Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
  • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
  • B29B15/10—Coating or impregnating independently of the moulding or shaping step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
  • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
  • B29B15/10—Coating or impregnating independently of the moulding or shaping step
  • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/16—Fillers
  • B29K2105/162—Nanoparticles
• • 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
• • 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
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
  • Y10T428/292—In coating or impregnation
• • 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
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

• the present invention relates to a process for impregnating continuous fibers, comprising coating said fibers with a polymeric matrix comprising at least one semi-crystalline thermoplastic polymer having a glass transition temperature (Tg) less than or equal to 130 ° C. and nanotubes of at least one chemical element selected from the elements of columns IHa, IVa and Va of the periodic table. It also relates to the composite fibers obtainable by this process, as well as their uses.
• Tg glass transition temperature
• composite fibers have been used to manufacture, in particular, various aeronautical or automobile parts.
• These composite fibers which are characterized by good thermomechanical and chemical resistances, consist of a reinforcement filament reinforcement intended to ensure the mechanical strength of the material, and of a matrix which bonds and encapsulates the reinforcing fibers, intended to distribute the forces ( tensile, flexural or compressive strength), in some cases to give chemical protection to the material and to give it its shape.
• Methods of making composite parts from these coated fibers include various techniques such as / for example, contact molding, projection molding, autoclave draping or low pressure molding.
• a technique for making hollow parts is that called filament winding, which consists in impregnating dry fibers with a resin and then winding them on a mandrel formed of reinforcements and of a shape adapted to the part to be manufactured. The piece obtained by winding is then cured by heating.
• Another technique for making plates or shells consists in impregnating fiber fabrics and then pressing them into a mold in order to consolidate the laminated composite obtained.
• thermosetting resin such as an epoxy resin, for example diglycidyl ether of bisphenol A, combined with a hardening agent
• a particular rheology regulating agent miscible with said resin , such that the composition has a Newtonian behavior at high temperature (40 to 150 ° C.).
• the rheology regulating agent is preferably a block polymer comprising at least a block compatible with the resin, such as a horaopolymer of methyl methacrylate or a copolymer of methyl methacrylate with in particular dimethylacrylamide, a block incompatible with the resin, consisting for example of 1,4-butadiene or acrylate monomers; butyl, and optionally a polystyrene block.
• the rheology regulating agent may comprise two mutually incompatible blocks and with resxne, such as a polystyrene block and a polybutadiene-1, 4 block.
• thermosetting resin-based composites which are not easily thermoformable in contrast to thermoplastic polymers, the composites obtained also having limited impact strength and storage time.
• thermoplastic coating composition consists in coating the fibers with a polyetheretherketone (PEEK), poly (pylene sulfide) (PPS) or polyphenylsulfone (PPSU), for example.
• PEEK polyetheretherketone
• PPS poly (pylene sulfide)
• PPSU polyphenylsulfone
• thermoplastic polymeric matrix which is more economical to implement than the known processes, while at the same time making it possible to obtain composite fibers having mechanical properties that are particularly suitable for applications. aeronautics and automobiles.
• the present invention more precisely relates to a process for impregnating continuous fibers, comprising coating said fibers with a polymeric matrix comprising at least one semicrystalline thermoplastic polymer having a glass transition temperature (Tg) less than or equal to 130 0 C and nanotubes of at least one chemical element selected from the elements of columns IHa, IVa and Va of the periodic table.
• Tg glass transition temperature
• materials constituting said fibers include, without limitation:
• stretched polymer fibers based in particular on: polyamide such as polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 6.6 (PA-6.6) , polyamide 4.6 (PA-4.6), polyamide 6.10 (PA-6.10) or polyamide 6.12 (PA-6.12), polyamide / polyether block copolymer (Pebax '3 ), high-density polyethylene, polypropylene or polyester such as polyhydroxyalkanoates and polyesters marketed by Du Pont under the trade name Hytrel 0 ;
• glass fibers in particular of the E, R or S2 type
• the coating composition used according to the present invention comprises at least one semi-crystalline thermoplastic polymer having a glass transition temperature (Tg) less than or equal to 130 ° C.
• Such a polymer may especially be chosen, without limitation, from: polyamides such as polyamide 6 (PA-6), polyamide II (PA-II), polyamide 12 (PA-12), polyamide 6.6 (PA-6.6), polyamide 4.6 (PA-4.6), polyamide 6.10 (PA-6.10) and polyamide 6.12 (PA-6.12), some of these polymers being sold in particular by Arkema under the name Rilsan 0 and preferred being those of fluid grade such as Rilsan AMNO TLD and as copolymers, including block copolymers containing amide monomers and other monomers such as polytetramethylene Glycol (PTMG) (Pebax "); aromatic polyamides such as polyphthalamide;
• polyamides such as polyamide 6 (PA-6), polyamide II (PA-II), polyamide 12 (PA-12), polyamide 6.6 (PA-6.6), polyamide 4.6 (PA-4.6), polyamide 6.10 (PA-6.10) and polyamide 6.12 (PA-6.12
• polymers being sold in particular by Arkem
• fluoropolymers comprising at least 50 mol% and preferably consisting of monomers of formula (I):
• thermoplastic polyurethanes TPU
• the glass transition temperatures of some polymers that can be used according to the invention are given in Table 1 below.
• thermoplastic polymer can be made of the same material as that constituting the continuous fibers, in which case we obtain a composite called “self-reinforced” (or SRP for "self-reinforced polymer”).
• the polymer matrix used according to the invention contains, in addition to the thermoplastic polymer as mentioned above, na ⁇ otubes of at least one chemical element chosen from the elements of columns IHa, IVa and Va of the periodic table.
• These nanotubes may be based on carbon, boron, phosphorus and / or nitrogen (borides, nitrides, carbides, phosphides) and for example consisting of carbon nitride, boron nitride, boron carbide, boron phosphide, phosphorus nitride or carbon boronitride.
• Carbon nanotubes hereinafter, CNTs are preferred for use in the present invention.
• the nanotubes that can be used according to the invention can be single-walled, double-walled or multi-walled.
• the double-walled nanotubes can in particular be prepared as described by FLAHAUT et al in Chem. Corn. (2003), 1442.
• the multi-walled nanotubes may themselves be prepared as described in WO 03/02456.
• the nanotubes usually have a mean diameter ranging from 0.1 to 200 nm, preferably from 0.1 to 100 nm, more preferably from 0.4 to 50 nm and better still from 1 to 30 nm and advantageously a length of from 0 to 100 nm. , 1 to 10 ⁇ m.
• Their length / diameter ratio is preferably greater than 10 and most often greater than 100.
• Their specific surface area is for example between 100 and 300 m 2 / g and their apparent density may especially be between 0.05 and 0.5. g / cm 3 and more preferably between 0.1 and 0.2 g / cm J.
• the multiwall nanotubes may for example comprise from 5 to 15 sheets and more preferably from 7 to 10 sheets.
• crude carbon nanotubes is in particular commercially available from ARKEMA under the trademark Graphistrength C100.
• nanotubes can be purified and / or treated (for example oxidized) and / or ground and / or functionalized, before being used in the process according to the invention.
• the grinding of the nanotubes may in particular be carried out cold or hot and be carried out according to known techniques used in devices such as ball mills, hammers, grinders, knives, gas jet or any other system. Grinding capable of reducing the size of the entangled network of nanotubes. It is preferred that this grinding step is performed according to a gas jet grinding technique and in particular in an air jet mill.
• the purification of the crude or milled nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metallic impurities originating from their preparation process.
• the weight ratio of the nanotubes to the sulfuric acid may in particular be between 1: 2 and 1: 3.
• the purification operation may also be carried out at a temperature ranging from 90 to 120 ° C., for example for a period of 5 to 10 hours. This operation may advantageously be followed by rinsing steps with water and drying the purified nanotubes.
• the oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite containing from 0.5 to 15% by weight of NaOCl and preferably from 1 to 10% by weight of NaOCl, for example in a weight ratio of nanotubes to sodium hypochlorite ranging from 1: 0.1 to 1: 1.
• the oxidation is advantageously carried out at a temperature below 60 ° C. and preferably at ambient temperature, for a duration ranging from a few minutes to 24 hours. This oxidation operation may advantageously be followed by filtration and / or centrifugation, washing and drying steps of the oxidized nanotubes.
• the functionalization of the nanotubes can be carried out by grafting reactive units such as vinyl monomers on the surface of the nanotubes.
• the material constituting the nanotubes is used as a radical polymerization initiator after having been subjected to a heat treatment at more than 900 ° C., in an anhydrous and oxygen-free medium, which is intended to eliminate the oxygenated groups from its surface. It is thus possible to polymerize methyl methacrylate or hydroxyethyl methacrylate on the surface of carbon nanotubes in order, in particular, to facilitate their dispersion in PVDF or polyamides.
• Crude nanotubes that is to say nanotubes that are not oxidized, purified or functionalized and have undergone no other chemical treatment, are preferably used in the present invention.
• the nanotubes may represent from 0.5 to 30% and preferably from 0.5 to 10%, and even more preferably from 1 to 5% by weight of the thermoplastic polymer.
• the nanotubes and the thermoplastic polymer are mixed by compounding using conventional devices such as twin-screw extruders or co-kneaders.
• polymer pellets are typically melt blended with the nanotubes.
• the nanotubes may be dispersed by any suitable medium in the thermoplastic polymer in solution in a solvent.
• the dispersion can be improved, according to an advantageous embodiment of the present invention, by the use of particular dispersing systems or dispersing agents.
• the process according to the invention may comprise a preliminary step of dispersing the nanotubes in the thermoplastic polymer by means of ultrasound or a rotor-stator system.
• Such a rotor-stator system is in particular marketed by SILVERSON under the trade name Silverson * L4RT.
• Another type of rotor-stator system is marketed by the company
• IKA-WERKE under the trade name Ultra-Turrax.
• rotor-stator systems still consist of colloid mills, deflocculating turbines and high-shear mixers of the rotor-stator type, such as the devices manufactured by the company IKA-WERKE or the company ADMIX.
• the dispersing agents may in particular be chosen from plasticizers which may themselves be chosen from the group consisting of: alkyl esters of phosphates, of hydroxybenzoic acid (the alkyl group of which, preferably linear, contains from 1 to 20 carbon atoms) , xauric acid, azelaic acid or pelargonic acid, phthalates, especially dialkyl or alkylaryl, in particular alkylbenzyl, alkyl groups, linear or branched, independently containing from 1 to 12 atoms carbon, adipates, in particular dialkyls, sebacates, in particular dialkyl and in particular dioctyl, in particular in the case where the polyme ⁇ que matrix contains a fluoropolymer, benzoates of glycols or glycerol, dibenzyl ethers, chloroparaffins , propylene carbonate, sulfonamides, in particular in the case where the polyme ⁇ que matrix contains a polyamide, including aryl s
• the dispersant may be a Agert o ⁇ polviere ccriprericmt the mo ⁇ ns a monomer nydrophile anionic and at least one monomer including at least one aromatic ring, such as the copolymers described in document FR-2 766 106, the ratio by weight of the dispersing agent to nanotubes preferably ranging from 0.6: 1 to 1, 9: 1.
• the dispersing agent may be a vinylpyrrolidone homo- or copolymer, the ratio by weight of the nanotubes to the dispersing agent preferably ranging from 0.1 to less than 2.
• the dispersion of the nanotubes in the polymer matrix can be improved by putting them in contact with at least one compound A which can be chosen from among various polymers, monomers, plasticizers, emulsifiers, coupling agents and / or carboxylic acids, the two components (nanotubes and compound A) being mixed in the solid state or the mixture being in pulverulent form, optionally after removal of one or more pure solvents.
• at least one compound A which can be chosen from among various polymers, monomers, plasticizers, emulsifiers, coupling agents and / or carboxylic acids, the two components (nanotubes and compound A) being mixed in the solid state or the mixture being in pulverulent form, optionally after removal of one or more pure solvents.
• the polymer matrix used according to the invention may also contain at least one adjuvant chosen from plasticizers, anti-oxygen stabilizers, light stabilizers, dyes, anti-shock agents, antistatic agents, flame retardants, lubricants, and mixtures thereof.
• the volume ratio of the continuous fibers to the polymeric matrix is greater than or equal to 50% and preferably greater than or equal to 60%.
• the coating of the fibers by the polymer matrix can be done according to different techniques, depending in particular on the physical form of the matrix (pulverulent or more or less liquid) and fibers.
• the fibers may be used as such, in unidirectional son form, or after a weaving step, in the form of fabric consisting of a bidirectional network of ⁇ ibres.
• the coating of the fibers is preferably carried out according to a fluidized bed impregnation process, in which the polymer matrix is in powder form.
• the coating of the fibers can be done by passing through an impregnating bath containing the polymeric matrix in the molten state.
• the polymer matrix then solidifies around the fibers to form a semi-finished product consisting of a pre-impregnated fiber ribbon that can then be wound or a pre-impregnated fiber fabric.
• the manufacture of the finished part comprises a step of consolidating the polymeric matrix, which is for example melted locally: for create zones for fixing the fibers together and secure the fiber ribbons in the filament winding process.
• a film from the polymer matrix in particular by means of an extrusion or calendering process, said film having for example a thickness of about 100 ⁇ m, and then to place it between two mats of fibers, the whole being then hot pressed to allow the impregnation of the fibers and the manufacture of the composite.
• the composite fibers obtained as described above have an interest in various applications, due to their high modulus (typically greater than 50 GPa) and high resistance, resulting in a stress at break greater traction than 200 MPa at 23 0 vs.
• the present invention more specifically relates to the use of the aforementioned composite fibers for the manufacture of nose, wings or rocket or aircraft cabins; off-shore flexible armor; automotive bodywork components, engine chassis or automobile support parts; or structural elements in the field of building or bridges and roadways.
• Example 1 Process for producing laminated composite plates using carbon fibers coated with PA-11 / CNT.
• Composite carbon nanotubes are manufactured by first adding 21 g of carbon nanotubes (Graphistrengtlv * ClOO) to 800 g of methylene chloride and then sonicating with a Sonics unit. & Materials VC-505 set at 50% amplitude for about 4 hours, with continuous stirring using a magnetic bar. 64 g of cyclic butylene terephthalate (CBT) are then introduced. The mixture is rolled for about 3 days, then cast on aluminum foil and the solvent is evaporated. The resulting powder contains about 25% by weight of CNTs.
• CBT cyclic butylene terephthalate
• Example 2 Process for producing laminated composite plates using carbon fibers coated with PA-12 / CNT.
• Composite carbon nanotubes are manufactured by first adding 21 g of carbon nanotubes (Graphistrength 'ClOO) to 800 g of methylene chloride and then sonicating with a Sonics unit. & Materials VC-505 set at 50% amplitude for about 4 hours, with continuous stirring using a magnetic bar. 64 g of cyclic butylene terephthalate (CBT) are then introduced. The mixture is rolled for about 3 days, then cast on aluminum foil and the solvent is evaporated. The resulting powder contains about 25% by weight of CNTs.
• CBT cyclic butylene terephthalate
• composite nanotubes are then added to polyamide-11 (Rilban 0 BMNO PCG), in a ratio of 5:15:80 NTCrCBT: PA12, by melt blending on a mid-DSM extruder, the parameters of extrusion being as follows: temperature: 210 ° C; speed: 75 rpm; duration: 10 minutes.
• a composite matrix is then obtained which is used to coat continuous carbon fiber fabrics in a fluidized bed before transferring the pre-impregnated fiber fabrics, via a guidance system, to a press suitable for the manufacture of a laminated composite plate.
• Their hot pressing temperature of about 180-190 ° C.
• pre-impregnated fabrics allows consolidation of the composite.
• Example 3 Production method of laminated composite sheets using carbon fibers coated Pebax ® / NTC.
• Composite carbon nanotubes are produced by first adding 21 ⁇ of carbon nanotubes (Graphistrength 0 ClOO) at 800 g methylene chloride, and then sonicated using a Sonics & Materials VC-505 unit set at 50% amplitude for about 4 hours, with continuous stirring. using a magnetic bar. 64 g of cyclic butylene terepntalate (CBT) are then introduced. The mixture is rolled for about 3 days, then cast on aluminum foil and the solvent is evaporated. The resulting powder contains about 25% by weight of CNTs.
• CBT cyclic butylene terepntalate
• composite nanotubes are then added to polyamide-11 (Rilsan 0 BMNO PCG), in a proportion of CNT: CBT: Pebax G of 5:15:80, by melt blending on a midi-DSM extruder, the extrusion parameters being as follows: temperature: 210 0 C; speed: 75 rpm; duration: 10 minutes.
• a composite matrix is then obtained which is used to coat continuous carbon fiber fabrics in a fluidized bed before transferring the pre-impregnated fiber fabrics, via a guidance system, to a press suitable for the manufacture of a laminated composite plate. Pressing them to eha ⁇ d (temperature of about 180-190 0 C) pre-impregnated fabrics allows consolidation of the composite.

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