WO2014108511A2 - Procédé de préparation d'un matériau allongé muni de nanostructures de carbone greffées, appareil et produit associés - Google Patents
Procédé de préparation d'un matériau allongé muni de nanostructures de carbone greffées, appareil et produit associés Download PDFInfo
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- WO2014108511A2 WO2014108511A2 PCT/EP2014/050406 EP2014050406W WO2014108511A2 WO 2014108511 A2 WO2014108511 A2 WO 2014108511A2 EP 2014050406 W EP2014050406 W EP 2014050406W WO 2014108511 A2 WO2014108511 A2 WO 2014108511A2
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- elongated
- elongated material
- carbon nanostructures
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/08—Flame spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/08—Flame spraying
- B05D1/10—Applying particulate materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
- D06M2400/01—Creating covalent bondings between the treating agent and the fibre
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- 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
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric
Definitions
- the present invention relates to a process for preparing an elongated material provided with grafted carbon nanostructures.
- Such a method is intended in particular to manufacture products comprising an elongated material in fibrous or solid form, on which are grafted carbon nanostructures, such as carbon nanotubes or carbon nanofibers.
- the products obtained by a process according to the invention are functionalized by the presence of grafted carbon nanostructures to modify and improve the properties of the elongated starting material.
- the products thus produced have properties different from those of the base elongated material, including mechanical, electrical or chemical properties which are improved.
- the elongate base material is preferably a fiber, an assembly of fibers such as a yarn, or a network of fibers, woven, braided, knitted, or non-woven. It is preferably rollable and unrollable from a storage assembly, this assembly may be a drum or a coil.
- a "fiber” is a filamentous substance that can be spun and / or woven.
- the fiber may be of animal, vegetable, artificial, mineral or synthetic origin.
- a "thread” is generally a long and thin strand of material, especially fibers, where a meeting of the strands of these materials twisted and spun.
- the yarns can be uniformly joined by interlacing to form a braid, or knit fabric.
- a nonwoven is generally a sheet or a veil of natural fibers and / or fibers or filaments manufactured, excluding paper, which have not been woven and which can be bonded together in different ways, for example by assembly mechanical (needling) or chemical.
- the elongate material is a non-fibrous solid such as a film.
- CVD chemical vapor deposition chamber
- the elongated fibrous material is first desensitized and then a metal catalyst is deposited on its surface.
- the material thus treated is then introduced into a chemical vapor deposition chamber.
- This enclosure is for example a quartz tubular furnace swept by a hydrocarbon gas.
- carbon nanotubes then grow on the surface of the fibrous material, after a time greater than several tens of minutes, for example between 15 minutes and 60 minutes.
- EP 2,290,139 discloses a grafting process in which successive lengths of an elongate material are introduced sequentially into a plasma furnace, after treatment of the surface of the elongate material, to generate, in the plasma, a grafting of carbon nanotubes.
- Such a method improves the grafting productivity, but remains complicated to implement. Indeed, on the one hand, the presence of the plasma furnace requires controlling the interface by which the elongated material is introduced into the furnace and complicates the maintenance of a controlled atmosphere in the furnace, and on the other hand, the fiber must be maintained at a temperature between 500 ° C and 1000 ° C before passing into the plasma, which complicates the control of the process.
- An object of the invention is to obtain a method for preparing an elongated material provided with grafted carbon nanostructures, which is very simple and economical to implement, while producing a high quality product.
- the object of the invention is a process of the aforementioned type, characterized in that it comprises the following steps:
- a grafting device comprising a torch producing a flame in a volume of ambient air, and a cooling medium disposed opposite the flame;
- the method according to the invention may comprise one or more of the following characteristics, taken separately or in any technically possible combination:
- the continuous movement of the elongated material comprises the destocking of the elongated raw material out of an upstream destocking assembly, the passage of the elongated material crude destocked through the flame, then storing the elongated material provided with carbon nanostructures on a downstream storage assembly;
- the elongated material is pressed against the base portion in the flame as it is continuously traveling through the flame;
- the cooling support comprises at least one inclined deflection surface of at least one main section of the flame produced by the torch, the flame produced by the torch comprising a deflected section situated downstream of the inclined deflection surface, the material elongated passing through the deflected section;
- the temperature of the region of the flame through which the elongate material passes is less than 700 ° C., and is especially between 400 ° C. and 700 ° C .;
- the torch produces a flame generated by the combustion of a hydrocarbon fuel gas, such as acetylene, with oxygen, the ratio of the fuel gas flow rate to the oxygen flow rate delivered in the torch being advantageously greater than 1; ;
- a hydrocarbon fuel gas such as acetylene
- a catalytic agent capable of initiating the growth of carbon nanostructures, the catalytic agent being advantageously deposited from a diluted metal solution;
- the speed of travel of the elongate material in the flame is greater than 1 mm / min, especially greater than 5 mm / min, preferably greater than 300 mm / min and is in particular between 300 mm / min and 10000 mm / min;
- the speed of travel is greater than 1 m / min, preferably greater than 3 m / min especially greater than 5m / min.
- the invention also relates to an installation for preparing an elongated material provided with grafted carbon nanostructures, characterized in that it comprises:
- a grafting device comprising a torch producing a flame in a volume of ambient air, the grafting device comprising a cooling support arranged opposite the flame;
- the grafting device being suitable for continuously grafting carbon nanostructures onto the elongate material as it travels through the flame.
- the installation according to the invention can comprise one or more of the following characteristics, taken in isolation or in any technically possible combination:
- the continuous running assembly of the elongated material comprises an upstream assembly of destocking of the raw elongated material, a mechanism for passing the raw elongated material destocked through the flame, and a downstream storage assembly of the elongate material provided with carbon nanostructures;
- the cooling support comprises a base part and an opposite part arranged between the base part and the torch, the base part and the opposite part being each cooled, the scroll assembly being adapted to guide the elongate material between the base part and the torch, the base part and the opposite part being each cooled, base part and the opposite part;
- the cooling support comprises at least one inclined deflection surface of at least one main section of the flame produced by the torch, the flame produced by the torch comprising a deflected section situated downstream from the inclined deflection surface; scroll assembly being adapted to guide the elongate material to pass through the deflected section.
- the subject of the invention is also a product comprising an elongate material provided with grafted carbon nanostructures, in particular carbon nanotubes and / or carbon nanofibers, characterized in that it is capable of being obtained by the process such as described above.
- FIG. 1 is a schematic view of a first installation for preparing an elongated material provided with grafted carbon nanostructures according to the invention
- FIG. 2 is a schematic view of the grafting device of the installation of FIG. 1;
- FIG. 3 is a partial view from above of the cooling support of the elongate material in the grafting device of FIG. 2;
- FIG. 4 is a partial sectional view taken along the plane IV-IV of FIG.
- FIG. 5 is a diagrammatic view, taken in section, of a torch of the grafting device of FIG. 2;
- FIG. 6 is a view similar to Figure 5 of another torch for the device of Figure 2;
- FIG. 7 is a front view of a second grafting device according to the invention for the installation of FIG. 1;
- FIG. 8 is a side view of the variant of the grafting device of FIG.
- FIG. 9 is a view similar to FIG. 7 of a third grafting device according to the invention.
- FIG. 10 is a photograph illustrating a product obtained in the preparation plant of Figure 1;
- Figure 1 1 is an enlarged view of the product of Figure 10.
- FIG. 12 is a view from above of an apparatus for mechanical characterization of products containing an elongate material according to the invention.
- FIG. 13 is a graph comparing the mechanical behavior of a product containing an elongated material according to the invention with a product devoid of elongated material according to the invention.
- FIGS. 1 to 6 show a first installation 10 for the preparation of a product 12 provided with carbon nanostructures according to the invention, the product 12 being visible in FIGS. 10 and 11.
- the product 12 comprises an elongated material 14 on which carbon nanostructures 16 are grafted.
- the elongated material 14 is for example formed based on individual macroscopic fibers 18, the carbon nanostructures 16 being grafted onto the fibers.
- macroscopic fibers are ceramic fibers, such as silica fibers, in particular glass fibers, carbon fibers, basalt fibers, organic fibers, in particular high temperature organic fibers such as aramid fibers, especially meta-aramid fibers such as poly (m-phenyleneisophthalamide) (NOMEX®), or poly (p-phenyleneterephthalamide) (KEVLAR®) fibers, fluoropolymer fibers, especially polytetrafluoroethylene fibers (TEFLON®), polyazole fibers, such as poly (p-phenylene-2,6-benzobisoxazole), polysulfide fibers, such as poly (phenylene sulfide) (PPS), imidazole fibers such as as poly (benzimidazole) (ZYLON®), oxidized acrylic fibers (LASTAN®).
- ceramic fibers such as silica fibers, in particular glass fibers, carbon fibers, basalt fibers, organic fibers, in particular high temperature organic fibers such
- organic fibers with moderate temperature resistance can form the elongate material 14.
- a fiber is an elongated material having a length much greater than its maximum transverse dimension.
- the minimum transverse dimension of a macroscopic fiber is for example greater than 5 ⁇ .
- the elongate material 14 is for example in the form of an individual fiber, a fiber assembly forming a wire, a ribbon, a strand, or a wick.
- the elongated material 14 may also be obtained from an assembly of woven, braided, knitted fibers, or a nonwoven. It can then form a web, or a veil of fibers.
- the elongated material 14 has a length much greater than its other dimensions, for example greater than 1 cm, especially greater than 10 cm.
- the elongated material 14 is adapted to be wound on a rotary storage member such as a drum or a reel, or to be unrolled from such a member.
- the elongated material 14 is formed from a non-fibrous solid, such as a solid matrix. It forms for example a film.
- the carbon nanostructures 16 grafted onto the elongate material are, for example, carbon nanofibers or carbon nanotubes.
- carbon nanofibers is generally meant a solid cylindrical nanostructure formed of layers of graphene stacked, the layers having for example a cone-shaped or plate.
- Nanofibers have at least one dimension at the nanoscale, that is to say less than one micrometer.
- the nanofibers thus have a transverse dimension of less than 100 nanometers, in particular less than 50 nanometers, and for example between 15 and 20 nanometers. They have a length of less than 1 mm, especially less than 100 micrometers, for example between 20 and 30 micrometers.
- nanotube is meant a particular crystalline structure of hollow tubular form, composed of atoms advantageously regularly arranged pentagon, hexagon or heptagon defining a central hollow passage.
- Nanotubes are produced from carbon atoms to form carbon nanotubes.
- the nanotubes have at least one dimension at the nanoscale, that is to say less than one micrometer.
- the nanotubes thus have a transverse dimension of less than 100 nanometers, especially less than 50 nanometers and for example between 15 and 20 nanometers. They have a length of less than 1 mm, in particular less than 100 micrometers, for example between 20 and 30 micrometers.
- Carbon nanotubes are in particular an allotropic form of carbon.
- the nanotubes are nanotubes of single-walled carbon nanotubes (or “single walled nanotubes” in English).
- the nanotubes are carbon nanotubes multifilettes (or
- Multi walled nanotubes having several sheets of graphene wound around each other, for example concentric cylinders.
- the nanostructures 16 are grafted onto the surface of the elongate material 14.
- This grafting is for example carried out by a covalent chemical bond between the elongated material 14 and the atoms constituting the nanostructure 16.
- the nanostructures 16 are fixed on the elongate material 14 and are movable together with it.
- This grafting can result in an anchoring of several nanometers of the nanostructure 16 to the surface of the elongate material 14.
- the nanostructures 16 constitute a sheet around the elongate material 14, each nanostructure 16 being fixed at a first point on the elongated material 14 or on another nanostructure 16.
- Each nanostructure 16 has in addition a free end or linked to another nanostructure 16.
- the surface density of grafted nanostructures 16 on the elongate material 14 is advantageously greater than 0.01 mg of nanostructures per square centimeter and is for example between 0.01 mg / cm 2 and 5 mg / cm 2 of nanostructure 16.
- the nanostructures 16 modify the properties of the elongated material 14, for example to increase the conductivity of the elongated material 14 or its mechanical strength.
- the preparation installation 10 comprises a grafting device 20 of nanostructures 16 on the elongate material 14, and a set 22 for continuously moving the elongate material 14 in the device of FIG. grafting 20.
- the installation 10 further comprises a set 24 of pretreatment of the elongate material 14 before it passes through the grafting device 20.
- the grafting device 20 is illustrated in FIG. 2. It comprises, according to the invention, a torch 26 for generating a flame 28 in a volume of ambient air 30, a gas conveying assembly 32 to the torch 26. to supply the flame 28, and a cooling support 33 disposed under the torch 26.
- the grafting device 20 further comprises a control and regulation unit 34.
- the torch 26 advantageously extends along a vertical axis A-A '. It comprises a body 40 defining at least one channel 42 for conveying a mixture of gases.
- the torch 22 defines a central channel 42 single gas injection.
- the channel 42 is connected upstream to the gas conveying assembly 32. It opens downstream through a downstream opening 46 extending opposite the reception assembly 32.
- the channel 42 extends here along the axis A-A ', in the center of the torch 22.
- the torch 22 defines a plurality of peripheral auxiliary channels 44 for the injection of a cooling gas.
- the channels 44 are arranged around the central channel 42.
- Each auxiliary channel 44 has a section smaller than that of the central channel 42.
- the auxiliary channel 44 is connected upstream to the gas conveying assembly
- the flame 28 is generated at the outlet and below the torch 26, facing the opening 46. It has a substantially frustoconical divergent profile away from the torch 22 by distributing on the cooling support 33.
- the gas conveying assembly 32 comprises at least one source 50 of combustible gas, at least one source 52 of oxidizing gas, a pipe 54 for conveying the combustible gas from the source 50 to the torch 22 and a conveying line 56 of oxidizing gas from the source 52 to the torch 22.
- the conveyor assembly 32 further comprises a first regulator 58 of combustible gas and a second regulator 60 of combustion gas.
- the fuel gas present in the source 50 contains atoms for forming the carbon nanostructures.
- the combustible gas contains, for example, a hydrocarbon. It comprises or is advantageously constituted of acetylene.
- the fuel gas source 50 thus contains pure acetylene or in mixture.
- the oxidizing gas contained in the source 52 is for example oxygen, pure or mixed.
- the lines 54, 56 respectively connect each source 50, 52 respectively to the channel 42.
- a mixer can be interposed between the sources 50, 52 and the torch 22 to mix the gases from the lines 54, 56 before its introduction into the channel 42.
- Each regulator 58, 60 is adapted to regulate the flow of gas flowing in the pipe 54, 56 on which it is mounted.
- the regulators 58, 60 are connected to the control unit 34.
- the regulators 58, 60 are able to advantageously maintain a ratio of the volume flow rate of the fuel gas to the volume flow rate of the oxidizing gas of between 1.2 and 1.5, advantageously between 1, 25 and 1, 30.
- the regulators 58, 60 are furthermore capable of maintaining a total gas volume flow rate of less than 1 liter / minute, for example between 0.2 liters / minute and 0.8 liters / minute, in particular between 0 , 4 liters / minute and 0.5 liters / minute.
- the conveyor assembly 32 further comprises a source 62 of cooling gas, and a pipe 64 for supplying the cooling gas into each of the auxiliary channels 44.
- the pipe 64 is provided with a regulator 68 for cooling gas.
- the cooling gas is, for example, argon, or helium.
- the cooling support 33 comprises a lower base portion 70 and an opposite upper portion 72, the elongated material 14 being intended to circulate in the flame 28 between the lower portion 70 and the upper portion. 72.
- the cooling support 33 further comprises a heat regulation assembly 74 able to cool, in a controlled manner, the lower part 70 and / or the upper part 72.
- the lower part 70 comprises a substrate 76 intended to come into contact with the elongated material 14 and a thermal regulation block 78 placed under the substrate 76.
- the substrate 76 is advantageously made of a flat metal plate. It defines an upper surface 80 for supporting the elongated material 14 extending transversely with respect to the axis A-A ', opposite the torch 26.
- the upper part 72 is disposed axially between the torch 26 and the lower part 70.
- the upper body 82 which, in this example, has a jumper shape.
- the upper body 82 delimits a lower surface 84 placed facing the upper bearing surface 80 of the elongate material 14, and an inclined upper surface 86 to deflect the flame 28 towards the elongate material 14.
- the upper body 82 defines, in the upper surface 86, a notch 88 central passage of the elongate material 14.
- the lower surface 84 is substantially parallel to the upper bearing surface 80.
- the inclined surface 86 has a non-zero inclination, and less than 90 ° with respect to the upper surface 80, in projection in a plane passing through the axis A-A '.
- the notch 88 has a curved shape corresponding to a part of the contour of the flame 28.
- the upper part 72 is able to ensure the plating of the elongated material
- the heat regulation assembly 74 comprises a coolant source 90, a first refrigerant circulation pipe 92 through the lower part 70, and a second refrigerant circulation pipe 94 through the upper part 72.
- the assembly 74 further comprises a temperature sensor 96, for example a pyrometer, capable of measuring the temperature of the region of the flame 28 facing a point of contact of the elongated material 14 with the upper surface 80, in the vicinity from the bottom 70.
- a temperature sensor 96 for example a pyrometer
- the coolant is able to evacuate by heat exchange without contact the heat generated by the flame 28. It is for example formed of water, a mixture of water with another refrigerant such as glycol, or carbon dioxide .
- the control unit 34 is able to control the gas conveying assembly 32 to provide an adequate mixture of fuel gas and oxidizing gas, possibly with refrigerant gas.
- the unit 34 is also suitable for controlling the thermal regulation assembly
- the torch 26, the flame 28, and the cooling support 33 are placed in a volume of ambient air, for example in a building, without being placed in a confinement enclosure in which a particular atmosphere is defined.
- the volume content of oxygen in the ambient air volume is greater than 19%, and is especially between 20% and 22%.
- the volume content of nitrogen in the ambient air volume is greater than 70%, and is especially between 75% and 80%.
- the preparation method according to the invention can therefore be implemented in a very simple manner, without providing a containment enclosure in which a particular atmosphere must be controlled.
- the atmosphere prevailing around the torch 26, and in particular between the torch 26 and the cooling support 33 around the flame 28 is not controlled.
- the scroll assembly 22 comprises an upstream element 100 for retrieval of the elongate material 14, before it passes through the grafting device 20, a mechanism (not shown) for guiding the elongate material 14 through the grafting device 20, and a downstream element 102 for storing the elongate material 14 provided with grafted carbon nanostructures 16, originating from the grafting device 20.
- the upstream element 100 comprises for example an upstream winding member of the elongated raw material 14.
- the elongated raw material 14 is adapted to be destocked out of the upstream element 100 in a continuous manner.
- the guide mechanism of the elongate material 14 is adapted to guide the material 14 in the grafting device 20 to apply it to the surface 80 and position it in the flame 28 facing the inclined surface 86 of the upper part 72.
- It comprises means for adjusting the position of the elongate material 14 with respect to the upper surface 80 and with respect to the inclined surface 86 which can be controlled by the control unit 34.
- the downstream element 102 comprises, for example, a downstream member for winding the elongated material 14 grafted.
- the grafted elongate material 14 is adapted to be stored in the downstream element 102 in a continuous manner.
- downstream element 102 and / or the guiding mechanism comprise means for driving the elongated material 14 at a given speed in the grafting device 20.
- the given speed is, for example, greater than 1 mm / min, and is in particular greater than 5 mm / min. This speed is advantageously greater than 300 mm / min and for example between 300 mm / min and 10000 mm / min.
- the pretreatment assembly 24 is disposed between the upstream destocking element 100 and the grafting device 20. It comprises a device 10 for applying a catalytic agent capable of initiating the growth of carbon nanostructures on the outer surface of the elongate 14 raw material.
- the catalytic agent is for example formed a metal such as iron, nickel, cobalt. It is deposited in the form of a plurality of sites suitable for generating the growth of carbon nanostructures 16 on the surface of the elongated material 14.
- the device 1 10 comprises means 1 12 for dipping the elongate material 14 in a dilute solution containing a metal, and means 1 14 for drying.
- the grafting device 20 is provided and is disposed in a volume of ambient air.
- Raw elongated material 14 is disposed in the upstream destocking assembly 100 and is deployed through the pre-treatment assembly 24, when present, through the grafting device 20, to the downstream element. 102 storage.
- the grafting device 20 is activated.
- the thermal regulation assembly 74 is started to cause cooling of the lower part 70 and the upper part 72 of the cooling support 33.
- a mixture of oxidizing gas and combustible gas is supplied in the torch 26 to ignite and feed the flame 28.
- the temperature sensor 96 is further activated to adjust the temperature of the flame 28.
- the control unit 34 controls the volume ratio of the fuel gas to the oxidizing gas to advantageously maintain it between 1, 1 and 1, 4, especially between 1, 25 and 1, 3.
- the total volume of fuel gas and oxidizing gas is greater than 0.3 l / min and is in particular between 0.4 l / min and 0.5 l / min.
- the flame 28 is created in a volume of ambient air, without the need to create a particular atmosphere around the torch 26, which is particularly easy to use.
- the position of the upper surface 80, and the lower portion 70 is adjusted to ensure that a temperature of between 400 ° C and 700 ° C, preferably between 500 ° C and 700 ° C is present in the area of the flame 28 in which the elongate material 14 will circulate.
- the axial distance separating the free end of the torch 26 from the surface 80 is for example between 3 mm and 5 mm, in particular between 4 mm and 4.5 mm.
- the elongated material 14, for example a carbon wire is driven to continuously scroll between the upstream destocking element 100 and the downstream storage element 102, through the pre-treatment assembly 24 and the grafting device 20.
- the elongated raw material 14 When passing through the pre-treatment assembly 24, the elongated raw material 14 is provided with metal graft sites on its outer surface. Advantageously, it quenched in a metal solution provided in the means 1 12 of soaking, then it dries in the drying means 1 14.
- the elongate material 14 then passes into the grafting device 20. It is applied against the upper surface 80 and penetrates into the flame 28. As illustrated in FIG. 4, it passes opposite the inclined surface 86 of the upper part 70.
- the flame 28 being projected against the surface 86, it has a main section 120, upstream of its contact with the inclined surface 86 and a section 122 deflected on the surface 86, in which the elongate material 14 circulates.
- a cooling gas such as argon, is added to the flame 28.
- the elongated material 14 is subjected to a part of the flame 28 which has a controlled temperature, and whose cooling is controlled.
- the elongated material 14 flows continuously in the flame 28 at a speed of between 300 mm / min and 6000 mm / min.
- This passage causes the continuous grafting of carbon nanostructures 16 on the elongated material 14, on the surface of the elongated material 14 placed opposite the flame 28.
- the length of the nanostructures 16 is for example greater than 10 ⁇ , and in particular between 20 ⁇ and 30 ⁇ .
- the maximum diameter of the nanostructures 16 is for example less than 1 ⁇ and is in particular less than 50 nm.
- the elongate material 14, provided with carbon nanostructures 16 is then stored in the downstream assembly 102, continuously.
- the method according to the invention is therefore particularly simple to put, while allowing optimum productivity. It allows efficient grafting of carbon nanostructures on various elongated materials, such as fibers, yarns, structured matrices, sails, etc.
- This method is moreover very safe for the operators since it involves a grafting of the nanostructures 16 onto the elongate material 14.
- the grafting is carried out continuously, as the elongate material 14 passes through the flame 28.
- the upper surface 80 of the lower part 70 of the support has a curved shape, convex towards the torch 26, with the exception of a section 132 plane situated opposite the upper part 72 and the flame 28.
- the upstream assembly 100 and the downstream assembly 102 each comprise a coil.
- the coil of the upstream assembly 100 is able to unwind the elongated raw material 14, the coil of the downstream assembly 102 being suitable for winding the elongated material 14 provided with the nanostructures 16.
- the installation 10 comprises a first upstream grafting device 20A of an upper part of the elongate material 14 and a second downstream grafting device 20B of a lower part of the elongate material 14. .
- the first grafting device 20A is oriented opposite the second grafting device 20B.
- the torch 26 of the first grafting device 20A opens in a first direction (downwards in FIG. 9) towards the cooling support 33 of this device 20A.
- the torch 26 of the second grafting device 20B opens opposite the first direction in a second direction (upwards in FIG. 9) facing the cooling support 33 of this device 20B.
- elongated materials 14 provided with grafted carbon nanostructures 14 which can be used in numerous technical fields, such as, for example, the reinforcement of matrices made of polymer material, the production of composite materials to obtain high-performance composite parts (eg for aeronautics, sports and recreation, rail, automotive), or the development of intelligent materials (filtration, smart textiles, fuel cells).
- an elongate material 14 formed of carbon son has been provided with carbon nanostructures 16 consisting of nanotubes, using a method according to the invention.
- the modified carbon yarns were molded by manual lamination using a 2025 epoxy resin from AXON.
- test pieces containing raw carbon son, not treated by the method according to the invention were molded.
- the electrical resistance of the test pieces comprising wires treated by the process according to the invention is less than 30 ohms, whereas the test pieces comprising untreated wires have an electrical resistance close to 235 ohms.
- thermomechanical dynamic analysis DTMA
- the distance between supports was 60 mm, the frequency 5 Hz, the rate of rise in temperature of 2 ° C / min and the travel of ⁇ 10 ⁇ .
- the tests were conducted between 25 ° C and 110 ° C, before the glass transition of the resin.
- a top view of the assembly is shown in FIG.
- FIG. 12 shows the evolution of the storage module E 'as a function of temperature, the composite bars on which nanostructures 16 are grafted onto carbon fibers have a storage module 310 10% higher than the storage module 312 of the reference bar.
- the method according to the invention is therefore particularly simple to implement, since it does not require introducing the particles into a furnace, nor to regulate a particular atmosphere in the oven.
- the method can be implemented simply and conveniently, directly in a volume of ambient air.
- the growth of nanotubes obtained is then rapid, unlike that of the processes of the state of the art, in particular that described in Shaffer et al., Carbon, 48, 277-286, 2010, which makes it possible to obtain high yields. .
- the inventors have discovered in a particularly surprising manner that the flame methods used in the state of the art to produce free carbon nanostructures (see for example US201 1/0059006 and US 2010/01 19724) could, in the presence of an elongated material passing through the flame, lead to the grafting of nanostructures on the elongated material.
- the method according to the invention makes it possible to fix the nanostructures on the elongate material to produce a modified elongate material having improved properties.
- the elongated products thus obtained can be used in particular to be embedded in a wide variety of polymer matrices to improve the properties of the matrix.
- the method according to the invention comprises continuously moving the elongate material through the flame in a free air volume, which ensures fast and efficient grafting of a long length of the elongate material.
- the method therefore does not need to immobilize for a significant time the samples to be treated in a confined atmosphere (as in EP 2,224,830, in Yoon et al., Science of the Total Environment, 409, 4132-4138, 201 1, or in Shaffer et al., Carbon, 48, 277-286, 2010) or to immobilize the samples to be treated in a flame (see Amini et al., Carbon 48, 3131 -3138, 2010 or Mai et al., Carbon 50, 2347-2374, 2012).
- the method according to the invention also avoids providing complex interfaces with a CVD furnace, when the material is introduced continuously in such a furnace as in EP 2,290,139.
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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CA2897247A CA2897247A1 (fr) | 2013-01-10 | 2014-01-10 | Procede de preparation d'un materiau allonge muni de nanostructures de carbone greffees, appareil et produit associes |
EP14700303.2A EP2943288A2 (fr) | 2013-01-10 | 2014-01-10 | Procédé de préparation d'un matériau allongé muni de nanostructures de carbone greffées, appareil et produit associés |
US14/759,576 US20150361613A1 (en) | 2013-01-10 | 2014-01-10 | Method for preparing an elongate material provided with grafted carbon nanostructures, and associated device and product |
CN201480007724.7A CN105307782A (zh) | 2013-01-10 | 2014-01-10 | 制备配备有接枝的碳纳米结构的细长材料的方法以及相关的设备和产品 |
AU2014204822A AU2014204822A1 (en) | 2013-01-10 | 2014-01-10 | Method for preparing an elongate material provided with grafted carbon nanostructures, and associated device and product |
JP2015552056A JP2016508945A (ja) | 2013-01-10 | 2014-01-10 | 融合カーボンナノ構造体を備えた細長い材料を調製する方法および関連する装置と生成物 |
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FR1350228 | 2013-01-10 | ||
FR1350228A FR3000691B1 (fr) | 2013-01-10 | 2013-01-10 | Procede de preparation d'un materiau allonge muni de nanostructures de carbone greffees, appareil et produit associes |
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WO2014108511A2 true WO2014108511A2 (fr) | 2014-07-17 |
WO2014108511A3 WO2014108511A3 (fr) | 2014-12-04 |
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PCT/EP2014/050406 WO2014108511A2 (fr) | 2013-01-10 | 2014-01-10 | Procédé de préparation d'un matériau allongé muni de nanostructures de carbone greffées, appareil et produit associés |
Country Status (8)
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US (1) | US20150361613A1 (fr) |
EP (1) | EP2943288A2 (fr) |
JP (1) | JP2016508945A (fr) |
CN (1) | CN105307782A (fr) |
AU (1) | AU2014204822A1 (fr) |
CA (1) | CA2897247A1 (fr) |
FR (1) | FR3000691B1 (fr) |
WO (1) | WO2014108511A2 (fr) |
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CN114960190A (zh) * | 2022-05-13 | 2022-08-30 | 西南交通大学 | 一种用于太阳能水蒸发的玄武岩纤维原位生长碳纳米管海绵制备方法 |
Citations (4)
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US20100119724A1 (en) | 2005-04-13 | 2010-05-13 | Jean-Baptiste Donnet | Methods and systems for synthesis on nanoscale materials |
EP2224830A2 (fr) | 2007-12-29 | 2010-09-08 | Braun GmbH | Filament et procede pour produire des filaments |
EP2254830A2 (fr) | 2008-02-20 | 2010-12-01 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Croissance de nanotubes de carbone sur substrats de carbone ou metalliques |
EP2290139A1 (fr) | 2007-01-03 | 2011-03-02 | Applied NanoStructured Solutions, LLC | Fibre à infusion CNT et cable |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US20030099592A1 (en) * | 2000-03-03 | 2003-05-29 | Rodriguez Nelly M. | Method for preparing carbon nanostructures |
CN103118975A (zh) * | 2010-09-22 | 2013-05-22 | 应用奈米结构公司 | 具有碳纳米管成长于其上的碳纤维基板及其制造方法 |
CN102635164B (zh) * | 2012-04-26 | 2013-12-11 | 上海亿霖润滑材料有限公司 | 高层建筑玻璃幕墙的润滑结构和方法 |
-
2013
- 2013-01-10 FR FR1350228A patent/FR3000691B1/fr not_active Expired - Fee Related
-
2014
- 2014-01-10 US US14/759,576 patent/US20150361613A1/en not_active Abandoned
- 2014-01-10 WO PCT/EP2014/050406 patent/WO2014108511A2/fr active Application Filing
- 2014-01-10 CN CN201480007724.7A patent/CN105307782A/zh active Pending
- 2014-01-10 JP JP2015552056A patent/JP2016508945A/ja active Pending
- 2014-01-10 CA CA2897247A patent/CA2897247A1/fr not_active Abandoned
- 2014-01-10 EP EP14700303.2A patent/EP2943288A2/fr not_active Withdrawn
- 2014-01-10 AU AU2014204822A patent/AU2014204822A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100119724A1 (en) | 2005-04-13 | 2010-05-13 | Jean-Baptiste Donnet | Methods and systems for synthesis on nanoscale materials |
US20110059006A1 (en) | 2005-04-13 | 2011-03-10 | Continental Carbon Company | Methods for Production of Carbon Nanomaterials in the Presence of a Carbon Black Catalyst |
EP2290139A1 (fr) | 2007-01-03 | 2011-03-02 | Applied NanoStructured Solutions, LLC | Fibre à infusion CNT et cable |
EP2224830A2 (fr) | 2007-12-29 | 2010-09-08 | Braun GmbH | Filament et procede pour produire des filaments |
EP2254830A2 (fr) | 2008-02-20 | 2010-12-01 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Croissance de nanotubes de carbone sur substrats de carbone ou metalliques |
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Title |
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AMINI ET AL., CARBON, vol. 48, 2010, pages 3131 - 3138 |
MAI ET AL., CARBON, vol. 50, 2012, pages 2347 - 2374 |
SHAFFER ET AL., CARBON, vol. 48, 2010, pages 277 - 286 |
YOON ET AL., SCIENCE OF THE TOTAL ENVIRONMENT, vol. 409, 2011, pages 4132 - 4138 |
Also Published As
Publication number | Publication date |
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AU2014204822A1 (en) | 2015-07-30 |
US20150361613A1 (en) | 2015-12-17 |
WO2014108511A3 (fr) | 2014-12-04 |
CN105307782A (zh) | 2016-02-03 |
FR3000691B1 (fr) | 2015-02-13 |
JP2016508945A (ja) | 2016-03-24 |
CA2897247A1 (fr) | 2014-07-17 |
FR3000691A1 (fr) | 2014-07-11 |
EP2943288A2 (fr) | 2015-11-18 |
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