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1. WO2018156899 - PROCÉDÉS POUR LA FABRICATION DE FEUILLE ET DE FIL HYBRIDES DE NANOTUBES DE CARBONE (CNT) PAR ASSEMBLAGE EN PHASE GAZEUSE, ET MATÉRIAUX HYBRIDES DE CNT

Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

CLAIMS

1. A system for the gas-phase production of carbon nanotube (CNT)-hybrid materials in a pyrolytic reactor, the system comprising:

a flow-through pyrolytic reactor tube comprising a reactant inlet, an inlet zone, a furnace zone, an exit zone, and an exit port;

a fuel injector positioned to deliver a fuel flow through the reactant inlet, said fuel flow comprising at least one carbon source and a carrier gas;

at least one particle injector positioned to deliver a particle flow through the reactant inlet, said particle selected from a ceramic, a polymer, a metal, and

combinations thereof;

a harvest box comprising at least one processing apparatus for receiving and processing the CNT- hybrid material as it exits the exit port.

2. The system according to claim 1 wherein the fuel injector comprises a controller for controlling the composition and flow rate of the fuel flow through the inlet, and the at least one particle injector comprises a controller for controlling the composition and flow rate of the particle flow through the inlet, each controller being operationally connected to a system controller such that the controller of fuel injector and the controller of the particle injector may be independently or interdependently controlled.

3. The system according to claim 1, wherein a delivery position of the particle injector is closer to the furnace zone than a delivery position of the fuel injector.

4. The system according to claim 1, wherein the processing apparatus is selected from one or more of a rotating drum, a rotating spool, a spinner, a winder, a drawer, a stretcher, a compressor, and combinations thereof.

5. The system according to claim 4, wherein the processing apparatus comprises a rotating drum and further comprises a water bath positioned such that as the drum rotates to wind the exiting CNT -hybrid material, the material passes through the water intermittently according to a rotational frequency.

6. The system according to claim 1, further comprising a feeder apparatus located exterior to the reactant inlet and positioned to feed a fiber material along a horizontal axis of the reactor tube to the processing apparatus at a feeder rate corresponding to a rate of formation of the CNT -hybrid material such that CNT-hybrid material deposits on the fiber material.

7. The system according to claim 6, wherein the fiber material comprises a fiber cord or a fiber tape and the processing apparatus is a spool or a drum, respectively, such that as the fiber cord or tape comprising deposited CNT-hybrid material exits the exit port it is spun or rolled and compressed onto the spool or drum.

8. The system according to claim 1, wherein a particle injector comprises a flow type particle dispenser comprising a canister configured to receive carrier gas flow and particles, a mixer for mixing the carrier gas and particles, and an injection nozzle, said injection nozzle positioned to deliver the gas particle mixture through the reactor inlet.

9. The system according to claim 1, wherein a particle injector comprises a venturi eductor comprising a carrier gas flow inlet, a coupling port, a particle dispenser coupled to the coupling port, and an injection outlet, wherein the coupling port is aligned with a point of greatest constriction of the eductor, and the injection outlet is located proximate the reactor inlet.

10. The system according to claim 1, wherein the fuel injector comprises a positive displacement fuel injector.

11. The system according to claim 10, wherein the positive displacement fuel injector comprises a syringe.

12. The system according to claim 1, wherein the furnace zone comprises a longitudinal axis and a diameter that increases or decreases along the axis toward the exit zone.

13. The system according to claim 1, wherein the reactor tube comprises a surface area to volume ratio of from about 1.3 to about 2, and comprises a circular or ovate cross-section.

14. The system according to claim 1, further comprising at least one quadrupole mass spectrometer to map chemical species present in one or more of the furnace zone, exit zone, and the harvest box during a material production time.

15. The system according to claim 1, further comprising a dispenser proximate the exit port for spraying or injecting the CNT -hybrid material with one or more of a polymer and a solvent as it exits the exit port.

16. The system according to any of the above claims further comprising an exhaust gas by-pass system comprising a collecting hood disposed about at least a portion of the exit zone, at least one bubbler located exterior to the harvest box and in fluid

communication with the exit zone via a tube extending from the collecting hood, and at least one bubbler located exterior to the harvest box and in fluid communication with an interior of the harvest box exterior, wherein the at least two bubblers are subject to independent or interdependent control by the system controller.

17. The system according to any of the above claims further comprising a pressure equilibration mechanism comprising at least one hose connecting an interior of the harvest box to an interior of a particle injector, aid pressure equilibration mechanism sufficient to substantially equilibrate pressure throughout the system.

18. The system according to any of the above claims further comprising at least one electrostatic charger for applying a voltage to one or more of the particle injector, the fuel injector, the reactor, and the processing device.

19. A gas-phase method for the production of carbon nanotube (CNT)-hybrid yarn and sheets using a pyrolytic reactor tube comprising an inlet port, an inlet zone, a furnace zone, an exit zone, and an exit port, the method comprising:

optionally, delivering an atomized fuel flow to the furnace zone at a point proximate the inlet port at a fuel flow rate, said fuel flow comprising a carrier gas and at least one source of carbon;

delivering a particle flow to the furnace zone at a point in the inlet zone at or beyond the delivery point of the fuel flow at a particle flow rate, said particle flow comprising carrier gas and at least one particle selected from ceramic, polymer, metal, a carbon source, and combinations thereof;

independently controlling the fuel flow rate and the particle flow rate to achieve a production time sufficient to continuously form a CNT -hybrid sock at a furnace zone temperature of between 1200 °C and 1600 °C;

optionally, treating the sock as it emerges from the exit port; and

collecting the emerging CNT-hybrid sock in a harvest box;

wherein the collected CNT -hybrid sock comprises carbon nanotube bundles integrated with the injected particles.

20. The method according to claim 19, wherein the furnace zone temperature is maintained at about 1400 °C across the production time.

21. The method according to claim 19, further comprising twisting the emerging CNT -hybrid sock into yarn or rolling the emerging CNT-hybrid sock into sheets.

22. The method according to claim 21, wherein the twisting and/or rolling is accompanied by one or more of water densification and electric charging.

23. The method according to claim 22, wherein the emerging CNT-hybrid sock is wound onto a rolling drum partially submerged in a water bath.

24. The method according to claim 23, wherein the CNT-hybrid sock is rolled with a backing sheet, tape or fiber.

25. The method according to claim 24, wherein the backing sheet comprises polytetrafluoroethylene.

26. The method according to claim 19, wherein the fuel flow and/or the particle flow comprises at least one catalyst.

27. The method according to claim 26, wherein the catalyst comprises ferrocene.

28. The method according to claim 26, wherein the fuel flow further comprises thiophene.

29. The method according to claim 26, wherein the fuel flow further comprises xylene.

30. The method according to claim 19, wherein the fuel flow carbon source comprises a C 1-6 hydrocarbon, optionally as an alcohol.

31. The method according to claim 19, wherein the fuel flow comprises a carbon source and the particle flow comprises particles selected from the particles set forth in column 1 of Table 3.

32. The method according to claim 19, wherein the particles comprise a nanopowder and the particles are, optionally, functionalized, passivated, and/or coated with carbon.

33. The method according to claim 32, wherein the particles are functionalized with one or more of -OH, -COOH, -CHO, -X (F, CI, Br, I), N2, and epoxide.

34. The method according to any of the preceding method claims wherein the carrier gas comprises Argon and, optionally, hydrogen.

35. The method according to claim 19, wherein there is no independent fuel flow and particles comprising a high aspect ratio carbon are injected from a particle injector.

36. The method according to claim 35, wherein the high aspect ratio carbon particles are selected from carbon nanotubes, carbon nanofibers, carbon microfibers, and C-60.

37. The method according to claim 36, wherein one or more non-carbon particles are mixed with the high aspect ratio carbon particles in a particle injector, or delivered into the reactor inlet by different particle injectors.

38. The method according to claim 19, wherein to achieve continuous product the fuel flow rate is adjusted to between 10 ml/hr and 60 ml/hr, and the particle delivery rate is roughly adjusted to between 1 g/hr and 100 g/hr for a 2 inch outer diameter reactor tube.

39. The method according to claim 19, wherein hydrogen exhaust gas generated in the furnace is vented through one or more openings in the exit port to a hood at least partially surrounding the exit port, and through a conduit in communication with a first bubbler located exterior to the harvest box.

40. The method according to claim 39, wherein hydrogen gas present in the harvest box is vented via a conduit from the harvest box to a second bubbler situated exterior to the harvest box.

41. The method according to any of the above claims further comprising delivering a dilution gas flow into the harvest box at a dilution gas flow rate of from about 2 SLM to about 15 SLM.

42. The method according to claim 19 wherein hydrogen exhaust gas generated in the furnace is vented through one or more openings in the exit port to a hood at least partially surrounding the exit port, and through a conduit in communication with a first bubbler located exterior to the harvest box, hydrogen gas present in the harvest box is vented via a conduit from the harvest box to a second bubbler situated exterior to the harvest box, said first bubbler at a pressure of about 0.5 inches of water, said second bubbler at a pressure of about 1.0 inches of water and further comprising a dilution gas flow into the harvest box at a dilution gas flow rate of from about 2 SLM to about 15 SLM.

43. The method according to claim 19, wherein "delivering a particle flow" comprises injecting particles via at least one particle injector selected from a flow type injector and a venturi eductor, and combinations thereof, wherein prior to delivering the particle flow, the particles are mixed with the carrier gas in the at least one injector, and, optionally, applying a voltage to the particle injector.

44. The method according to claim 43, wherein particles are delivered from at least two different particle injectors, each particle injector comprising a different particle.

45. The method according to claim 19, wherein "delivering an atomized fuel flow" and "delivering a particle flow" are effectuated via a dual injection device comprising a first nozzle and a second nozzle that meet at a merged injection outlet, the first nozzle providing carrier gas and particles at a first flow rate, the second nozzle providing fuel at a second flow rate via a positive displacement pump, whereby the first flow rate and the second flow rate are independently controlled.

46. The method according to claim 45, wherein the positive displacement pump comprises a syringe.

47. The method of claim 45, wherein a voltage between about -20 kV and +3 kV is applied to the duel injection device during a production time.

48. The method according to claim 19, further comprising applying an

electromagnetic field to the reactor during the production time.

49. A carbon nanotube (CNT)-NP hybrid material having NPs integrated into the CNT at a nanoscale level.

50. A CNT-hybrid material according to claim 49 comprising a filter comprising a porosity defined by pore size and pore density, the material comprising CNT bundles integrated with one or more particles selected from granulated activated carbon, epoxy resin and iron.

51. The filter according to claim 50, wherein the pore size and density are uniform or variable.

52. A CNT-hybrid material according to claim 49 comprising a CNT-Cu wire.

53. A CNT-hybrid material according to claim 49 comprising CNT-A1 sheet.

54. A CNT-hybrid material according to claim 49 comprising CNT-(Ag-coated-Cu) sheet.

55. A CNT-hybrid material according to claim 49 comprising CNT-Si sheet.

56. A CNT-hybrid material according to claim 49 comprising a magnetic CNT-Fe material.

57. A CNT-hybrid material according to claim 49 comprising CNT-nitinol sheet.

58. A CNT-hybrid material according to claim 49 comprising CNT-Y-X, wherein Y is selected from carbon nanofiber (CNF), carbon microfiber (CMF), and

59. A CNT-hybrid material according to claim 49 comprising a CNT-X material, wherein X is selected from the particles set forth in column 1 of Table 3.

60. The CNT-hybrid material according to claim 49, wherein X is selected from one or more of lithium, sodium, potassium, rubidium, cesium, and francium, and, prior to removal from the harvest box, the CNT-X material is coated with a dialetric coating.

61. The CNT-hybrid material according to claim 49, wherein X is selected from one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag and Cd.

62. A fuel injector for injecting fuel into a pyrolytic reactor for gas phase assembly of CNT-hybrid materials, the injector comprising a first nozzle for delivery of carrier gas at a first flow rate, and a second nozzle for delivery of fuel at a second flow rate, said first and second nozzles merging at a single outlet such that mixing of carrier gas and fuel occurs external to the outlet, further wherein the second nozzle comprises a positive displacement mechanism for independent control of the second flow rate.

63. The fuel injector according to claim 62, wherein the positive displacement

mechanism comprises a syringe.