• 专利附录
  • 专利说明
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    • 专利摘要:
    The present invention relates to inorganic particles having the particular property of being spontaneously individualized, both in the dry state in powder form, and when dispersed in a matrix. The invention also relates to a process for preparing these particles, as well as to materials obtained by including these particles in matrices.
    公开号:FR3020766A1
    申请号:FR1454141
    申请日:2014-05-07
    公开日:2015-11-13
    发明作者:Loic Marchin
    申请人:Pylote SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to inorganic particles having the particular property of being spontaneously individualized, both in the dry state in the form of powder, and when they are dispersed in a matrix. The invention also relates to a process for preparing these particles, as well as to materials obtained by including these particles in matrices.
    [0002] STATE OF THE ART OF THE INVENTION In the field of materials, it is common to use particles to impart to a material the desired properties, since there is a very wide range of particles, which make it possible to obtain a equally wide range of properties. The properties imparted to the material by the nano and / or microparticles are generally related to the properties of the particles themselves, such as their morphological, structural and / or chemical properties in particular. Particles of spherical morphology are particularly interesting in different fields. The particles which are said to be spherical are often either aggregates of non-spherical particles, the aggregate having itself a shape approaching a sphere, or have an unsatisfactory sphericity. Various methods have been developed to optimize the sphericity of the synthesized particles. Most of these methods are optimized for a single type of particles, for example a chemical type (silica particles for example) or a morphology (hollow particles for example). It would therefore be interesting to have new methods for the synthesis of spherical particles of all kinds and all morphologies.
    [0003] The dispersion of particles in matrices is also a conventional technique for imparting a desired property to said matrix. For example, pigments can be dispersed in matrices to impart color properties. The nature of the particles, their surface properties, and possibly their coating must be optimized to obtain a satisfactory dispersion in the matrix. The optimization of the dispersibility of the particles in the matrix will depend both on the nature of the particles and the nature of the matrix. It is important to be able to disperse the particles in the matrix relatively homogeneously so as to homogeneously distribute the desired property in the entire volume of the matrix. When the particles agglomerate in the matrix, the desired properties are not homogeneously conferred on the matrix and the desired result (the matrix with the desired property) is not obtained satisfactorily.
    [0004] It would therefore be interesting to have new methods for dispersing any kind of particles in any matrix as satisfactorily as possible. In this context, the Applicant has found a method for preparing perfectly spherical micrometric inorganic particles of different chemical natures and different morphologies. Surprisingly, the particles obtained by this process, whatever their chemical nature and their morphology, remain in the individualized state and do not form aggregates both in the dry state and when they are dispersed in a matrix. .
    [0005] SUMMARY OF THE INVENTION The first object of the present invention is a set of micrometric spherical inorganic particles, characterized in that the particles are individualized, especially in the dry state or in a matrix. A second subject of the invention is a material comprising a set of particles according to the invention dispersed substantially homogeneously in a matrix.
    [0006] A third object of the invention is a method for preparing a set of particles according to the invention.
    [0007] A final subject of the invention is a process for preparing a material according to the invention, comprising contacting a matrix with a set of particles according to the invention.
    [0008] BRIEF DESCRIPTION OF THE FIGURES FIG. 1: Schematic representation of a reactor adapted for carrying out the process according to the invention. Figure 2: SEM image (Scanning Electron Microscopy) of mesoporous silica particles according to the invention. FIG. 3: Images of SEM (Scanning Electron Microscopy) of mesoporous boehmite particles according to the invention (FIGS. 3a, 3b, 3c, 3d). Figure 4: SEM images (Scanning Electron Microscopy) of hollow copper oxide particles according to the invention (Figures 4a, 4b, 4c).
    [0009] Figure 5: SEM images (Scanning Electron Microscopy) of mesoporous alumina particles according to the invention (Figures 5a, 5b, 5c). FIG. 6: Images of SEM (Scanning Electron Microscopy) of mesoporous mixed SiO 2 / TiO 2 particles according to the invention: SITI 01 (FIG. 6a), SITI 02 (FIG. 6b) and SITI 03 (FIG. 6c).
    [0010] Figure 7: SEM images (Scanning Electron Microscopy) of hollow alumina particles according to the invention (Figures 7a and 7b). Figure 8: SEM images (Scanning Electron Microscopy) of dense silica particles according to the invention (Figures 8a and 8b). Figure 9: SEM image (Scanning Electron Microscopy) of hollow magnesium oxide particles according to the invention. Figure 10: SEM image (Scanning Electron Microscopy) of mesoporous boehmite particles according to the invention in a polyethylene matrix. Figure 11: SEM image (Scanning Electron Microscopy) of hollow ZrO2 particles according to the invention in an enamel matrix.
    [0011] Figure 12: SEM images (Scanning Electron Microscopy) of dense ZnO particles according to the invention in an ABS matrix (Acrylonitrile Butadiene Styrene) (Figures 12a and 12b).
    [0012] Figure 13: SEM image (Scanning Electron Microscopy) of commercial mesoporous silica particles. DETAILED DESCRIPTION OF THE INVENTION The first object of the present invention is a set of micrometric spherical inorganic particles, characterized in that the particles are individualized, in particular in the dry state or in a matrix.
    [0013] In the present invention, a set of individualized particles refers to a set of particles in which the particles are not aggregated, i.e. each particle of the set is not bound to other particles by strong chemical bonds such as covalent bonds. A set of particles according to the invention may optionally contain particles that do not meet this characteristic, insofar as the non-aggregation criterion is met by at least 50% by number of the particles of the assembly. Preferably, at least 60%, at least 70%, at least 80%, at least 90%, at least 95% by number of the particles of the set considered are individualized.
    [0014] Preferably, a particle of the assembly according to the invention is not constituted by the aggregation of several particles of smaller size. This can be clearly visualized for example by microscopy studies, in particular by scanning electron microscopy or transmission. This means that the only possible constituents of the particles according to the invention are crystallites of much smaller size than the particles according to the invention. A particle according to the invention is preferably formed of at least two crystallites. A crystallite is a domain of matter having the same structure as a single crystal, that is to say within each atomic plane defining this structure there is no major discontinuity of the crystalline order except for point defects (gaps, atoms in insertion or substitution) or linear defects (dislocations).
    [0015] By way of comparison, the atomization techniques conventionally used in the art generally provide aggregated nonspherical particles. The objects that are formed by these aggregates of particles can be spherical. Figure 13 shows a scanning electron microscopy image of commercial mesoporous silica particles. The particles are not perfectly spherical and can be aggregated, which is not the case with the particles of the present invention. The particles according to the invention are spherical, that is to say they have a sphericity coefficient greater than or equal to 0.75. Preferably, the sphericity coefficient is greater than or equal to 0.8, greater than or equal to 0.85, greater than or equal to 0.9, or greater than or equal to 0.95. The sphericity coefficient of a particle is the ratio of the smallest diameter of the particle to the largest diameter of the particle. For a perfect sphere, this ratio is equal to 1. The sphericity coefficient can be calculated for example by measuring the aspect ratio by means of any software adapted from images, for example images obtained by microscopy, in particularly scanning electron microscopy or in transmission, particles. In one embodiment, the invention relates to a set of particles as defined above. In this embodiment, the assembly may optionally contain particles that do not have the required sphericity criteria insofar as the number average sphericity on all the particles meets the criteria set in the present invention. Thus, the term "set of spherical particles" denotes a plurality of particles of which at least 50% of the particles in number have a sphericity as defined above. Preferably, at least 60%, at least 70%, at least 80%, at least 90%, at least 95% by number of the particles of the set considered have a sphericity as defined above. By inorganic particle is meant in the present invention a particle consisting at least in part of a non-organic product, that is to say that is not derived from the chemistry of carbon (except C032-). The chemical diversity of the inorganic particles is well known to those skilled in the art. The inorganic particles may especially be particles of metal (or alloy), metal oxide, silicate, phosphate (or apatite), borate, fluoride, carbonate, hydroxycarbonate, vanadate, tungstate , sulfide and / or oxysulfide, optionally combined with organic compounds such as for example latex, this list is not limiting. In particular, the inorganic particles may comprise oxides of metal or semiconductor elements, such as silica, zinc oxide, magnesium oxide, titanium dioxide, alumina, barium titanate or a mixture of these. The inorganic particles may also include transition metals such as copper, zinc or iron, or rare earths such as yttrium or lanthanides, and / or derivatives thereof such as oxides. The inorganic particles according to the invention may optionally comprise at least one dopant, such as, for example, aluminum, erbium, europium or ytterbium. The dopant is in a proportion of not more than 10% by weight, preferably not more than 5% by weight, in particular not more than 2% by mass.
    [0016] Of course, the particles according to the invention may comprise a minimum proportion, for example less than or equal to 5% by weight, of contaminants which may have a chemical nature different from that of said particles. In a preferred embodiment, the inorganic particles are particles of ZnO, in particular hexagonal ZnO, optionally doped, for example doped with aluminum, particles of alumina, in particular amorphous, cubic or rhombohedral alumina, particles of boehmite, in particular orthorhombic particles, particles of silica, in particular of amorphous silica, particles of copper oxide, preferably cubic copper oxide, particles of titanium oxide, in particular anatase or rutile, particles of mixed oxide of titanium and silicon, in particular anatase, particles of montmorillonite, in particular monoclinic, particles of hydrotalcite, in particular hexagonal, particles of magnesium dihydroxide, in particular hexagonal, magnesium oxide particles, in particular cubic, zirconium dioxide particles, in particular quadratic, yttrium oxide particles Y203, in particular cubic, optionally doped with europium and / or erbium and / or ytterbium, particles of cerium dioxide, particles of yttrium-stabilized zirconia, CaCu3Ti4012 particles, BaTiO3 particles, preferably cubic, iron oxide particles, preferably in hematite form, magnesium sulfate particles, preferably orthorombic, particles of ZnO, 18MnO, 82Fe 2 O 4, preferably cubic, particles of Mn 2 P 2 O 7, preferably monoclinic. , nickel manganese oxide particles, mullite particles, ZnFe2O4 particles, MnFe2O4 particles, NiFe2O4 particles, CoFe2O3 particles, MgAl2O4 particles, or Y3A15O12 particles. realization, the inorganic particle comprises several chemical elements, preferably from 2 to 16 different chemical elements, this number of elements not taking into account the elements O and H possibly included in the particle. It is then heterogeneous particles, that is to say which comprise different elements whose stoichiometry is preferably controlled by the synthesis method.
    [0017] Because of the speed of the process for preparing the particles, and the possible existence of a quenching step at the end of the process for preparing the particles according to the invention, these may comprise any chemical constituent which it It is possible to densify, in particular to crystallize, even the metastable phases. In fact, the particular conditions used in the process make it possible to obtain, in densified form, compounds whose degradation temperature is lower than the temperature actually applied, because the time spent at high temperature is very short. In this context, the term "high temperature" preferably denotes a temperature greater than 40 ° C. "Time spent at high temperature" generally refers to the time spent on the drying, pyrolysis and densification steps. Preferably, the time spent at high temperature does not exceed 70 seconds, in particular it is between 30 and 70 seconds. Preferably, quenching is characterized by a cooling rate greater than or equal to 100 ° C per second. In one embodiment, the particles according to the invention comprise a type of oxide which requires a supply of energy to densify, in particular to crystallize. For example, mention may be made of alumina, zinc oxide, iron oxide, titanium dioxide (rutile), cubic or monoclinic ZrO 2, and rare earth oxides (lanthanides and / or yttrium). Such particles can not be obtained in the same way by the conventional methods used in the prior art, especially those which do not include a quenching step. The heterogeneous particles can either comprise several chemical elements (except 0 and H), preferably all the chemical elements (except O and H) constituting the particle, within each crystallite, or comprise crystallites each formed of a single chemical element (except O and H). In a particular embodiment, each crystallite of the heterogeneous particle comprises a single chemical element (except O and H).
    [0018] The particles according to the invention are micrometric, that is to say that the particle diameter is between 0.1 and 1000 microns. Preferably, the diameter of the particles according to the invention is between 0.1 and 600 microns, in particular between 0.1 and 100 microns. In a preferred embodiment, it is between 0.1 and 10 microns. Those skilled in the art know the appropriate techniques for determining the diameter of the particles or sets of particles according to the invention, and he also knows the degree of uncertainty existing on these measurements. For example, the average particle diameter of a set, the standard deviation and the size distribution in particular can be determined by statistical studies from microscopy images, for example scanning electron microscopy or transmission. In the case where the particles are within a set, the above diameter values may correspond to the average particle diameter in number even though some of the particles in the set have diameters outside this range. Advantageously, all the particles of the population have a diameter as defined above. In one embodiment, the relative standard deviation of the particle size in a population of particles according to the invention is less than or equal to 25%, preferably less than or equal to 20%. The size distribution of the particles in the set of particles according to the invention may be monomodal or multimodal.
    [0019] The use of micrometric particles in the present invention makes it possible to promote the particle dispersion properties because they are not too large but do not have the disadvantages (difficulties of implementation, toxicity, ...) of the nanoparticles.
    [0020] The particles according to the invention can have different morphologies. For example, they may be solid, hollow, porous, mesoporous, non-porous, and may also encapsulate other entities such as organic molecules, in which case they are organic-inorganic hydride particles, or inorganic compounds, in particular in the form of nanoparticles. The encapsulation can be carried out either during the synthesis of the particles or in post-treatment. In the case where the particles are hollow, the wall thickness can be controlled, in particular by means of the parameters of the synthesis process. In the present invention, according to the IUPAC definition, a material is said to be microporous when it has pores less than 2 nm in size. A material is said to be mesoporous when it has pores between 2 and 50 nm in size. A material is said to be macroporous when it has pores larger than 50 nm. Typically, the mesoporous materials may be amorphous or paracrystalline silica compounds in which the pores are generally randomly distributed, with a pore size distribution that can be very broad. A second subject of the invention is a material comprising particles according to the invention, dispersed substantially homogeneously in a matrix.
    [0021] According to the present invention, the term "matrix" designates any material that can advantageously benefit from the inclusion of particles according to the invention. It may be in particular solid or liquid matrices, regardless of the viscosity of the liquid matrix.
    [0022] In one embodiment, the matrix is a liquid matrix, for example a solvent, preferably an aqueous solvent, such as water or an alcohol such as ethanol or ethylene glycol, or an organic solvent such as methyl methacrylate. The liquid matrix may also comprise a mixture of solvents, or a premix concentrate or not solvents. In one embodiment, the matrix is a solid matrix, for example a metal, ceramic or polymeric matrix, in particular a thermoplastic polymeric matrix. Among the thermoplastic polymer matrices that can be used according to the invention, mention may be made in particular of polyethylene, polyethylene terephthalate, polypropylene, polyoxymethacrylate, ABS (acrylonitrile butyrene styrene) or polyethylenevinylacetate.
    [0023] The inclusion of the particles according to the invention in a matrix makes it possible to confer properties, in particular mechanical, thermal and / or physicochemical, particular to the matrix. The inclusion of the particles in the matrix can be carried out by the techniques conventionally used in the art, in particular by mechanical stirring when the matrix is liquid.
    [0024] The material according to the invention may in particular be obtained in the form of a liquid, powder, beads, pellets, granules, and / or extrudates, the shaping operations being carried out by the conventional techniques known from the art. those skilled in the art, in particular when the matrix is a polymeric matrix.
    [0025] In particular, the process of shaping the material does not require an additional step of dispersing the particles within the matrix with respect to the shaping method conventionally used for matrices without inclusion of particles. The shaping process may preferably be carried out on equipment and processing lines conventionally used for matrices without inclusion of particles. The dispersion of the particles within the matrix may, in some embodiments, be carried out without additional chemical dispersing agent. In a particular embodiment, the dispersion of the particles within the matrix is carried out in the presence of a chemical dispersing agent such as a surfactant.
    [0026] Those skilled in the art are able to determine whether the use of a dispersing agent is necessary to obtain the desired dispersion and to adjust the amount of dispersing agent to be used if necessary. For example, the dispersing agent may be used in an amount of 0.5 to 50% by weight relative to the mass of particles, especially in an amount of 0.5 to 20% by weight relative to the mass of particles . The particles according to the invention have the particularity of being dispersed substantially homogeneously in volume in the matrix, whatever their chemical nature, their morphology and the nature of the matrix. This means that the particle density per unit volume is the same at every point of the matrix. In the case of a solid matrix, the density of particles per unit area is preferably about the same regardless of the surface of the matrix considered, whether it is an end surface of the matrix, or a surface obtained by cutting the material for example. Thus, the property (s) that is / are conferred on the matrix by the inclusion of the particles according to the invention is / are distributed substantially homogeneously throughout the matrix volume.
    [0027] The material according to the invention may comprise particles according to the invention in any proportion adapted to give it the desired properties. For example, the material may comprise from 0.1 to 80% by weight of particles relative to the total mass of matrix + particles, preferably from 1 to 60% by weight, in particular from 2 to 25% by weight.
    [0028] Preferably, the particles according to the invention are non-deformable individualized particles. Also, the surface of each particle that is in contact with other particles is very small. In one embodiment, the radius of curvature of the meniscus forming the contact between two different particles of the assembly is less than 5%, preferably less than 2%, of the radius of each of the two particles, in particular within a matrix or in powder form. The sphericity of the particles according to the invention also makes it possible, for the same charge rate in a liquid matrix, to obtain a lower viscosity than with nonspherical particles.
    [0029] Another object of the present invention is a method for preparing a set of particles according to the invention. The process according to the invention is a process by aerosol pyrolysis (or pyrolysis spray). This process is an improved process compared to the aerosol pyrolysis process described in particular in application FR 2 973 260. More specifically, the process according to the invention is generally carried out in a reactor. This process comprises the following steps: (1) nebulization of a liquid solution containing a precursor of the inorganic material or materials from which it is desired to form particles at a given molar concentration in a solvent, so as to obtain a fog of droplets of solution, (2) the heating of the fog at a so-called drying temperature capable of ensuring the evaporation of the solvent and the formation of particles, (3) the heating of these particles to a so-called pyrolysis temperature capable of ensuring the decomposing the precursor to form the inorganic material, (4) densifying the particles, and (5) recovering the particles thus formed. The nebulizing step (1) is preferably carried out at a temperature of 10 to 40 ° C, and / or preferably for a duration of less than or equal to 10 seconds, in particular less than or equal to 5 seconds. The heating step (2) (drying) is preferably carried out at a temperature of 40 to 120 ° C, and / or preferably for a period of less than or equal to 10 seconds, in particular between 1 and 10 seconds. The pyrolysis step (3) is preferably carried out at a temperature of 120 to 400 ° C., and / or preferably for a duration of less than or equal to 30 seconds, in particular of between 10 and 30 seconds. The densification step (4) can be carried out over a wide temperature range, especially between 200 and 1000 ° C. This step is preferably carried out at a temperature of 400 to 1000 ° C when the particles that are to be prepared are at least partly in crystallized form. When it is desired to obtain dense but uncrystallized particles, in particular amorphous particles, the densification temperature may be lower, for example it may be around 200 ° C. to 300 ° C., in particular for amorphous silica. . Preferably, the densification step is carried out for a duration of less than or equal to 30 seconds, in particular between 20 and 30 seconds. The recovery step (5) is preferably carried out at a temperature below 100 ° C, and / or preferably for a duration of less than or equal to 10 seconds, in particular less than or equal to 5 seconds. The step (5) for recovering the particles is preferably carried out by depositing the particles on a filter at the outlet of the reactor.
    [0030] The temperatures of each of the steps may be outside the range of temperatures provided above. Indeed, for the same particles, the temperature to be applied may depend on the speed at which the drops and the particles circulate in the reactor. The more the drops then the particles circulate quickly in the reactor, the less time they spend there and the higher the set temperature must be high to obtain the same result. Preferably, the steps (2), (3) and (4) are carried out in the same reactor. In particular, all the steps of the process (except the post-treatment stages) are carried out in the same reactor.
    [0031] All the steps of the process, in particular steps (2), (3) and (4), are carried out in continuity with one another. The temperature profile applied in the reactor is adapted according to the particles that it is desired to form so that these three steps take place one after the other. Preferably, the temperature in the reactor is adjusted through at least one, preferably 3, heating elements whose temperatures can be set independently. The process according to the present invention preferably further comprises between the densification step of the particles (4) and the step of recovering the particles (5) a step (4 ') of quenching the particles. The quenching step (4 ') is preferably carried out by entering a gas, preferably air, cold over all or part of the circumference of the reactor. A gas is said to be cold in the present invention if it is at a temperature of between 15 and 50 ° C, preferably between 15 and 30 ° C. In one embodiment, the gas entering the reactor is a different gas from the air. In particular, it may be a neutral gas (such as nitrogen or argon), a reducing gas (such as hydrogen or carbon monoxide), or any mixture of such gases.
    [0032] The method is preferably implemented in the absence of a flow of gas vectorizing the fog from the bottom of the reactor. The laminar flow making it possible to bring the material into the zone in which the temperature is lower is advantageously created solely by suction at the top of the reactor, producing a depression for example of the order of a few pascals or a few tens of pascals.
    [0033] Such an embodiment makes it possible to use a reactor without gas entry in its lower part, thus limiting process disturbances and losses, and thus optimizing the process efficiency and the size distribution of the particles obtained. In another embodiment, the reactor in which the process is carried out also comprises a gas inlet at the level where the mist is formed. The gas entering the reactor at this level is preferably air, in particular hot air, that is to say at a temperature of 80 to 200 ° C. Preferably, the process according to the invention does not comprise any other heating step than those carried out inside the aerosol pyrolysis reactor.
    [0034] FIG. 1 shows an example of a reactor scheme for carrying out the process according to the invention. The lower part (1) of the reactor comprises the liquid solution containing a precursor of the inorganic material or materials from which it is desired to form particles at a given molar concentration in a solvent. This solution is nebulized at the intermediate portion (2), and the droplets rise by suction in the reactor. The entry of cold gas, in particular cold air, allows quenching of the particles. The upper part (3) of the reactor is also at a cold temperature (below 100 ° C., for example between 15 and 50 ° C.).
    [0035] The precursor of the inorganic material or materials from which one wishes to form particles may be of any origin. The precursor (s) of the inorganic material (s) is (are) chosen according to the particles that it is desired to form.
    [0036] In a particular embodiment, this precursor is at least partly derived from plant or food waste, which represents biosources. Examples of such precursors of inorganic material include sodium silicate from rice husks. Slaughterhouse residues, such as bones, can be used as a source of calcium phosphate, blood can be used as an iron oxide precursor, and / or shellfish shells can be used as a source of calcium carbonate. The process according to the invention makes it possible to obtain particles having a high degree of purity. These particles do not necessarily require the implementation of subsequent processing steps, such as washing, heat treatment, milling, etc., prior to use. In the process according to the invention, all the entities introduced into the reactor are transformed, which is an important advantage because the process generates little waste. In addition, the rate of use of atoms is high and complies with the requirements of green chemistry. The method according to the invention may comprise at least one stage of post-treatment of the particles. For example, it may be a washing step with a suitable solvent, a contacting step with reducing conditions, an encapsulation step inside the particles, a step heating the particles, and / or a particle coating step, in particular to "seal" said particles. In particular, a post-treatment step by heating the particles may be necessary to optimize the properties of the particles such as their composition or their crystalline structure. A post-treatment step by heating the particles will generally be less necessary as the speed of the drops and particles in the reactor will be less. The method according to the invention makes it possible to precisely control the size of the particles at the output of the process. Indeed, there is a constant ratio, which is around 5, between the diameter of the drops of the mist used and the diameter of the particles at the end of the process when the concentrations of precursors are molar, which is usually the case. The person skilled in the art knows how to determine, according to the concentration of precursor, the ratio between these two diameters. For example, if the precursor concentration is decreased by a factor of 10, then the size of the particles obtained is reduced by a cubic root factor of 10, or about 3. The diameter of the drops may also be controlled in particular by the parameters the nebulization mode, for example the frequency of the piezoelectric elements used to form the fog. In one embodiment, at least some of the drops comprise, in addition to the compound or compounds of which it is desired to form particles, at least one so-called sacrificial compound which is, for example, soluble in a solvent, such as water, acidic water or basic water, is heat-sensitive, in particular this sacrificial compound is vaporized or degraded at the reactor temperature. In the case where the sacrificial compound is soluble in a solvent, the process advantageously comprises a post-treatment step comprising washing the particles with said solvent. The presence of the so-called sacrificial compound in the drops finally makes it possible to obtain particles of properties such as the size, the porosity, the specific surface, which are different from those of the particles obtained directly from the drops. The sacrificial compound may be any liquid, solid or gaseous chemical compound that has the desired properties of, for example, solubility and / or thermosensitivity.
    [0037] The method according to the invention may comprise a step of encapsulation within the inorganic particles of other entities such as organic molecules, in which case it is organic-inorganic hydride particles, or inorganic compounds, in particular in the form of nanoparticles. The encapsulation can be carried out either during the synthesis of the particles or in post-treatment.
    [0038] Another subject of the invention is a set of particles capable of being prepared according to the process defined above. The particles thus prepared have the characteristics described above. This process makes it possible in particular to obtain individualized spherical particles. Preferably, it also allows that each particle is not constituted by the aggregation of several smaller particles. Preferably, the particles obtained by this method are individualized and non-deformable.
    [0039] A final subject of the invention is a method for preparing a material according to the invention, comprising contacting a matrix as defined above with at least one set of particles according to the invention. This process then preferably comprises a step of shaping the material as described above. Unless otherwise specified, the percentages mentioned in the present invention are percentages by weight.
    [0040] The following examples are provided by way of illustration, and not limitation, of the invention. EXAMPLES Unless otherwise specified, in the present examples, measurements of specific surface area, pore volume, and pore diameter were made by the BET method. The LASER granulometry measurements were carried out using a LASER Mastersizer 2000 granulometer (Malvern Instruments), on dispersions of the particles in the water. Example 1: Mesoporous silica particles Example 1.1: Mesoporous silica particles with in situ encapsulation of organic compounds Mesoporous silica particles encapsulating organic molecules were prepared from two different precursors: a commercial silica sol comprising particles from 10 to 30 nm, and TEOS (tetraethylorthosilicate). a) From the silica sol 51 mL of commercial silica sol mixed with 238 mL of deionized water are prepared. The organic compound is introduced at 50% by weight relative to the silica mass. The "precursor" solution is nebulized by the pyrolysis spray process. The maximum oven temperature in which the drying, pyrolysis and densification steps are carried out is set at 250 ° C. b) From the TEOS 145 mL of demineralized water whose pH is adjusted to 1.4 by a strong acid (HCl or HNO3 for example) and 23 mL of TEOS (tetraethylorthosilicate) are introduced into a 500 mL beaker and the everything is left stirring for 3 hours. The organic compound is introduced at a level of 50% by weight relative to the silicate mass. The precursor solution is nebulized by the pyrolysis spray method. The maximum oven temperature in which the drying, pyrolysis and densification steps are carried out is set at 250 ° C.
    [0041] EXAMPLE 1.2 Mesoporous Silica Particles with Encapsulation of Organic Molecules in Post-Treatment 25 Grams of Mesoporous Silica Particles Obtained by Pyrolysis Spray According to the Invention (Specific Surface Area of 124 m2 / g (BET), Average Diameter 1.2 Lm (laser granulometry)) are introduced into a 500 ml vial equipped with a vacuum outlet. The medium is heated at 140 ° C. under vacuum for 6 hours. 400 ml of a concentrated solution of organic compound (25 g) are then introduced and the whole is left vigorously stirred for 12 hours.
    [0042] The particles are then centrifuged and dried under air. The charge rate is then determined by mass difference and is of the order of 50% by weight. An SEM (Scanning Electron Microscopy) image of the mesoporous silica particles obtained in Example 1.1a) is presented in FIG. 2. Similar particles were obtained in Examples 1.1b) and 1.2. Example 2: Mesoporous Boehmite AlOOH Particles The particles were synthesized according to the method below. 1- Heat 300 mL of water at 80 ° C. 2- During the rise in temperature (around 60 ° C), add the aluminum oxide to 0.7M (42.9g) under very vigorous agitation. 3- Cover and shake for one hour at 80 ° C. 4- After one hour, add 2.6% by weight (ie 1.11 g) of nitric acid. 5- Cover and shake for two hours at 80 ° C. The precursor solution is nebulized by the pyrolysis spray method (SP100) according to the invention. The profile of the maximum temperatures reached in the reactor in which the drying, pyrolysis and densification steps take place is as follows: 350 ° C., 500 ° C., 500 ° C. Figure 3 shows SEM images of the boehmite particles obtained. X-ray diffraction analysis revealed that it is orthorhombic boehmite. The BET surface area of the powder obtained is 402 m 2 / g, and the average pore diameter (BET) is 3 nm. The analyzes in LASER granulometry provided the following values: d10 = 0.761.tm, d50 = 1.091.tm and d90 = 1.81.tm. Example 3 Preparation of hollow CuO particles An aqueous solution is prepared with 241 g of copper nitrate trihydrate Cu (NO3) 2, 3H2O powder, dissolved in 1L of water. The precursor solution is nebulized by the pyrolysis spray method. The maximum oven temperature in which the drying, pyrolysis and densification steps take place is set at 800 ° C.
    [0043] The particles are then heat-treated in an oven under air for 2 hours at 500 ° C. in order to complete the nitrate decomposition which is not complete at the outlet of the reactor. Figure 4 shows SEM images of the obtained CuO particles. X-ray Diffraction analyzes have identified that it is monoclinic CuO.
    [0044] The analyzes in LASER granulometry provided the following values: d10 = 0.416ffl, d50 = 0.700ffl and d90 = 0.999ffl. Example 4 Preparation of hollow metallic copper particles The CuO powder obtained in Example 3 is placed in the enclosure of an oven. A reducing gas stream (for example 5% H 2, 95% N 2) circulates in this oven throughout the reaction. The reduction is carried out for 3 hours at 500 ° C. X-ray Diffraction analyzes showed that all the particles obtained are copper.
    [0045] Example 5: Mesoporous alumina A1203 particles The particles were prepared according to the method below. 1- Heat 300mL of water at 80 ° C. 2- During the rise in temperature (around 60 ° C), add the aluminum oxide to 0.7M (42.9g) under very vigorous agitation. 3- Cover and shake for one hour at 80 ° C. 4- After one hour, add 2.6% by weight (ie 1.11 g) of nitric acid. 5- Cover and shake for two hours at 80 ° C.
    [0046] The precursor solution is nebulized by the pyrolysis spray method according to the invention. . The profile of the maximum temperatures reached in the reactor in which the drying, pyrolysis and densification steps take place is as follows: 350 ° C., 600 ° C., 800 ° C. Figure 5 shows SEM images of the A1203 particles obtained. X-ray Diffraction analyzes have identified that it is amorphous A1203. The BET specific surface area of the powder obtained is 383 m 2 / g, and the average pore diameter is 2.4 nm. LASER particle size analyzes provided the following values: d10 = 0.95itm, d50 = 1.331.tm and d90 = 2.26ffl.
    [0047] EXAMPLE 6 Mesoporous SiO2 / TiO2 Mixed Particles Silica Sol In a beaker, 627 ml of demineralized water and 8 grams of a surfactant (poloxamer such as Pluronic, CTAB (hexadecyltrimethylammonium bromide) or polyoxyethylene derivative) are introduced. Brij brand for example). After dissolution of the surfactant, 28 g of TEOS are introduced with stirring at once. The mixture is stirred vigorously for 15 hours to allow the hydrolysis and condensation of TEOS and thus form the silica gel. The titanium oxide sol In parallel, in a flask containing 100 ml of demineralized water, a volume of 1.5 ml of nitric acid is introduced. The solution is brought to 70 ° C, and 17 grams of titanium butoxide are added. The synthesis is stirred vigorously for 12 hours to allow the synthesis of titanium oxide nanoparticles. The dispersion is left to settle for 2 hours to remove butanol on the surface. Pyrolysis Spray The titanium sol is introduced into the silica sol with magnetic stirring for 5 minutes. The precursor solution is nebulized by the pyrolysis spray method according to the invention. The maximum oven temperature in which the drying, pyrolysis and densification steps take place is set at 500 ° C. Post-treatment The particles are then heat-treated in an oven under air for 4 hours at 700 ° C. The process is reproduced by varying the amount of TiO 2, to obtain the following three samples: SITI 01, SITI_02 and SITI_03 (see Table 1 below). Reference Mass Weight Mass ratio TiO2 / mass Si02 Surface Area Volume Volume Diameter TEOS Porous specific butoxide specific porous medium titanium BET BJH BJH BET pore BET SITI_01 28 g 17.0 g 0.48 563 m2 / g 581 m2 / g 0.45 cm3 / g 0.45 cm3 / g 3.2 nm SITI_02 28 g 22.4 g 0.65 518 m2 / g 614 m2 / g 0.41 cm3 / g 0.45 cm3 / g 3.5 nm SITI_03 28 g 11.2 g 0.32 595 m2 / g 544 m2 / g 0.37 cm3 / g 0.46 cm3 / g 3.0 nm Table 1 Figure 6 shows SEM images of the particles obtained: SITI 01 (a), SITI_02 (b) and SITI_03 (c). Table 2 below summarizes the properties of the three samples obtained. Reference Diameter Diameter Surface Surface DRX diameter of the average phase laser particle size (number) average specific pore TiO2 BET BJH (amorphous Si02) SITI_01 1,1i.tm d10 = 0,52 gm 563 m2 / g 581 m2 / g 3, 2 nm rutile / ± 0.6 μm d50 = 0.78 pm brookite d90 = 1.60 gm SITI_02 2 0 iim _Ln 'd10 = 0.49 gm 518 m2 / g 614 m2 / g 3.5 nm Rutile /' '' 11111 d50 = 0.73 pm brookite d90 = 1.48 gm SITI_03 1 m d10 = 0.53 gm 595 m2 / g 544 m2 / g 3.0 nm / ', 81'lm d50 = 0.79 pm brookiteRutile ± 1 ii d90 = 1.64gm Table 2 Mean diameter values are obtained by statistical study on electron microcopy images. Example 7: Other types of particles Other particles were prepared and characterized according to the invention. For example, FIGS. 7 to 9 present scanning electron microscopy images of particles according to the invention: hollow alumina particles, (FIG. 7), dense silica particles (FIG. 8), and oxide particles. of magnesium (MgO) hollow (Figure 9).
    [0048] Table 3 below gives examples of different types of synthesized particles according to the invention. The elements following the sign ":" in the name of the particles in Table 3 are dopants of the particles. The term "Bio-SiO 2" refers to a biosourced silica derived from sodium silicate that can be obtained by extracting scrap from food plants. Size (μm) Morphology Crystalline phase h-ZnO 0.5 dense Hexagonal h-ZnO: Al 1 hexagonal hollow h-ZnO: Al 5 hexagonal hollow A1203 1.2 hollow amorphous y-A1203 1.2 cubic hollow oc-A1203 1, 5 hollow rhombohedral SiO2 1.9 dense amorphous SiO2 1.2 meso amorphous O-AIOOH 1.1 meso Orthorombic C-CuO 0.7 hollow Cubic Anatase-TiO2 0.8 meso mixture anatase rutile Rutile-TiO2 1 meso quadratic A1203 1, 1 meso amorphous y-Al2O3 1,4 meso cubic α-Al2O3 1,2 dense rhombohedral SiO2TiO2 1,3 meso Anatase m-MMTHPS 1 meso monoclinic = Montmorillonite ((Na, Ca) o, 3 (Al, Mg) 2S14010 (0 H) 2.nH2O) h-LDHMG63HT 1 meso Hexagonal = hydrotalcite (aluminum magnesium hydroxy carbonate) h-Mg (OH) 2 0.7 hexagonal meso h-ZnO: Al 1 meso hexagonal C-MgO 1.9 hollow cubic Q- Zr02 0.4 quadratic hollow Q-Zr02 0.6 dense quadratic h-ZnO: Al 1 hexagonal hollow h-ZnO: Al 1 hollow hexagonal C Y203 0.6 hollow Cubic C-MgO 1.9 cubic hollow C-Y203: Eu 0.5 cubic hollow C Y203: Er: Eu: Yb 0.6 cubic hollow C-Ce02 0.7 hollow Cubic YSZ 0.7 cr quadratic = Yttria-stabilized zirconia YSZ 0.6 dense quadratic = Yttria-stabilized zirconia C-CCTO 0.3 dense cubic = CaCu3Ti4012 Bio-Si02 1 meso amorphous Q-Zr02 0.6 meso quadratic c-BaTiO3 unmeasured Cubic a-Fe203 1 dense hematite O-MgSO4 1.5 hollow Orthorombic C-ZMFO (Zno, i8Mno, 82Fe204) 1.5 dense Cubic M-Mn2P2O7 0.8 dense monoclinic NiMnOxide 0.8 dense mixture Mullite (SiO2, Al2O3) hollow not measured Fe3O4 not measured not measured ZnFe2O4 not measured not measured MnFe2O4 not measured not measured NiFe2O4 not measured not measured CoFe2O3 not measured not measured MgA1204 not measured not measured Y3A15012 not measured not measured Table 3 Size values in Table 3 are obtained by statistical study on images of electronic microcopy.
    [0049] Example 8 Incorporation of the Particles Obtained in Example 2 into a Polyethylene Matrix The boehmite particles obtained according to Example 2 are introduced into a polyethylene matrix by extrusion-compounding. The extruder is a corotative twin-screw Clextral model EVOLUM HT 32 with an L / D = 44 and a screw diameter of 32 mm. The proportions are as follows: 80% polyethylene, 20% boehmite particles by mass. The extrusion temperature profile is as follows: I The screw speed is 250 rpm, the motor torque is 44%, the pressure at the top is 40 bar, the temperature of the material is 180 ° C and the drying is carried out at 50 ° C for 4 hours.
    [0050] Figure 10 shows SEM images of the boehmite particles according to the invention within the polyethylene matrix. Example 9 Incorporation of Particles Obtained in Example 4 into a Matrix The metallic copper particles obtained in Example 4 were dispersed in a proportion of 58% by weight in an aqueous matrix comprising in particular 13% of alcohol (ethanol or ethylene glycol + citric acid). The protocol is as follows: The surface of the copper particles is washed: the copper particles are suspended in a concentrated solution of citric acid for 24 hours at room temperature. The particles are then filtered and suspended in a solution of ethanol and citric acid for 24 hours at room temperature. The particles are filtered and dried. The particles are mechanically dispersed in ethanol to obtain a paste. This is mixed with the aqueous solution. The final solution obtained consists of 58% by weight of copper particles, 13% by weight of alcoholic solution (for example 90% ethanol + 10% citric acid by weight) and 29% by weight of aqueous solution.
    [0051] Example 10 Incorporation of hollow ZrO 2 particles in an enamel matrix Hollow ZrO 2 particles according to the invention were dispersed in an aqueous slip enamel matrix according to the following protocol: 1 / Pre-dispersion of the hollow particles in aqueous solution: the hollow particles are suspended in an aqueous solution. The proportion of hollow particles can vary between 50% and 90% by mass of solid matter. 2 / Pre-dispersion of the enamel powder in aqueous solution. The proportion of enamel powder may vary between 50% and 90% by mass of solid matter. 3 / The suspension of hollow particles is added with mechanical stirring to the enamel slip. This slip may consist finally of 30% to 60% by weight of solids and 40% to 70% by weight of aqueous solution. The slip obtained can be deposited on a metallic substrate by projection. The substrate, coated with enamel, is dried under air at around 100 ° C. and then fired at a high temperature (between 800 and 1000 ° C.) depending on the quality of the enamel.
    [0052] Figure 11 shows a SEM image of a dense enamel matrix containing 20% hollow zirconium oxide particles deposited by spraying onto a steel substrate. Example 11: Incorporation of dense ZnO particles into an ABS matrix Figure 12 is a SEM image of dense ZnO particles according to the invention incorporated into an ABS (Acrylonitrile Butadiene Styrene) matrix.
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. Set of micrometric spherical inorganic particles, characterized in that the particles are individualized.
    [0002]
    2. A set of particles according to claim 1, wherein each particle is not constituted by the aggregation of several smaller particles.
    [0003]
    3. Particle assembly according to claim 1 or 2, wherein the particles are solid or hollow.
    [0004]
    The particle assembly of any one of claims 1 to 3, wherein the particles are porous, mesoporous or non-porous.
    [0005]
    5. A set of particles according to any one of claims 1 to 4, wherein the particles have a sphericity coefficient greater than or equal to 0.75.
    [0006]
    6. Particle assembly according to any one of claims 1 to 5, wherein the particles have a diameter between 0.1 and 1000 micrometers.
    [0007]
    The particle assembly according to any of claims 1 to 6, wherein the particles are ZnO particles, alumina particles, boehmite particles, silica particles, copper oxide particles, titanium oxide particles, titanium-silicon mixed oxide particles, montmorillonite particles, hydrotalcite particles, magnesium dihydroxide particles, magnesium oxide particles, carbon dioxide particles, zirconium, yttrium oxide particles Y203, cerium dioxide particles, yttrium stabilized zirconia particles, CaCu3Ti4012 particles, BaTiO3 particles, iron oxide particles, magnesium sulfate, ZnO, 18MnO, 82Fe2O4 particles, Mn2P207 particles, manganese nickel oxide particles, mullite particles, ZnFe2O4 particles, MnFe2O4 particles, NiFe2O4 particles, of CoFe2O3, MgAl2O4 particles, or Y3A15012 particles.
    [0008]
    8. Material comprising a set of particles according to any one of claims 1 to 7 dispersed substantially homogeneously in a matrix.
    [0009]
    The material of claim 8, wherein the matrix is a liquid matrix.
    [0010]
    The material of claim 8, wherein the matrix is a solid matrix.
    [0011]
    11. The material of claim 10, wherein the matrix is a thermoplastic polymeric matrix. 15
    [0012]
    12. Process for the preparation of a set of particles according to one of claims 1 to 7 by aerosol pyrolysis, comprising: the nebulization of a liquid solution containing a precursor of the inorganic material or materials from which it is desired to form particles at a given molar concentration in a solvent, so as to obtain a mist of droplets of solution, the heating of the fog at a so-called drying temperature capable of ensuring the evaporation of the solvent and the formation of particles, the heating of these particles at a so-called pyrolysis temperature capable of ensuring the decomposition of the precursor to form the inorganic material, the densification of the particles, the quenching of the particles, and the recovery of the particles thus formed. 30
    [0013]
    A process for preparing a material according to any one of claims 8 to 11, comprising contacting a matrix with at least one set of particles according to any one of claims 1 to 7.
    [0014]
    The method of claim 13, further comprising a step of shaping the material, said shaping step not requiring an additional step of dispersing the particles within the die with respect to the shaping process. conventionally used for matrices without inclusion of particles.
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    同族专利:
    公开号 | 公开日
    FR3020766B1|2020-05-08|
    CN107074542B|2020-10-16|
    IL248761D0|2017-01-31|
    KR20170020326A|2017-02-22|
    US20170190867A1|2017-07-06|
    ZA201608300B|2019-04-24|
    CN107074542A|2017-08-18|
    AU2015257525A1|2017-01-05|
    JP2017514786A|2017-06-08|
    UA120850C2|2020-02-25|
    IL248761A|2021-04-29|
    EA035971B1|2020-09-08|
    EA201692251A1|2017-03-31|
    AU2015257525B2|2019-03-28|
    EP3140255A1|2017-03-15|
    MA39883A|2017-03-15|
    US9982109B2|2018-05-29|
    TN2016000478A1|2018-04-04|
    CA2947499A1|2015-11-12|
    JP2020172435A|2020-10-22|
    WO2015170060A1|2015-11-12|
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    优先权:
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    FR1454141A|FR3020766B1|2014-05-07|2014-05-07|INDIVIDUALIZED INORGANIC PARTICLES|
    FR1454141|2014-05-07|FR1454141A| FR3020766B1|2014-05-07|2014-05-07|INDIVIDUALIZED INORGANIC PARTICLES|
    JP2017510775A| JP2017514786A|2014-05-07|2015-05-07|Individualized inorganic particles|
    MA039883A| MA39883A|2014-05-07|2015-05-07|Individualised inorganic particles|
    US15/308,651| US9982109B2|2014-05-07|2015-05-07|Individualised inorganic particles|
    EA201692251A| EA035971B1|2014-05-07|2015-05-07|Individualised inorganic particles|
    PCT/FR2015/051223| WO2015170060A1|2014-05-07|2015-05-07|Individualised inorganic particles|
    CA2947499A| CA2947499A1|2014-05-07|2015-05-07|Individualised inorganic particles|
    CN201580036351.0A| CN107074542B|2014-05-07|2015-05-07|Individualized inorganic particles|
    UAA201612399A| UA120850C2|2014-05-07|2015-05-07|Individualised inorganic particles|
    KR1020167032792A| KR20170020326A|2014-05-07|2015-05-07|Individualised inorganic particles|
    EP15725838.5A| EP3140255A1|2014-05-07|2015-05-07|Individualised inorganic particles|
    TN2016000478A| TN2016000478A1|2014-05-07|2015-05-07|INDIVIDUALIZED INORGANIC PARTICLES.|
    AU2015257525A| AU2015257525B2|2014-05-07|2015-05-07|Individualised inorganic particles|
    IL248761A| IL248761A|2014-05-07|2016-11-06|Individualised inorganic particles|
    ZA2016/08300A| ZA201608300B|2014-05-07|2016-12-01|Individualised inorganic particles|
    JP2020121995A| JP2020172435A|2014-05-07|2020-07-16|Individualized inorganic particles|
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