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  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/10—Treatment with macromolecular organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
  • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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  • C01B32/90—Carbides
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  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/90—Carbides
  • C01B32/914—Carbides of single elements
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/36—Compounds of titanium
  • C09C1/3607—Titanium dioxide
  • C09C1/3653—Treatment with inorganic compounds
  • C09C1/3661—Coating
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  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/36—Compounds of titanium
  • C09C1/3607—Titanium dioxide
  • C09C1/3669—Treatment with low-molecular organic compounds
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  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/36—Compounds of titanium
  • C09C1/3607—Titanium dioxide
  • C09C1/3676—Treatment with macro-molecular organic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/36—Compounds of titanium
  • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/06—Treatment with inorganic compounds
  • C09C3/063—Coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated

Definitions

• the present invention relates to the field of nanomaterials based on transition metal can be included in the composition of nuclear reactor elements. It relates in particular to a process for manufacturing nanoparticles of at least one carbon-coated transition metal oxide.
• Transition metal carbides are particularly suitable materials for manufacturing some of the elements of next-generation nuclear reactors (particularly so-called Generation reactors).
• transition metal oxide particles coated with amorphous carbon of medium size ranging from a few nanometers to a few hundred nanometers (called “oxide nanoparticles” in the following description). This reduction must be as complete as possible so that the nanocrystallites of transition metal carbides are as free as possible from any impurity.
• the carbothermic reduction is most often carried out at a high temperature, which temperature must be higher as the crystallites of the nanoparticles of oxides are of medium size and / or initially contain a large quantity of impurities.
• One of the aims of the invention is therefore to provide a process for manufacturing oxide nanoparticles of the smallest possible average size, such nanoparticles making it possible, after moderate carbothermic reduction, to obtain nanocrystallites of transition metal carbide. of a higher degree of purity and / or a smaller average size than the nanoparticles obtained by the best current processes, in particular of the sol-gel type.
• the subject of the invention is therefore a process for producing nanoparticles of at least one transition metal oxide selected from Ti, Zr, Hf, V, Nb and Ta coated with amorphous carbon, the process comprising the following successive steps: (i) a liquid mixture containing as precursors at least one transition metal alkoxide, an alcohol, excess acetic acid with respect to the transition metal is prepared, and then diluted in water to to form an aqueous solution, the precursors being present in the aqueous solution in a molar ratio such that it prevents or sufficiently limits the formation of a sol so that the aqueous solution is lyophilizable and such as the transition metal, carbon and oxygen are present according to the stoichiometric ratio in which they are found in the nanoparticles,
• the lyophilizate obtained in the preceding step is pyrolyzed under vacuum or under an inert atmosphere in order to obtain the nanoparticles.
• the transition metal oxide nanoparticles are said to be “coated” with amorphous carbon in the sense that their surface is partially or totally covered with amorphous carbon.
• Carbon is said to be “amorphous” because, essentially or mainly, it does not occur in the form of crystallites, although a short-range atomic order can exist locally.
• the freeze-drying comprises spraying the aqueous solution in a liquid nitrogen bath in order to obtain frozen particles having the homogeneous composition of this solution, and then putting these particles under vacuum in order to remove the water therefrom. sublimation, whereby a powder is obtained which leads to the lyophilisate following its secondary desiccation.
• the term "homogeneous composition” means a composition which is the same or essentially the same for any volume of micron size, preferably of nanometric size.
• the spraying can be carried out with a wide variety of sprayers, for example with a nozzle sprayer or an ultrasonic sprayer.
• the lyophilisate contain no element other than the transition metal, carbon, hydrogen or oxygen.
• the alkoxide is advantageously chosen from isopropoxide and n-propoxide. Alkoxides comprising different transition metals may also be mixed to form nanoparticles containing a mixture of the corresponding oxides, for example a mixture of Ti oxides and Zr oxides.
• the alcohol acts as a diluting agent for the alkoxide. It may be chosen from isopropanol (or 2-propanol) and propanol-1, these alcohols having carbon chains derived from the same family as those of the abovementioned preferred alkoxides.
• Acetic acid is a chemical modifier that allows, within the metal alkoxide, the substitution of alkoxy groups with acetate groups.
• it therefore provides a modified alkoxide which, compared to the starting alkoxide, has a lower reactivity with respect to water, which has the effect of preventing or limiting the spontaneous reaction of condensation (sol-gel reaction) of the alkoxide, a reaction that can lead to the formation of precipitates.
• sol-gel reaction a sol can then begin to form by initiating the sol-gel reaction, this sol being within the meaning of the invention as it comprises oligomers and / or colloids suspended in the water.
• acetic acid which also has the function of reducing the viscosity of the solution, is in excess relative to the alkoxide and alcohol.
• acetic acid which also has the function of reducing the viscosity of the solution.
• the precursors of the oxide nanoparticles namely the transition metal alkoxide, acetic acid, alcohol and possibly the carbon compound
• the precursors of the oxide nanoparticles are for example in the form of a clear aqueous solution guarantees the homogeneous distribution of these precursors at the molecular level and consequently favors a homogeneous composition of the oxide nanoparticles.
• oxide obtained according to the process of the invention There is theoretically no lower limit to the concentration of the solution, however, especially for economic reasons, it is generally preferable not to use a concentration too low for the solution, especially to limit costs implementation.
• the term "average size" is used to define the average value of the diameter of the considered objects (oxide nanoparticles, transition metal carbide nanocrystallites, etc.) when they are substantially spherical, or the average value. major dimensions of these objects when they are not substantially spherical.
• the aqueous solution can be sprayed in liquid nitrogen contained in a Dewar vessel and / or the spray is carried out using a sprayer having a spray nozzle having a calibrated orifice, for example a calibrated orifice of 0.51 mm, through which the aqueous solution is injected at a pressure of between 0.03 and 0.4 MPa, preferably at a pressure of 0.3 MPa, generally under the effect of a carrier gas which may be compressed air, or else a neutral industrial gas advantageously filtered, such as argon or nitrogen.
• a carrier gas which may be compressed air, or else a neutral industrial gas advantageously filtered, such as argon or nitrogen.
• a conical insert allows, by centrifugal effect, to press the aqueous solution on the inner wall of the nozzle before this solution is injected through the outlet orifice.
• a liquid jet is generally obtained in the form of an axial hollow cone with a turbulence effect.
• Lyophilization can be carried out in all types of conventional lyophilizer. In this step, the conditions used are not critical, the particles are, however, preferably maintained in the frozen state until the elimination of water, in particular to avoid interparticle agglomeration phenomena.
• the conditions of this step ultimately lead to a substantial elimination of the water, in particular to avoid the creation of a porosity within the oxide nanoparticles during the pyrolysis of the water.
• lyophilisate the freeze-drying is advantageously carried out between -200 ° C. and + 50 ° C., and more preferably between -20 ° C. and + 30 ° C., and at a pressure of between 0.1 Pa and 100 Pa and more preferably less than or equal to 10 Pa.
• it can for lyophilization to take place efficiently and as quickly as possible, it can for example be conducted at a temperature of the order of -2O 0 C and under a pressure of 1 order. 0.1 Pa.
• the freeze-drying step may advantageously comprise an adsorbed water removal step which consists in maintaining the lyophilizate under the pressure of freeze-drying, preferably at 0.1 Pa, and then raising the temperature to a value preferably between 30 ° C. and 100 ° C., more preferably equal to 30 ° C.
• the lyophilizate obtained from the aqueous solution makes it possible to dispose the precursors in a form which has several characteristics: the freeze-dried product has a homogeneous composition throughout its volume due in particular to the fact that freeze-drying is a process which makes it possible to to eliminate the water without causing a concentration gradient in the solution, the lyophilisate is finely divided, which increases its reactivity, for example with respect to a heat treatment, and, on the other hand, has the advantage that it can be handled in the open air and makes it possible to obtain oxide nanoparticles of reduced average size.
• the average size of the transition metal oxide crystallites (equivalent to the average size of the oxide nanoparticles) is generally between 10 and 100 nm, preferably between 10 and 50 nm, more preferably between 10 and 20 nm. .
• the characteristics of the lyophilizate make, after pyrolysis, obtaining oxide nanoparticles with properties such that they can undergo the most complete carbothermic reduction possible to obtain nanocrystallites of transition metal carbide of medium size. reduced and high degree of purity, without this requiring the use of high temperatures.
• the pyrolysis step of the lyophilizate be conducted i) under vacuum or under an inert atmosphere in order to avoid the formation of by-products such as oxycarbides and ii) at a temperature such that it allows crystallization oxide nanoparticles without leading by carbothermic reduction to unwanted carbide nanocrystallites at this stage of the manufacture of oxide nanoparticles.
• This temperature is most often between 400 ° C. and 900 ° C., preferably between 400 ° C. and 600 ° C., more preferably still between 400 ° C. and 450 ° C.
• the invention also relates to the application of the manufacturing process.
• This carbothermic reduction can be in continuity with the process for manufacturing oxide nanoparticles in that the lyophilisate undergoes a single heat treatment which comprises both the pyrolysis (in order to form the oxide nanoparticles) followed directly by the reduction. carbothermal. It may also be successive in that the lyophilisate undergoes a first thermal treatment in an inert atmosphere which constitutes pyrolysis, then the oxide nanoparticles thus obtained subsequently undergo a second heat treatment which constitutes the carbothermic reduction.
• the carbon, oxygen and transition metal element necessary for the formation of the oxide nanoparticles can be provided solely by the alkoxide, acetic acid and alcohol. These contributions can be determined beforehand by calculation from the precursor chemical formula and / or after ThermoGravimetric Analysis (ATG) precursors or oxide nanoparticles with respect to the carbon and oxygen inputs.
• the carbon and / or oxygen element may be provided in a complementary manner with a precursor consisting of at least one carbon compound added to the aqueous solution.
• This compound is within the aqueous solution that is chemically inert with respect to the alkoxide, and in particular it does not comprise an OH group (s) that can cause the hydrolysis of the alkoxide: it can therefore be chosen from a derivative cellulose meeting these criteria.
• cellulose preferably methyl cellulose.
• the process according to the invention is therefore flexible in that it makes it possible to obtain oxide nanoparticles having a large variety in the molar ratio of amorphous carbon to transition metal oxide, and thus to oxide nanoparticles in which the oxide of the metal transition has a wide variety of amorphous carbon coating rates.
• This ratio is preferably between 1 and 4, even more preferably between 2 and 3.
• the excess of acetic acid in the aqueous solution of the invention is such that the molar ratio between the amount of the amount of alcohol and the amount of alkoxide is between 20: 6: 1 and 3: 1: 1, even more preferably 16: 4: 1.
• such molar ratio also makes it possible to limit the increase in viscosity after the possible addition of the carbon compound according to the invention.
• the solution obtained was clear, thus marking the absence of the significant formation of a soil and a homogeneous composition. It was diluted in water to obtain 600 ml of concentrated aqueous solution.
• the dry powder or freeze-dried product obtained in the preceding step was placed in a graphite nacelle and pyrolysed in a tubular furnace made of alumina (Adamel) under an argon flow U (Arcal, flow of 1.2 liters / minutes) by a increasing in temperature at a rate of 5 ° C./minutes until a temperature of 45 ° C. was reached which was maintained for 0.1 hour and then decreased at a rate of 5 ° C./minutes to room temperature. At the end of this pyrolysis, a black powder is obtained.
• X-Ray Diffraction XRD
• SEM Scanning Electron Microscopy
• the lyophilizate obtained at the end of the freeze-drying step placed in a graphite boat was heat-treated in the above-mentioned alumina (Adamel) tubular furnace under argon flow with an increase in temperature at a rate of 5 °. C / minutes until reaching a temperature of 1300 0 C which was maintained for 2 hours, and then decreased at a rate of 5 ° C / minute to room temperature.
• the carbothermic reduction is in this case in the continuity of the pyrolysis which led to the formation of oxide nanoparticles: the lyophilisate has therefore undergone a single heat treatment.
• a measurement by ATG made it possible to determine the stoichiometric composition of the TiC and showed a residual oxygen content of less than 1% by mass as well as the presence of an excess of carbon (revealed by a mass gain of 30.4% instead of a theoretical value of 33.40%).
• the knowledge of the value of this excess of carbon which constitutes an impurity can make it possible to readjust, possibly by successive tests, the quantity of carbon provided by the methylcellulose in order to reduce or render null the carbon content of the transition metal carbide.
• TiO 2 titanium dioxide
• Titanium dioxide nanoparticles (TiO 2) coated in which the molar ratio of carbon / Ti0 2 is from 0.05 were manufactured according to a procedure similar to that of Example 1, except that intakes carbon element have been adapted.
• such nanoparticles are used as constituent materials for the electrodes of lithium batteries. They then generally have a coating rate such that the carbon / TiO 2 molar ratio is between 0.01 and 0.06, preferably between 0.02 and 0.05.
• ZrO 2 zirconium dioxide
• HfO 2 hafnium dioxide
• Zirconium dioxide (ZrO 2 ) nanoparticles and hafnium dioxide nanoparticles (HfO 2 ) both coated with amorphous carbon was conducted under conditions similar to those of the previous examples.
• They generally include increasing the temperature at a rate between 5 ° C / minute and 10 ° C / min, preferably 5 ° C / minute in order to reach a temperature between 1000 and 1600 0 C 0 C preferably at 1300 ° C. or 1400 ° C., which temperature is maintained for a period of between 2 and 6 hours, preferably 2 hours for TiC, 3 hours for ZrC and 5 hours for HfC.
• the carbothermic reduction is carried out with a carrier gas comprising argon and more advantageously U or Arcal argon.
• the process of the invention makes it possible to manufacture oxide nanoparticles of a reduced average size which make it possible to obtain nanocrystallites of transition metal carbide after moderate carbothermal reduction. a higher degree of purity and / or a smaller average size than the nanoparticles currently obtained by the sol-gel type processes. It is also simple to implement and in particular makes it easy to obtain oxide nanoparticles in which the transition metal oxide has a wide variety of amorphous carbon coating rates.

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