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  • C04B35/6267—Pyrolysis, carbonisation or auto-combustion reactions
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
  • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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  • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
  • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm

Definitions

• the present invention relates to a process for producing a powder comprising carbon, silicon and boron, the silicon being in the form of silicon carbide and the boron being in the form of boron carbide and / or boron alone.
• Such powders especially because they comprise boron, such as powders comprising less than 5% by weight of boron, are powders which lend themselves easily to sintering and thus to the design of consolidated parts from said powders. .
• the powders obtained by the process of the invention can find their application in the design of parts obtained by sintering.
• the powders obtained by the process of the invention can also be used for the design of self-healing matrices, especially when they comprise boron at a content greater than 5% by weight of boron.
• the self-healing phase of said matrices must have a contact surface with the highest possible oxygen. Due to the surface / volume ratio, the reactivity towards oxygen is increased and boron carbide oxidizes as B2O3 at lower temperatures and kinetically faster.
• the technique of mechanosynthesis consists of a mechanical grinding, in a device of the grinder or attritor type, of submicron-sized silicon carbide (SiC) and boron carbide (B 4 C) powders for a sufficient time.
• powders comprising carbon, silicon and boron have been synthesized by sol-gel using silicon-based precursors, carbon-based precursors and boron-based precursors.
• sol-gel using silicon-based precursors, carbon-based precursors and boron-based precursors.
• the powders comprising carbon, silicon and boron can be prepared from gaseous precursors using different heat sources such as a laser (in which case we will speak of laser pyrolysis) or a plasma.
• Vassen et al. (Journal of Materials Science 31 (1996) 3623-3637) have synthesized, by laser pyrolysis, powders comprising both carbon, silicon and boron, from a mixture of precursors: SiH 4 -C 2 H 4 -B 2 H6 with a boron content not exceeding 4% by mass.
• This method of synthesis has, among others, the disadvantage of using diborane B 2 H 6 , which is an unstable gas with a high cost, and therefore difficult to use for the production of powders having higher levels of boron than the above-mentioned content.
• Guo et al. (Journal of Materials Science,
• the powders obtained by this process have a submicron size.
• a boron content which may be high (for example up to 30% by weight relative to the total mass of the other elements present in the powder);
• the invention relates to a process for producing a powder comprising carbon, silicon and boron, the silicon being in the form of silicon carbide and the boron being in the form of boron carbide and or boron alone comprising the following steps:
• a step of subjecting the resulting mixture to laser pyrolysis the boron precursor BX 3 being heated, prior to the contacting step and / or simultaneously with the contacting step, at a temperature above its condensation temperature.
• the invention comprises a step of heating the boron precursor BX 3 , X being a halogen atom, at a temperature above its condensation temperature before the contacting step. and / or during said contacting step, for example, at a temperature ranging from 40 to 60 ° C.
• a condensation of the precursor is prevented, before being subjected to pyrolysis, and thus to have a quantity of precursor that can not be incorporated in the powder due to this condensation. Thanks to this step, all the boron resulting from the precursor used in the context of this process will enter into the constitution of the powders.
• This heating step in that it excludes the condensation of the boron precursor, also prevents the apparatus, in which the process is implemented, from being damaged, for example by clogging of the injection nozzles by the product resulting from the condensation of the boron precursor.
• the heating step can take place before the contacting step, for example, before contacting the boron precursor with the other precursors (ie, the silicon-based precursor and the precursor-based of carbon), this heating step can be carried out in an enclosure comprising the boron precursor (this chamber may be a bottle having, for example, an outlet pressure of at least 0.4 bar) and / or in the injection pipe of said precursor for conveying said precursor into the chamber where it will be brought into contact with the other precursors.
• this chamber may be a bottle having, for example, an outlet pressure of at least 0.4 bar
• the heating step may make it possible, in addition to avoiding the condensation of BX 3 , to increase the flow rate of BX 3 , and in particular to have access to a flow rate sufficient to obtain large quantities of powder (for example, a rate of at least 100 g / h).
• the heating step can also take place during the contacting step in which case the heating step will concern all the precursors contacted during this step. It is not excluded within the meaning of the invention that the heating step can take place at a time before the contacting step and during the contacting step, so that there is no condensation of the boron precursor before the pyrolysis step.
• the boron precursor may be BCI3 boron trichloride.
• the boron precursor is boron trichloride BCI3
• the latter may be heated prior to the contacting step and / or simultaneously with the contacting step at a temperature ranging from 40 ° C. to 50 ° C. 0 C.
• the method of the invention comprises a step of contacting, prior to laser pyrolysis, a boron precursor BX 3 , X being a halogen atom, a precursor based on carbon and a precursor based on silicon.
• the boron precursor is boron trichloride.
• the carbon-based precursor may be a compound selected from alkanes, such as methane, alkenes, such as ethylene and alkynes, such as acetylene.
• the carbon-based precursor may be a gaseous alkyne, such as acetylene C2H2, which has the particularity of being very reactive during the pyrolysis step, because it decomposes more rapidly than the methane CH 4 and ethylene C2H4 and at lower temperature.
• acetylene C2H2 gaseous alkyne
• the silicon-based precursor is preferably a silane compound, such as SiH 4 .
• the boron-based precursor is BCI3
• the carbon-based precursor is C2H2 acetylene
• the silicon-based precursor is SiH 4 , this precursor mixture being advantageous from a cost point of view and having also thermokinetic properties particularly suited to the process of the invention, in particular to obtain homogeneous powders in terms of size and composition.
• the carbon-based precursor, the silicon precursor and the boron precursor are conventionally contacted in a mixing chamber, which can be heated to a temperature above the condensation temperature of the precursor based on silicon. boron.
• the introduction of the carbon-based precursor, the silicon-based precursor and the boron-based precursor is advantageously carried out separately in the enclosure, so that there is no contact precursors before contacting in the enclosure. This also makes it possible to avoid chemical reactions between the precursors before they are introduced into the mixing chamber.
• the mixing chamber can be provided with three separate injection ports.
• the injection of the precursors into the chamber takes place vertically, which means, in other words, that the precursors are injected into a vertical enclosure in the upper part thereof and are concentrated by the effect of gravity in the lower part of the enclosure after introduction.
• the precursors are introduced at predetermined flow rates according to the desired powder characteristics (in terms in particular of boron content, carbon content and silicon content).
• the resulting mixture is then subjected to a laser pyrolysis step.
• Laser pyrolysis is based on the interaction between gaseous precursors (in this case, the carbon-based precursor, the boron precursor, and the silicon-based precursor) and a laser , generally a CO2 laser, which interaction results in a resonance between the emission spectrum of the laser and the absorption spectrum of the precursors.
• Absorption is the excitation of the vibrational levels of the precursor molecules, which absorb the energy of the laser radiation.
• the energy of the excited precursor molecules propagates from molecules to molecules, causing the dissociation thereof to form a supersaturated vapor, in which the nucleation and growth of the constituent particles of the powder occur.
• a so-called "incandescent" flame can then be observed.
• the particles formed undergo a quenching effect at the flame outlet, which has the effect of stopping the growth of the particles.
• the mixture obtained during the aforementioned mixing step is conventionally injected via an injection nozzle into a laser pyrolysis chamber, where a laser beam is emitted.
• the pressure in the pyrolysis chamber can range from 100 mbar to 900 mbar.
• the laser used may be a gas laser, in particular a carbon dioxide laser capable of emitting in the infrared (their main wavelength band being centered between 9.4 and 10.6 ⁇ m).
• the power of such a laser can be up to 20000 W, for example ranging from 200 to 700 W.
• Each fraction of the mixture i.e., the mixing fraction passing through the laser beam
• a short residence time for example from 1 to 10 ms and at a temperature ranging from 1000 ° C. to more than 2500 ° C. .
• nanoscale powders comprising carbon, silicon and boron, the silicon being in the form of silicon carbide, the boron being in the form of boron carbide and / or free boron, the carbon in addition to its presence in the form of carbide (s) may also be in the form of free carbon.
• the powders obtained have a narrow size distribution and may have a boron content ranging from 1 to 30% by weight relative to the total mass of the other elements present in the powder.
• the powder obtained advantageously consists of nanometric grains, themselves advantageously constituted by B 4 C boron carbide and silicon carbide SiC phases.
• the powders obtained by this process can then be collected in a collection device.
• These powders can be used to produce parts by sintering having advantageous mechanical characteristics due to the fact that nanometric nature of the powders or to make self-healing matrices.
• the method of the invention can be implemented in a device comprising respectively: an injection chamber, in which the precursors are injected, which chamber can consist of a heated mixing chamber, a rod of injection connected to the upper part of the chamber, two injection rods connected to the lateral part of the chamber, which allow the separate injection of the various precursors, an injection nozzle for injection into a pyrolysis chamber;
• a pyrolysis chamber in which a laser beam is emitted which will interact with the precursor mixture to form the aforementioned powder.
• FIG. 1 relates to a schematic representation of a reactor capable of enabling the implementation of the method of the invention.
• FIG. 2 is an X-ray diffractogram (the abscissa representing the angle 2 ⁇ and the ordinate the intensity I (in arbitrary units ua)) of the powder obtained according to the example given below.
• the present example illustrates the preparation of a powder comprising both a silicon carbide phase and a boron carbide phase by laser pyrolysis implemented in a reactor 1 shown in FIG. 1 comprising the following elements:
• an injection chamber into which the precursors are injected and then mixed before being subjected to laser pyrolysis, which chamber consists of a heated mixing chamber 5, an injection rod 7 connected to the part upper chamber, two injection rods 9, 11 connected to the side portion of the chamber, an injection nozzle 13 for injecting the mixture in a pyrolysis chamber; a containment chimney 15 disposed around the injection nozzle;
• a pyrolysis chamber 17 in which a laser beam 19 is emitted from a laser emission device 21 which will interact with the precursor mixture to form the aforementioned powder.
• the confinement chimney makes it possible on the one hand to keep the powders produced in a laminar flow and, on the other hand, it prevents any contact with the metal walls of the reaction chamber and thus to avoid any pollution.
• the operating protocol is as follows.
• a silicon-based precursor SiH 4
• a precursor based on carbon acetylene C2H2;
• boron precursor BCI3 at the following flow rates: 3.6, 1.8 and 0.14 L / min, the flow rates being controlled by mass flow controllers, which precursors are mixed in said heated enclosure at a temperature of 45 ° C.
• BCI3 boron trichloride is injected into the chamber by the injection rod 7, while the acetylene and SiH 4 are injected into the chamber by the injection rods 9 and 11.
• BCI3 boron precursor is preheated before being injected into the reactor at 45 ° C both before and during its passage in the injection rod.
• BCI3 boron precursor is derived from a bottle containing it, this bottle having an outlet pressure of at least 0.4 bar, this bottle being heated to 45 ° C and stirred to accelerate the diffusion of heat inside and thus BCI3 boron precursor transfer.
• the mixture of precursors obtained in the mixing chamber is then injected through the injection nozzle into the pyrolysis chamber at a flow rate of 7.2 L.min -1 where it is subjected to an infrared laser beam (IR), more precisely a CO2 laser used at a working power of 5000 W for a residence time of 2.8 ms.
• IR infrared laser beam
• the rate of production of powder at the outlet of the pyrolysis chamber is of the order of 391 g / h.
• the powder obtained was analyzed by the following techniques: X-ray diffraction, the diffractogram of which is represented in FIG. 2;
• a crystalline boron carbide phase and an amorphous boron carbide phase the presence of which is indicated by two distinct arrows, the amorphous boron carbide phase being a minority.
• the powder obtained was also the subject of elementary chemical analysis, so as to determine the percentage by mass of each of the chemical elements present in it.
• Silicon 36% by weight; Carbon: 28% by weight; Oxygen: 8% by mass measurement errors can be of the order of 2 to 3% by mass depending on the elements.
• the average size of the constituent grains of the powder ie the average diameter of the latter has also been measured by two methods:

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