    FR1661979|2016-12-06|FR1661979A| FR3059661B1|2016-12-06|2016-12-06|METHODS OF MANUFACTURING COATED METAL NANOPARTICLES AND A COMPOSITE MATERIAL CONTAINING THEM, USE OF SUCH MATERIAL AND DEVICE CONTAINING IT|
    EP17205217.7A| EP3332893A1|2016-12-06|2017-12-04|Methods for manufacturing coated metal nanoparticles and a composite material comprising same, use of such a material and device including same|
    US15/831,583| US10899895B2|2016-12-06|2017-12-05|Methods for manufacturing coated metal nanoparticles and a composite material comprising same, use of such a material and device comprising same|
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