• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to thermally insulating materials comprising said particles and a process for preparing these particles and materials obtained by including these particles in matrices. The present invention also relates to spherical and hollow inorganic particles of low bulk density imparting thermal properties in various types of matrices in which they are dispersed.
    公开号:FR3043572A1
    申请号:FR1560838
    申请日:2015-11-12
    公开日:2017-05-19
    发明作者:Loic Marchin；Marie-Laure Desse
    申请人:Pylote SA；
    IPC主号:
    专利说明:

    Thermally insulating materials incorporating spherical and hollow inorganic particles
    The present invention relates to materials incorporating micrometric, spherical, hollow and low density inorganic particles imparting thermal insulation properties in various types of matrices in which they are dispersed. The invention also relates to these particles, a process for preparing these particles and materials obtained by including these particles in matrices.
    State of the art of the invention
    In the field of thermally insulating materials, it is common to use particles to impart to these materials these insulating properties. The metal oxide particles can be used as a thermal barrier, and can thus enter into the constitution of thermally insulating materials in various fields, such as aeronautics, space, building, automotive, furnaces, personal protection systems against fire or temperature, etc.
    It has been described by the Applicant in the patent FR2973260 a process for preparing hollow particles of metal oxide. There is proposed a method using the aerosol pyrolysis technique, implemented under particular conditions. During nebulization, the liquid solution contains not only a precursor of a metal oxide in a solvent but also a swelling agent in an amount sufficient to form, during its decomposition, a single cavity concentrating in the core of the particle . The blowing agent is preferably an organic polyacid or ethylene glycol and its derivatives. The pore size of the particles is less than one micron. The particles thus obtained are described as being suitable for use as basic constituents for the production of materials forming a thermal barrier and in particular for the manufacture of engine protection parts for aircraft engines. However, the process described therein requires the use of blowing agent, which makes the process complicated to implement, in particular with the ethylene glycol derivatives which, when decomposing, can generate mono or carbon dioxide, ketones and / or aldehydes or leave carbon residues. In addition, ethylene glycol derivatives are currently recognized for their specific toxicity for certain target organs.
    In this context, the Applicant has developed hollow inorganic spherical particles of low density which gives them a very low intrinsic thermal conductivity, which allows them once dispersed in materials to give the latter satisfactory thermal insulating properties. . These advantageous thermal properties are found in materials that can be used at various temperatures, in particular at outside temperatures or ambient temperatures (for example between -30 ° C. and 40 ° C.), as in the building, or that can be used at temperatures ranging from 80 ° C. and 500 ° C, as in industrial or private furnaces, or used at extreme temperatures (beyond 800 ° C, for example), as in the thermal barriers for aircraft engine turbines. The Applicant has put in place a simple process for preparing such inorganic particles, not requiring in particular the use of blowing agent or sacrificial agent (or "template") chemically decomposed or carbonized at high temperature creating the void in the heart of the particle. Summary of the invention
    A first object of the present invention is a set of inorganic particles, characterized in that the particles are spherical, micrometric, hollow and of low density.
    A second object is the use of these particles as a thermal barrier.
    In particular, these particles have a very interesting thermal barrier effect and can thus lighten the materials in which they are located, which can be very advantageous especially in the field of aeronautics, engines, or in the building.
    Another subject of the invention is a thermally insulating material comprising the particles of the invention dispersed in a matrix.
    Another object is a method for preparing particles according to the invention.
    Another object of the invention is a method for preparing a material according to the invention, comprising contacting a matrix with a set of spherical, micrometric, hollow and low density particles.
    Brief description of the figures
    Figure 1: Schematic representation of a reactor adapted for implementing the method according to the invention.
    Figure 2: scanning electron microscopy image of hollow mullite microspheres according to the invention.
    Figure 3: scanning electron microscopy image of hollow microspheres of magnesium oxide according to the invention.
    Detailed description of the invention
    The first object of the present invention is a material comprising inorganic particles, characterized in that the particles are spherical, micrometric, hollow and for which the powder has a bulk density of less than 700 kg.m-3, preferably is from 100 to 700 kg.m-3.
    Throughout the present description, the term "hollow particle" means a particle having a dense or low porous outer shell and a free volume inside said shell. These particles are distinguished in particular porous particles, which have a plurality of pores which, although they can communicate with each other, do not form a single free volume located inside a shell of the particle. The particles according to the invention are hollow, the thickness of their wall can be controlled, in particular by means of the parameters of the synthesis process, and more specifically by adequately fixing the concentration of metal oxide precursor in the solution. initial. By transmission electron microscopy, it has been calculated that the wall of particles with diameters greater than 0.7 microns represents between 5% and 50% of the diameter, which may in particular represent a thickness of 0.02 nm to 0, 7 microns.
    The powders, consisting of all the hollow particles according to the invention, have a particularly low bulk density which is between 100 and 700 kg / m 3.
    The density, expressed in the international system (SI) in kg / m3, represents the mass per unit volume of the powder including the interstitial porosity within the particles. Given the hollow structure of the particles, the density value is given on the powder "not packed" or so called bulk (or "bulk density") and after settlement (see DEGALLAIX, Suzanne.) Experimental characterization of materials: Physical properties, thermal and mechanical, PPUR polytechnic presses, 2007, pages 103-112, HAUSSONNE, Jean-Marie, ceramics and glasses: principles and techniques of development, PPUR polytechnic presses, 2005, pages 73-74).
    The particles according to the invention are spherical, that is to say that they have a sphericity coefficient in 3D or circularity in 2D 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 circularity coefficient in 2D 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 particular scanning electron microscopy or transmission, particles. The circularity coefficient C of a particle, in 2D view, _. S'urfa is the ratio> - ™ (For a perfect circle, this ratio is equal to 1) (CAVARRETTA, L, O'SULLIVAN, C., and COOP, MR Applying 2D shape analysis techniques to granular materials with 3D particle POWDERS AND GRAINS 2009, 2009, 1145, 833-836.)
    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 of an inorganic product, that is to say that is not derived from carbon chemistry. The chemical diversity of the inorganic particles is well known to those skilled in the art. The inorganic particles are in particular particles of metal (or alloy) or metal oxide. In particular, the inorganic particles are particles of zirconium oxide (or zirconia, of formula ZrCh), optionally stabilized with a rare earth element, particles of magnesium oxide (of formula MgO), oxide of aluminum (of formula AI2O3), boehmite (of formula AlOOH), zinc oxide (of formula ZnO), in particular hexagonal ZnO, optionally doped, for example doped with aluminum, particles of aluminum silicate , such as mullite (S1O2 Al2O3), particles of perovskite structure (based on calcium titanate, of formula CaTiCb), mixed oxide particles, such as mixtures of aluminum oxides, magnesium oxide and / or silicon, in particular binary or ternary AhCb-SiCh-MgO (sapphirine, corderite, spinel, ...), or a mixture thereof.
    The inorganic particles according to the invention may optionally comprise at least one dopant, such as, for example, aluminum, erbium, europium, ytterbium, or gadolinium. 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.
    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, magnesium dihydroxide particles, in particular hexagonal particles, particles of magnesium oxide, in particular cubic, particles of zirconium dioxide, in particular quadratic, particles of zirconia stabilized with yttrium, mullite particles, MgAhCri particles, or Y3Al5O12 particles.
    In a particular embodiment, the inorganic particles are particles of ZnO, in particular of hexagonal ZnO, optionally doped, for example doped with aluminum, particles of alumina, in particular of amorphous, cubic or rhombohedral alumina, particles of boehmite, in particular orthorhombic, magnesium dihydroxide particles, in particular hexagonal particles, particles of magnesium oxide, in particular cubic, particles of yttrium-stabilized zirconia, particles of CaCu3Ti40i2, particles of mullite ( S1O2-Al2O3), particles of MgAhCL, or particles of Y3Al5O12.
    In a more particular embodiment, the particles are particles of MgO, ZnO, ZrO2 possibly partially or totally stabilized with a member chosen from rare earths (in particular yttrium), Mullite (SiO 2 -Al 2 O 3), alumina, such doped particles, or their mixture. In another more particular embodiment, the particles are particles of MgO, ZnO, Yttrium-stabilized ZrO 2, Mullite (SiO 2 -Al 2 O 3), or such doped particles.
    The particles according to the invention are micrometric, that is to say that the average particle diameter is between 0.1 and 10 microns. According to another particular embodiment, the diameter of the particles according to the invention is between 0.2 and 7 micrometers and preferably between 0.3 and 5 micrometers, and is preferably between 0.5 and 2. The man of the The art knows the appropriate techniques for determining the diameter of the particles or sets of particles according to the invention, and it 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 (SEM) or in transmission (MET).
    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 50%, preferably less than or equal to 20%.
    The size distribution of the particles in the set of particles according to the invention can be monomodal or multimodal.
    In the present invention, the set of particles according to the invention has the advantage of having individualized particles, that is to say non-aggregated particles. Thus, each particle of the assembly 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 70%, at least 80%, at least 90%, at least 95% by number of the particles of the whole considered are individualized.
    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). 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. The particles are not perfectly spherical and can be aggregated, which is not the case with the particles of the present invention which have a high coefficient of sphericity greater than 0.75.
    Preferably, the particles according to the invention are non-deformable individualized particles. Also, the surface of each particle that is possibly in contact with other particles is generally 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 present invention also relates to the use of the particles according to the invention as a thermal barrier. The particles according to the invention can advantageously reduce the thermal conductivity of the materials conventionally used as thermal insulators, in particular this reduction is at least 10% and can possibly be up to 50% relative to the thermal conductivity. materials conventionally used as thermal insulators. Thus, and as previously specified, the particles may have the advantage of lightening the materials in which they are integrated. For example, particles embedded in aeronautical materials can help to lighten these thermally insulating materials and thus reduce fuel consumption and / or reduce the carbon dioxide emitted.
    According to one aspect, the invention relates to a thermally insulating material comprising particles according to the invention and a matrix. More specifically, the material comprises particles dispersed in a matrix. The characteristics of the particles according to the invention make their dispersion particularly homogeneous, which contributes to the thermal insulation performance.
    According to the present invention, the term "matrix" denotes any material used for thermal insulation, and can advantageously benefit from the inclusion of particles according to the invention. These are generally solid matrices, such as materials based on ceramics, fibers, organic foams (polymers, resins, for example) or inorganic, enamel, or a mixture thereof (composite materials), which are generally used. as thermal insulators. These matrices can be used in a variety of industries, such as aeronautics, aerospace, motors, automotive, building, furnaces, personal fire and temperature protection systems, etc.
    According to one aspect of the invention, the materials may be insulating ceramics, or "thermal barriers", containing microparticles according to the invention. Thus, these materials can operate at a higher temperature than currently used systems, which are based on zirconia particles partially stabilized with yttrium oxide, and dense structure.
    It may be a ceramic matrix composite part, obtained by infiltration of a suspension of a ceramic powder in a fibrous reinforcement. Ceramic matrix composites (or mixed ceramic composites, or CMCs) are emerging materials with high thermomechanical properties that can be used under severe operating conditions, such as temperatures above 750 ° C or 800 ° C or higher. at 1000 ° C. Given their high thermomechanical performance, these materials find particular application in the production of mechanical parts, for example in the field of aeronautics or aerospace, for example, for engine parts, for gas turbines or combustion chambers. According to one particular embodiment, the invention relates to ceramic matrix composite materials comprising a set of particles according to the invention, and possibly a fibrous reinforcement.
    In the field of cooking or industrial furnaces, it is common to use cavities coated with an enamel layer. Enamelled steel is known to be resistant to high temperatures (generally between 100 and 500 ° C) and to have a capacity for heat reflection allowing it, already intrinsically to have as applications the columns and heat exchangers, furnaces , or hot gas pipes.
    Thus, according to a particular embodiment, the invention relates to a material comprising an enamel matrix and a set of particles according to the invention, and in particular particles of magnesium oxide (MgO). The AFNOR NF92-010 standard of 1977 defines the enamel as a substance resulting from the melting or sintering of non-organic constituents and intended to form a vitrified or melted product on a metal support. The melting temperature of the enamels is above 500 ° C (932 ° F).
    The main constituent of enamel is generally silica, in pure form or combined with feldspars, clays and / or micas. Other constituents may be conventionally used in enamel, such as refractories (for example alumina, Al 2 O 3), fluxes which lower the melting and baking temperatures and which increase the coefficient of expansion (they are composed mainly of borax-sodium tetraborate, NaiELCb- in anhydrous or hydrated form, and alkaline oxides - for example sodium oxides, Na2O, potassium K2O, lithium L12O, calcium CaO, magnesium MgO and strontium SrO- to give borosilicate salts , adhesion promoters (for example metal oxides), opacifiers or dyes Thus, the invention may consist in introducing particles according to the invention, in order to sufficiently reduce the diffusivity and / or thermal conductivity of a enamelled coating on a substrate to enable it to reduce thermal losses towards the outside of the substrate, for example using the particles of the present invention; n at the walls of domestic or industrial furnaces, whose service temperatures do not exceed 400 ° C. More generally, by limiting the thermal losses, the electric consumption of the furnace is more homogeneous and better optimized, resulting in energy cost reductions. Without being limited to a theory of the invention, in practice, the particles according to the invention are distributed homogeneously in the enamelled layer, which will induce porosity. We can then speak of composite / enamel layers because the particles are not melted at vitrification temperatures of the enamel below 1200 ° C. The particles according to the invention can be introduced at a level between 10 and 60% by weight in the slip relative to the dry extract. The energy gain provided can be evaluated according to the power consumption of the oven and, in this context, the particles according to the invention thus used can bring a gain between 5% and 30%.
    This enamel-based material can therefore be used as a constituent of columns, heat exchangers, furnaces, or hot gas pipes. This material is generally in the form of film or layer. This layer-like material preferably has a thickness of 50 to 400 μm.
    According to one particular embodiment, the solid matrix may be a polymeric matrix, in particular a thermoplastic polymeric matrix. Among the polymer matrices that can be used according to the invention, mention may be made especially of polypropylene, polyethylene, polyethylene terephthalate, polyoxymethacrylate, polyurethanes, ABS (Acrylonitrile Butyrene Styrene), PLA (PolyLactic Acid) or polyethylenevinylacetate. According to one particular embodiment, the invention relates to materials comprising a polymeric matrix, in particular chosen from polypropylene, polyethylene, polyethylene terephthalate, polyoxymethacrylate, polyurethanes, ABS (acrylonitrile butyrene styrene) or polyethylenevinylacetate, and set of particles according to the invention.
    In the field of building, the thermally insulating materials, the most common, are fibrous insulators, based on natural or synthetic fibers, such as glass wool or rock wool, cellular insulators, of the expanded polymer type, such as polystyrene, polypropylene, polyvinyl chloride, polyethylene (particularly low or high density) expanded or extruded, or phenolic foams or polyurethane. Thin reflective multilayer insulators are thin technical complexes composed of an assembly of reflective films and associated separators (wadding, foams, etc.). Reflective films have the function of reflecting thermal radiation: this is the principle of double glazing and the survival blanket applied to the insulation of the house. At equivalent thermal efficiency, thin reflective multilayer insulators allow the installation of insulation devices 3 to 5 times thinner (air blades included) than traditional thick insulators. They are ideally suited for the insulation of residential, commercial and industrial buildings - in roofs, attics, walls and floors. The performance of an insulator is related to thermal transfers by radiation, convection and conduction. The lower the conductivity, the better the insulation, ie the ability to pass a heat flow. The conductivity is measured by usual laboratory techniques: the insulation is placed between 2 different temperature environments in order to create a temperature difference (ΔΤ) and the amount of energy required to maintain a constant temperature on each side of the room. insulation, is measured and is equal to the heat flow through the product. From this measurement of thermal conductivity follows a value of thermal resistance R, which is the ratio between the thickness (e) and the thermal conductivity (λ) of an insulator, expressed in m2.K7W (R = e / (λ) ). The resulting mass per unit volume of the foam is dependent on the extrusion conditions and the nucleating agent present. Preferably, the mass per unit volume of the insulating foam is less than 20 kg / m3, in particular less than 17 kg / m3.
    Thus, without wishing to be bound to any theory of the invention, it seems that the use of the particles according to the invention in the context of thermal insulation for the building makes it possible to bring a double porosity to two scales: the one brought by the bubbles formed during "foaming", the other by the addition of hollow particles according to the invention; the particles being of mineral nature, they can also contribute to the formation of foam, as passive nucleating agent. It can thus be imagined that the air contained in the hollow particles could also be released during the final stage of the foam production, thus the hollow particles would act as an active and passive agent. The particles according to the invention being of low bulk density also contribute to a lightening of the material, measurable by the reduction of the density of the insulation foam for the same thickness.
    The particles according to the invention can be incorporated by conventional extrusion and / or granulation methods.
    According to one particular embodiment, the invention relates to thermally insulating materials for the building, comprising a matrix and a set of particles according to the invention, said matrix being in particular a matrix of natural or synthetic fibers, such as glass wool or rockwool, or a matrix of cellular insulators, of the expanded polymer type, such as polystyrene, polypropylene, polyvinyl chloride, or expanded or extruded polyethylene, or a matrix of phenolic foams or polyurethane. The inclusion of the particles according to the invention in a matrix makes it possible to confer particularly advantageous thermal properties on 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 in the slip, precursor of the solid matrix. This can be particularly the case when the materials are ceramic matrices. A method of manufacturing such a material comprises in particular the sintering of a slip comprising particles according to the invention and ceramic precursors, according to methods conventionally used for ceramics. When the matrix comprises fibers, the particles according to the invention can be incorporated into a composite including the fibers, as in the case of CMCs. The particles according to the invention can be introduced for example by intimately mixing fibers and particles according to the invention in the form of a single slip or by impregnating the fibers with a slip containing the particles according to the invention. invention. In the case where the matrix is conventionally extruded or granulated, the particles according to the invention may be incorporated into the masterbatch comprising the precursors of the matrix and intended to be then conventionally extruded and / or granulated.
    The material comprising the particles according to the invention may especially be in the form of powder, beads, pellets, granules, layers (or films) and / or extrusions, the subsequent shaping operations may be performed by conventional techniques known to those skilled in the art.
    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 method can preferably be implemented on the 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 or absence of a chemical dispersing agent, such as a surfactant. 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 dispersing substantially homogeneously in volume in the matrix, whatever their chemical nature and the nature of the matrix. This means that the amount of particles per unit volume is usually the same at every point of the matrix. In the case of a solid matrix, the quantity 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 improvement of the thermal insulation obtained and conferred on the matrix by the inclusion of the particles according to the invention is distributed substantially homogeneously throughout the volume of the matrix.
    The material according to the invention may comprise particles according to the invention in any proportion adapted to give it the desired thermal insulation property. For example, the material may comprise from 0.1 to 80% by weight of particles relative to the total mass of matrix and particles, preferably from 1 to 60% by weight, in particular from 2 to 25% by weight.
    Another object of the present invention is a method for preparing a set of particles according to the invention, as described above. The process according to the invention is a so-called "aerosol pyrolysis" process (or pyrolysis spray) which is carried out at drying and not pyrolysis temperatures. This process is an improved process compared to the aerosol pyrolysis method described in particular in application FR 2 973 260. More specifically, the process according to the invention is generally carried out in a reactor and does not require a blowing agent. . The set of particles thus obtained can thus correspond to large quantities, more specifically the quantity obtained can be of more than 100g, 500g, 1kg, 15kg, or 20kg, this quantity varying according to the supply of solution provided and / or desired at the reactor. The set of particles thus obtained has the advantage of being obtained in large quantities, while respecting the characteristics of the particles as described above.
    This process comprises the following steps: (1) 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 solution, (2) heating the fog at a temperature (called drying) capable of ensuring the evaporation of the solvent to increase the precursor concentration of the inorganic material or materials at the periphery of the droplets and capable of ensuring the formation of particles, (3) heating these particles to a temperature (called pyrolysis) capable of ensuring the decomposition of the precursor to form the inorganic material with simultaneous precipitation and complete extraction of the solvent to form the shell of the hollow particles, (4) the densification of the shell of the particles, and (5) the recovery of 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 less than or equal to 10 seconds, in particular less than or equal to 5 seconds. In step (1), the liquid solution is generally in the form of an aqueous or hydroalcoholic solution or in the form of a colloidal sol. More specifically, the liquid solution of step (1) is introduced into a reactor by nebulization. Preferably, the total concentration of precursor (s) of the inorganic material or materials from which one wants to form particles is greater than or equal to 0.5 mol / L in the solution, a concentration greater than or equal to 10 or 20 % by weight relative to the total mass of the solution. In a particular embodiment, the total concentration of precursor (s) is between 0.5 and 3.0 mol / L (M). The heating step (2) (drying) is preferably carried out at a temperature of 150 to 400 ° C, preferably 200 to 400 ° C (preferably 300 to 400 ° C), and / or preferably duration less than or equal to 10 seconds, in particular between 1 and 10 seconds. The step (3), called pyrolysis, is preferably carried out at a temperature of 400 to 700 ° C, and / or preferably for a duration less than or equal to 30 seconds, in particular between 10 and 30 seconds. The step (4) of densification of the shells can be carried out in a wide range of temperatures, in particular between 200 and 1000 ° C. This step is preferably carried out at a temperature of 400 to 800.degree. C., more particularly of 500 to 700.degree. C., in particular when the particles which it is desired to prepare are wholly or at least partly in crystalline form. 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.
    Thus, during steps (2), (3) and (4), there is evaporation of the solvent, formation of particles with saturation in precursor (s) at the periphery of the droplets, decomposition of the precursor to form the inorganic material with simultaneous precipitation and complete extraction of the solvent to form the shell of the hollow particles, then densification of the shell of the particles, these events succeeding but may overlap in time as the steps advance. 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.
    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. 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 as a function of the particles, and in particular of the chemical nature of the particles, which 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.
    Preferably, steps (2), (3), and optionally (4) are carried out at increasing temperatures.
    In a particular embodiment, the temperatures of step (4) are at least 200 ° C higher than the decomposition temperature of the precursor (s). In particular for metal nitrates, for example for magnesium nitrate which has a decomposition temperature of 300 ° C, step 4 will be at least 500 ° C.
    According to one particular embodiment of the invention, when particles of Al.sub.2O.sub.3 or ZrC.sub.2> are prepared, the corresponding nitrate decomposition temperature being 200.degree. C., the temperature of stage (4) is preferably at least 400 ° C. According to another particular embodiment of the invention, when MgO particles are prepared, the temperature of step (4) is preferably at least 500 ° C-550 ° C. According to another particular embodiment of the invention, when ZnO particles are prepared, the corresponding nitrate decomposition temperature being 350-380 ° C., the temperature of step (4) is preferably at least 550 ° C. C and preferably at 700 ° C.
    As specified above, the method according to the invention does not require the presence of blowing agent, such as in particular described in the patent FR2973260.
    The method according to the present invention preferably further comprises, between the densification step (4) of the shells of the hollow particles and the step of recovering the particles (5), a step (4 ') of quenching the particles. The quenching step (4 ') corresponds to a rapid decrease in temperature. The quenching step advantageously corresponds to a temperature decrease of at least 300 ° C./s, for example to reach a temperature of between 15 and 50 ° C. 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 a particular embodiment, the gas entering the reactor for this quenching step 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.
    The method is preferably implemented in the absence of gas flow vectorizing the fog from the beginning (e.g., bottom) of the reactor. The laminar flow making it possible to bring the material into the zone in which the temperature is higher is advantageously created solely by the end suction (eg high) of the reactor, producing a depression, for example of the order of a few pascals or a few dozen pascals.
    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 implemented also includes a gas inlet at the level where the mist is formed. The gas entering the reactor at this level is preferably air.
    Preferably, the process for preparing the particles according to the invention does not comprise any other heating step than those implemented inside the aerosol pyrolysis reactor.
    Figure 1 shows an example of a reactor scheme for implementing the method 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.).
    The precursor or precursors of the inorganic material or materials from which one wishes to form particles may be of any origin. It (they) is (are) introduced in step (1) of the process in the form of a liquid solution, in particular an aqueous or hydroalcoholic solution containing the metal ions (in the form of organic or inorganic salt, other than the chlorine of the metal in question, for example the nitrate of the metal in question, such as aluminum nitrate), and optionally the precursor molecules (such as organosilanes, for example tetraethylorthosilicate, or alkoxides, for example an aluminum alkoxide, as aluminum isopropoxide), or in the form of a colloidal sol (such as a colloidal dispersion of nanoparticles of the metal or oxide of the metal in question). Preferably, the precursor or the precursors of the inorganic material or materials is (are) introduced into the process step (1) in the form of a liquid solution, in particular an aqueous or hydroalcoholic solution containing the metal ions. (as an organic or mineral salt of the metal considered). Preferably, it is nitrate of the metal in question. The precursor (s) of the inorganic material (s) is (are) chosen according to the particles that it is desired to form. 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.
    According to one particular embodiment of the invention, the particles according to the invention consist entirely or partially of a metallic component, which may be an organic-inorganic hybrid. This component can be obtained by sol-gel from at least one metal molecular precursor comprising one or more hydrolyzable groups, optionally in the presence of a dispersing agent for the colloidal sols favoring the stability of the solution in the step ( 1) of the process. In the case where the particles obtained according to the process described above are hybridized (organic / inorganic), a post-treatment step is advantageously carried out, in particular a step of heating the particles is implemented, in order to render completely inorganic particles.
    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 step of heating the particles, and / or a step of coating the particles, 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 low.
    The method according to the invention makes it possible to control the size but especially the thickness of the shells of the particles at the output of the process.
    Another subject of the invention is a set of particles capable of being prepared according to the process defined above, and in particular by the implementation of the process comprising or consisting of steps (1) to (5), such as defined above. The particles thus prepared have the characteristics described above. This process makes it possible in particular to obtain hollow, spherical, micrometric particles having a low density as described above, and advantageously individualized. 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.
    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, since 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 or greater than 300 ° 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. There may be mentioned for example alumina, zinc oxide, and magnesium oxide, mullite or zirconium oxide stabilized or not. 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.
    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.
    The following examples are provided by way of illustration, and not limitation, of the invention. Examples
    In the following examples, the LASER granulometry measurements were carried out using a LASER Mastersizer 2000 granulometer (Malvem Instruments), on particles wet in water.
    EXAMPLE 1 Hollow Particles of Magnesium Oxide (MgO)
    The magnesium oxide (MgO) particles were prepared according to the method below.
    Dissolve 20.4 g of magnesium nitrate hexahydrate in 79.6 g of demineralized water, ie a molar precursor concentration of 1.0 mol / l.
    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: 300 ° C., 400 ° C., 500 ° C., respectively.
    FIG. 3 shows Scanning Electron Microscopy images of hollow microspheres of magnesium oxide obtained with an average diameter of 2.7 microns.
    Example 2: hollow particles of doped zinc oxide
    ZnO: Al doped zinc oxide particles were prepared according to the method below.
    Dissolution of 25.8 g of zinc nitrate hexahydrate and 1.6 g of aluminum nitrate nanohydrate in 72.5 g of demineralized water, ie a total molar precursor concentration of 1.2 mol / l. The Zn / Al ratios can be checked to achieve the desired doping rate.
    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: 300 ° C., 500 ° C., 700 ° C., respectively.
    Examples 3 and 4: Al2O3 Alumina Hollow Particles
    Al2O3 alumina particles were prepared according to the method below.
    Dissolution of 27 g of aluminum nitrate nanohydrate in 73 g of demineralized water, ie a molar precursor concentration of 1.0 mol / l.
    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: 300 ° C., 500 ° C., 700 ° C., respectively.
    For the Al 2 O 3 particles of Example 4, a calcination at 1200 ° C. makes it possible to crystallize the powder into corundum (alpha alumina).
    Example 5: hollow particles of mullite
    The mullite particles (3AI2O3, 2S1O2) were prepared according to the method below with a total precursor concentration of 2.7 mol / L. 1- Dissolution of 5.3 g of aluminum nitrate nanohydrate in 70.8 g of demineralized water. 2- Addition of 16.6 g of aluminum alkoxide (aluminum isopropoxide) with stirring. 3- Addition of 7.3 g of silicon alkoxide (Tetra Ethyl Ortho Silicate) with stirring. 4- After aging of the soil, heating for 2 hours at 80 ° C. in order to allow the hydrolysis-condensation of the alkoxides and to form the mullite sol.
    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: 300 ° C., 400 ° C., 500 ° C., respectively.
    A calcination at 1200 ° C makes it possible to crystallize the powder in mullite.
    FIG. 2 shows Scanning Electron Microscopy images of mullite hollow microspheres obtained with an average diameter of 1.5 microns.
    Example 6: Zirconium oxide hollow particles Z1O2
    The zirconium oxide particles ZrC> 2 were prepared according to the process of the invention.
    A precursor solution dosed at 0.6 mol / l in hydrated zirconium oxynitrate 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: 300 ° C., 400 ° C., 500 ° C., respectively.
    Example 7 Characteristics of Particles Granulometry and Sphericity
    Table 1 below summarizes the particle size characteristics of the particles obtained in Examples 1-6 and the calculation of sphericity by scanning electron microscopy image analysis by approximating the shapes with 2D ellipses and calculating the ratio. of circularity.
    Table 1
    Apparent density of powders
    A pillbox of 15 ml is weighed using a precision scale (to the nearest 0,001 g). Using a funnel, the powder is poured into the pill pillar until overflow and leveled with a spatula at the upper limit of the pillbox. The full pillbox is weighed. The unpacked density pbp is calculated (= mass of the powder / volume)
    The pillbox full is subjected to vibrations during 20 min. After the vibration stops, the height of the empty part of the pillbox is measured at 3 different places. The missing volume is calculated using the average of the 3 measurements. The packed density pbt is calculated (= mass of the powder / volume after settling).
    It is also calculated the Hausner index which reflects the cohesion and the flowability of the powders. The powders of the present invention have an index H = 1.2, which means that the powders have good flowability.
    Table 2 shows the densities obtained.
    Table 2
    Preparation of pellets to characterize the porosity and thermal conductivity of the particles
    In order to characterize the porosity and the thermal conductivity, the powders of hollow spheres (or particles) according to the invention can be pressed in dry forms. Another method is to make a slurry by suspending the powders of spheres in water by conventional mixing techniques or by wet milling.
    Organic binders or dispersants may be added to facilitate suspending, control viscosity, or to mechanically strengthen "green" pellets and improve the casting process.
    The casting technique involves casting a slip in a plaster mold and drying until a dry pellet is obtained.
    Isostatic pressing can also be chosen, namely to compact the powder in dry form or containing a small fraction of solvent, under a uni-axial pressure.
    Conventional hot pressing or Spark Plasma Sintering sintering can also be chosen and are compatible with the invention and the powders of spheres described in the present invention.
    Density and porosity of the pellets obtained
    The density and the porosity of the sintered pellets are determined by porosimetry with water at room temperature as described by PREVOST in 2007 for the application "thermal barrier" (PREVOST, Marie-Anne, Study of new ceramics for thermal barrier 2007 Ph.D. thesis, University Pierre and Marie Curie-Paris VI).
    Thermal conductivity
    The thermal conductivity λ (Τ), given in W.nr'.K "1, is related to thermal diffusivity by the expression: λ = p (T) CP (T) D (T)
    D (T) thermal diffusivity (m2 / s) as a function of Temperature T
    p (T): density (kg / m3) depending on the temperature T
    Cp (T): specific heat at constant pressure (J.K "1.kg'1), calculated from published data.
    Thermal diffusivity was measured by the flash laser method.
    The pellets were sintered to densify at a temperature of 1400 ° C.
    Table 3 below summarizes the results obtained for the Alumina (Al 2 O 3) of Example 4 and the mullite 3 Al 2 O 3, 2 SiO 2 of Example 5.
    Table 3 For comparison, and according to the same measurement methods, commercial dense Al 2 O 3 particles have a density of 600 kg / m 3. After sintering, the pellets made from these particles have a porosity of about 45%, a thermal conductivity at 20 ° C of about 4W / mK, a thermal conductivity at 500 ° C of about 3 and a thermal conductivity at about 1000 ° C of about 1.
    Thus, the thermal conductivities of pellets comprising particles according to the invention are much lower than those of commercial dense powders.
    Example 8 Incorporation of the Particles According to the Invention into a Polyethylene Foam Matrix
    Zinc oxide (ZnO), mullite, MgO magnesium oxide, Al 2 O 3 aluminum oxide hollow particles could be used in this example.
    The hollow particles according to the invention were incorporated into the polyethylene by standard extrusion / dies and granulation techniques in order to constitute a masterbatch.
    ZnO zinc oxide hollow particles:
    An expanded polyethylene foam was made by extrusion and addition of gas and calendered in film form. The polyolefin grade is low density polyethylene with about 1% hollow zinc oxide particles. The powders are incorporated in the form of masterbatches.
    A gain of about + 10% was obtained from a thermal conductivity point of view and a decrease of about -10% in the density of the foam.
    The size of the bubbles was analyzed by optical microscopy and the addition of hollow microspheres decreased the average bubble diameter.
    Table 4 summarizes the results obtained
    Table 4
    Example 9 Incorporation of hollow MgO particles in an enamel matrix MgO magnesium oxide hollow particles according to the invention were dispersed in an aqueous slip enamel matrix according to the following protocol: 1 / Pre-dispersion hollow particles in aqueous solution: the hollow particles are suspended in an aqueous solution. The proportion of hollow particles may vary between 10% and 60% by mass of solid matter. In the example, 40% of microspheres were tested in bulk on a dry basis. 2 / Pre-dispersion of the enamel powder in aqueous solution. The proportion of enamel powder may vary between 40% and 90% by mass of solid matter. In the example, was tested 60% by mass of enamel on dry extract. 3 / The suspension of hollow particles is added with mechanical stirring to the enamel slip. This slip may consist ultimately of 30% to 60% by weight of solids and 40% to 70% by weight of aqueous solution. In the example, was tested 40% by mass.
    The slip obtained is deposited on a metal substrate by spraying or brushing. The substrate, coated with enamel, is dried in air at about 100 ° C. and then fired at a high temperature between 500 ° C. and 900 ° C.
    The thermal conductivity λ (Τ), given in W.m'.K'1, is related to the thermal diffusivity
    by the expression: λ = p (T) CP (T) D (T)
    D (T) thermal diffusivity (m2 / s) as a function of Temperature T
    p (T): density (kg / m3) depending on the temperature T
    Cp (T): specific heat at constant pressure (J.K'fkg "1), calculated from published data
    Thermal diffusivity was measured by the steel plate flash laser method coated with an enamel layer, measured at 100 microns.
    It was possible to calculate the thermal conductivity λ from the data of measurements of the thermal diffusivity D of the "steel + enamel" plates.
    The specific heat capacity Cp is approximated by that of the steel (500 J / kg.K).
    Table 5 summarizes the results obtained.
    Table 5
    权利要求:
    Claims (12)
    [1" id="c-fr-0001]
    1. Thermally insulating material comprising a set of inorganic particles and a matrix, characterized in that the particles are spherical, micrometric in average diameter of 0.1 and 10 microns, hollow and whose apparent density is 100 to 700 kg / m3.
    [2" id="c-fr-0002]
    2. Material according to claim 1, characterized in that the particles are particles of MgO, ZnO, Z1O2, optionally stabilized with a rare earth element, Mullite (S1O2-Al2O3), alumina, such doped particles, or their mixture.
    [3" id="c-fr-0003]
    3. Material according to one of claims 1 and 2, characterized in that the matrix is a solid matrix, especially ceramics, fibers, foams, enamel, or a mixture thereof.
    [4" id="c-fr-0004]
    4. A set of inorganic particles characterized in that the particles are spherical, micrometric in average diameter of 0.1 and 10 microns, hollow and whose apparent density is 100 to 700 kg / m3.
    [5" id="c-fr-0005]
    5. The assembly of claim 4, characterized in that the particles are particles of MgO, ZnO, ZrO2, optionally stabilized with an element selected from rare earths, Mullite (S1O2-Al2O3), alumina, such doped particles, or their mixture.
    [6" id="c-fr-0006]
    6. An assembly according to one of claims 4 and 5, characterized in that the particle diameter is between 0.2 and 7 micrometers, and is preferably between 0.3 and 5.
    [7" id="c-fr-0007]
    7. Use of the particles according to any one of claims 4-6 as a thermal barrier.
    [8" id="c-fr-0008]
    8. Thermally insulating material for the building, comprising a matrix and a set of particles as defined in one of the preceding claims 4-6.
    [9" id="c-fr-0009]
    9. Thermally insulating insulating material, comprising a ceramic matrix and a set of particles as defined in one of the preceding claims 4-6, and optionally a fibrous reinforcement.
    [10" id="c-fr-0010]
    10. Thermally insulating insulating material, comprising an enamel matrix and a set of particles as defined in one of the preceding claims 4-6.
    [11" id="c-fr-0011]
    A process for preparing a set of inorganic particles according to one of the preceding claims 4-6 by aerosol pyrolysis, comprising: (1) nebulizing a liquid solution containing a precursor of the inorganic material or materials from which of which it is desired to form particles at a molar concentration greater than or equal to 0.5 mol / L in the solution, so as to obtain a mist of droplets of solution, (2) heating the fog at a temperature capable of ensuring the evaporation of the solvent to increase the precursor concentration of. or inorganic materials at the periphery of the droplets and capable of ensuring the formation of particles, (3) the heating of these particles to a temperature capable of ensuring the decomposition of the precursor to form the inorganic material with simultaneously the precipitation and the complete extraction of the solvent for forming the shell of the hollow particles, (4) densification of the shell of the particles, (4 ') optionally quenching of the particles, and (5) recovery of the particles thus formed.
    [12" id="c-fr-0012]
    A process for preparing a material according to one of claims 1-3 and 7-10, comprising contacting a matrix with a set of particles according to any one of claims 4-6.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3374075A1|2018-09-19|Thermally insulating materials including spherical, hollow inorganic particles
    KR101887245B1|2018-08-09|Inorganic oxide coating
    US20140179509A1|2014-06-26|Porous glass ceramic composition and method for manufacturing the same
    EP3024799B1|2018-10-03|Product having a high alumina content
    FR2742142A1|1997-06-13|NEW BONDING PHASE FOR PHOSPHOMAGNETIC CEMENTS AND THEIR USE FOR THE PREPARATION OF MORTARS
    FR3020766A1|2015-11-13|INDIVIDUALIZED INORGANIC PARTICLES
    US10221103B2|2019-03-05|Porous ceramic composite particle and method for preparing the same
    Soler-Illia et al.2004|Designed synthesis of large-pore mesoporous silica–zirconia thin films with high mixing degree and tunable cubic or 2D-hexagonal mesostructure
    EP3684739B1|2021-08-18|Ceramic foam
    EP2731986B1|2020-02-12|High-performance thermal insulation materials
    EP3700876B1|2022-01-26|Particulate ceramic composite material, part comprising the same, and method for the production of said part
    WO2020012553A1|2020-01-16|Coating liquid and coating film
    FR2973260A1|2012-10-05|Preparing hollow metal oxide particles e.g. yttrium stabilized zirconium oxide particles by pyrolysis of aerosol, comprises e.g. spraying liquid solution in solvent at given molar concentration, and vectorizing spray in carrier gas flow
    JP6588365B2|2019-10-09|Inorganic oxide micro hollow particles
    JP5990471B2|2016-09-14|Ceramic thick skin hollow particles and method for producing the same
    JP5974683B2|2016-08-23|Particle having void inside particle and method for producing the same
    TWI735919B|2021-08-11|Method for producing a hydrophilic aerogel particle and related application of its product
    FR2814740A1|2002-04-05|INSULATING REACTIVE MINERAL LOAD
    EP2855389B1|2019-12-25|High-performance thermal insulation products
    JP5942813B2|2016-06-29|Manufacturing method of ceramic composite material
    PUEPI KOM2013|DEVELOPMENT OF POROUS CONCRETE GEOPOLYMER USING HYDROGEN PEROXIDE AS BLOWING AGENT.
    KR20140131399A|2014-11-13|Porous ceramic structure and manufacturing method thereof
    同族专利:
    公开号 | 公开日
    EA201891131A1|2018-10-31|
    JP2021183871A|2021-12-02|
    FR3043572B1|2020-05-15|
    US10843970B2|2020-11-24|
    CA3003813A1|2017-05-18|
    JP2019504967A|2019-02-21|
    CN108698009B|2021-10-26|
    EP3374075A1|2018-09-19|
    CN108698009A|2018-10-23|
    EA037872B1|2021-05-28|
    JP6956082B2|2021-10-27|
    US20190100464A1|2019-04-04|
    WO2017081426A1|2017-05-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5958361A|1993-03-19|1999-09-28|Regents Of The University Of Michigan|Ultrafine metal oxide powders by flame spray pyrolysis|
    FR2973260A1|2011-03-31|2012-10-05|Pylote|Preparing hollow metal oxide particles e.g. yttrium stabilized zirconium oxide particles by pyrolysis of aerosol, comprises e.g. spraying liquid solution in solvent at given molar concentration, and vectorizing spray in carrier gas flow|
    WO2014160445A1|2013-03-13|2014-10-02|X-Tend Energy, Llc|Method for the use of slurries in spray pyrolysis for the production of non-hollow, porous particles|
    US5472461A|1994-01-21|1995-12-05|Norton Company|Vitrified abrasive bodies|
    US6733907B2|1998-03-27|2004-05-11|Siemens Westinghouse Power Corporation|Hybrid ceramic material composed of insulating and structural ceramic layers|
    GB0226997D0|2002-11-19|2002-12-24|Welding Inst|Heat resistant product|
    US7108925B2|2003-09-22|2006-09-19|Siemens Power Generation, Inc.|High temperature insulation utilizing zirconia-hafnia|
    JP5248054B2|2007-07-23|2013-07-31|関西電力株式会社|Method for producing spherical alumina particles|
    JP5082987B2|2008-03-31|2012-11-28|株式会社豊田中央研究所|Internal combustion engine|
    JP2010185290A|2009-02-10|2010-08-26|Toyota Central R&D Labs Inc|Heat insulating film and method of forming the same|
    CN102716701B|2012-06-21|2014-07-23|华中师范大学|Method for preparing nickel-doped bismuth silicon oxide microspheres by ultrasonic spray|
    JP6316153B2|2013-09-19|2018-04-25|太平洋セメント株式会社|Fine alumina hollow particles|
    JP6136861B2|2013-11-06|2017-05-31|マツダ株式会社|Formation method of heat insulation layer|
    CN103949192B|2014-01-16|2016-07-06|常州大学|A kind of method that microwave-assisted aerosol prepares hollow ball|JP2019172474A|2018-03-26|2019-10-10|太平洋セメント株式会社|Hollow particles|
    CN108987737A|2018-10-24|2018-12-11|遵义源创生产力促进中心有限公司|A kind of fluorapatite cladding nickel-cobalt lithium manganate cathode material method|
    CN111889028A|2020-07-31|2020-11-06|山东财富化工有限公司|Production process of full-water-soluble granular magnesium nitrate|
    法律状态:
    2016-11-10| PLFP| Fee payment|Year of fee payment: 2 |
    2017-05-19| PLSC| Publication of the preliminary search report|Effective date: 20170519 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-11-18| PLFP| Fee payment|Year of fee payment: 5 |
    2020-10-13| PLFP| Fee payment|Year of fee payment: 6 |
    2021-11-08| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1560838|2015-11-12|
    FR1560838A|FR3043572B1|2015-11-12|2015-11-12|THERMALLY INSULATING MATERIALS INCORPORATING SPHERICAL AND HOLLOW INORGANIC PARTICLES|FR1560838A| FR3043572B1|2015-11-12|2015-11-12|THERMALLY INSULATING MATERIALS INCORPORATING SPHERICAL AND HOLLOW INORGANIC PARTICLES|
    EA201891131A| EA037872B1|2015-11-12|2016-11-10|Thermally insulating materials including spherical, hollow inorganic particles|
    PCT/FR2016/052935| WO2017081426A1|2015-11-12|2016-11-10|Thermally insulating materials including spherical, hollow inorganic particles|
    CA3003813A| CA3003813A1|2015-11-12|2016-11-10|Thermally insulating materials including spherical, hollow inorganic particles|
    JP2018524374A| JP6956082B2|2015-11-12|2016-11-10|Insulation material containing spherical and hollow inorganic particles|
    EP16809981.0A| EP3374075A1|2015-11-12|2016-11-10|Thermally insulating materials including spherical, hollow inorganic particles|
    US15/774,537| US10843970B2|2015-11-12|2016-11-10|Thermally insulating materials including spherical, hollow inorganic particles|
    CN201680078663.2A| CN108698009B|2015-11-12|2016-11-10|Thermal insulation material comprising spherical and hollow inorganic particles|
    JP2021121477A| JP2021183871A|2015-11-12|2021-07-26|Heat insulating material containing spherical and hollow inorganic particles|
    [返回顶部]