Methods and apparatuses for producing dispersed nanostructures

• US 9,987,608 B2
• Filed: 09/18/2015
• Issued: 06/05/2018
• Est. Priority Date: 09/19/2014
• Status: Active Grant

• Current Assignee: Nanosynthesis Plus, Ltd.
• Original Assignee: Nanosynthesis Plus, Ltd.
• Inventors: Pigos, Elena
• Primary Examiner(s): McGinty, Douglas J
• Application Number:
  US14/858,786
• Publication Number:
  US 20160082404A1
• Time in Patent Office: 991 Days
• Field of Search: 427446, 422129, 422211
• CPC Class Codes: B01J 13/0095 Preparation of aerosols
• CPC Class Codes: B01J 19/2415 Tubular reactors
• CPC Class Codes: B01J 8/125 with multiple sections one above the other separated by distribution aids, e.g. reaction and regeneration sections
• CPC Class Codes: B01J 8/24 according to "fluidised-bed" technique B01J8/20 takes precedence
• CPC Class Codes: C09K 5/08 Materials not undergoing a change of physical state when used C09K5/16, C09K5/20 take precedence
• CPC Class Codes: H01B 1/04 mainly consisting of carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01B 1/06 mainly consisting of other non-metallic substances

Abstract

Methods and apparatuses are provided for the production of homogeneous dispersions of nanostructures within a matrix, which may be used as precursors of carbon-reinforced or boron nitride-reinforced composite materials. An apparatus for producing a nanostructure dispersion comprises a reactor and a mixing chamber, wherein the reactor is configured to produce an aerosol of nanostructures and is in fluidic communication with the mixing chamber. A matrix material is provided in the mixing chamber, and the aerosol of nanostructures can disperse into the matrix material to form a nanostructure dispersion. The apparatus may further comprise a matrix tank comprising a matrix material, wherein the matrix material is transferred to the mixing chamber. An aerosol of matrix particles may be produced from the matrix material and provided in the mixing chamber, so as to produce a fine dispersion of nanostructures in the matrix. The apparatus may be configured to continuously produce a nanostructure dispersion.

Claims

1. A method for producing a nanostructure dispersion, the method comprising:

providing a reactor and a mixing chamber, wherein;

the reactor is in fluidic communication with the mixing chamber;

the reactor comprises;

a nanostructure growth zone; and

a catalyst particle growth zone, and

the mixing chamber comprises;

a base of the mixing chamber, comprising a plurality of pores; and

a mixer;

producing an aerosol of nanostructures in the reactor;

providing a matrix material in the mixing chamber;

transferring the aerosol of nanostructures from the reactor to the mixing chamber;

introducing a first carrier gas into the mixing chamber through the plurality of pores of the base of the mixing chamber; and

using the mixer to disperse the aerosol of nanostructures into the matrix material, thereby producing the nanostructure dispersion.

2. The method of claim 1, further comprising:

producing an aerosol of matrix particles from the matrix material;

providing the aerosol of matrix particles in the mixing chamber; and

dispersing the aerosol of nanostructures into the matrix material comprising the aerosol of matrix particles, thereby producing the nanostructure dispersion.

3. The method of claim 1, wherein the mixer comprises a mechanical stirrer, a magnetic stirrer, a ball miller, a sonicator, or a combination thereof.

4. The method of claim 1, further comprising transferring the nanostructure dispersion to a collector as an aerosol.

5. The method of claim 1, further comprising:

providing a matrix tank in fluidic communication with the mixing chamber, wherein the matrix tank comprises the matrix material; and

transferring the matrix material from the matrix tank to the mixing chamber.

6. The method of claim 5, further comprising:

producing an aerosol of matrix particles from the matrix material in the matrix tank;

providing a tangential injection of a carrier gas to the matrix tank, thereby creating a vortex of the aerosol of matrix particles; and

transferring the matrix material comprising the vortex of the aerosol of matrix particles from the matrix tank to the mixing chamber.

7. The method of claim 1, further comprising producing a plurality of catalyst particles in the catalyst particle growth zone of the reactor.

8. The method of claim 7, comprising producing the aerosol of nano structures by decomposing a carbon precursor at the plurality of catalyst particles.

9. The method of claim 1, further comprising producing an aerosol of matrix particles in the mixing chamber by applying a tangential vortex to the mixing chamber, vertically shaking the mixing chamber, introducing the carrier gas into the mixing chamber, or a combination thereof.

10. The method of claim 5, further comprising:

providing a plurality of pores through a base of the matrix tank;

introducing a second carrier gas into the matrix tank through the plurality of pores; and

producing an aerosol of matrix particles in the second carrier gas in the mixing chamber.

11. The method of claim 1, wherein:

the aerosol of nano structures in the reactor is produced continuously;

the matrix material in the mixing chamber is provided continuously; and

the aerosol of nano structures is continuously transferred from the reactor to the mixing chamber,

thereby continuously producing the nanostructure dispersion.

12. The method of claim 1, wherein the reactor comprises a plurality of zones having different temperatures.

13. The method of claim 12, wherein the catalyst particle growth zone is held at a temperature of 400°

C. to 1000°

C., and the nanostructure growth zone is held at a temperature of 800°

C. to 1300°

C.

14. The method of claim 1, wherein the matrix material is a solid powder or liquid.

15. The method of claim 1, wherein the aerosol of nanostructures is transferred directly from the reactor to the mixing chamber.

16. The method of claim 1, further comprising transferring the nanostructure dispersion to a collector.

17. The method of claim 1, further comprising:

providing an injector in fluidic communication with the reactor; and

introducing a catalyst from the injector into the reactor.

18. The method of claim 17, wherein the catalyst is introduced from the injector into the reactor as a liquid, spray, or aerosol.

19. The method of claim 17, wherein the catalyst comprises a plurality of colloidal particles.

20. The method of claim 1, further comprising:

providing an injector in fluidic communication with the reactor; and

introducing a catalyst precursor, a promoter, or a combination thereof from the injector into the reactor.

21. The method of claim 5, wherein the matrix tank is positioned below the mixing chamber.

22. The method of claim 5, wherein the matrix tank is positioned above the reactor.

23. The method of claim 5, wherein the matrix tank is positioned below the reactor.

24. The method of claim 17, wherein the injector is positioned above the reactor.

25. The method of claim 17, wherein the injector is positioned below the reactor.

26. The method of claim 1, wherein the mixing chamber is positioned above the reactor.

27. The method of claim 5, wherein the mixing chamber is positioned above the reactor.

28. The method of claim 17, wherein the mixing chamber is positioned above the reactor.

29. The method of claim 1, wherein the mixing chamber is positioned below the reactor.

30. The method of claim 5, wherein the mixing chamber is positioned below the reactor.

31. The method of claim 17, wherein the mixing chamber is positioned below the reactor.

32. The method of claim 20, wherein the catalyst precursor is selected from a metallocene, a metal acetylacetonate, a metal phthalocyanine, a metal porphyrin, a metal salt, a metalorganic compound, or a combination thereof.

33. The method of claim 20, wherein the catalyst precursor is selected from ferrocene, nickelocene, cobaltocene, molybdenocene, ruthenocene, iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, molybdenum acetylacetonate, ruthenium acetylacetonate, iron phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine, iron porphyrin, nickel porphyrin, cobalt porphyrin, an iron salt, a nickel salt, a cobalt salt, a molybdenum salt, a ruthenium salt, or a combination thereof.

34. The method of claim 20, wherein the promoter is selected from thiophene, carbon disulfide or any other sulfur containing compound, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, or a combination thereof.

35. The method claim 1, wherein the reactor is positioned at an angle of from 60 to 180°

relative to the mixing chamber.

36. The method of claim 1, further comprising introducing a carbon precursor into the reactor.

37. The method of claim 36, wherein the producing of the aerosol of nano structures comprises decomposing the carbon precursor.

38. The method of claim 36, wherein the carbon precursor is a hydrocarbon, an alcohol, an ester, a ketone, an aromatic, an aldehyde, or a combination thereof.

39. The method claim 36, wherein the carbon precursor is selected from methane, ethane, acetylene, ethylene, ethanol, carbon monoxide, carbon dioxide, naphthalene, xylene, or a combination thereof.

40. The method of claim 36, further comprising mixing the carbon precursor with a second carrier gas prior to introducing the carbon precursor into the reactor.

41. The method of claim 40, wherein the second carrier gas is an inert gas.

42. The method claim 40, wherein the second carrier gas comprises a gas selected from argon, hydrogen, helium, nitrogen, or a combination thereof.

43. The method of claim 7, wherein the mean diameter of the plurality of catalyst particles is from 0.5 nm to 5 nm.

44. The method of claim 7, wherein the mean diameter of the plurality of catalyst particles is from 5 nm to 20 nm.

45. The method of claim 7, wherein the plurality of catalyst particles comprise a transition metal.

46. The method of claim 7, wherein the plurality of catalyst particles comprise a material selected from a d-block transition metal, an f-block transition metal, or a combination thereof.

47. The method of claim 46, wherein the d-block transition metal is selected from iron, nickel, cobalt, gold, silver, or a combination thereof.

48. The method of claim 7, wherein the catalyst particles are supported on a catalyst support, and wherein the catalyst support is selected from alumina, silica, zirconia, magnesia, or zeolites.

49. The method of claim 48, wherein the catalyst support is the same as or different from the matrix material.

50. The method of claim 8, wherein the decomposing is selected from thermal decomposing or catalytic decomposing.

51. The method of claim 10, wherein the second carrier gas is an inert gas.

52. The method of claim 10, wherein the second carrier gas comprises a gas selected from argon, hydrogen, helium, nitrogen, or a combination thereof.

53. The method of claim 1, wherein the nanostructure dispersion is a homogeneous mixture.

54. The method claim 53, wherein the homogeneous mixture comprises a mixture of individual nanostructures and a plurality of nanostructure bundles, wherein the plurality of nanostructure bundles comprises a plurality of nanotube bundles.

55. The method of claim 53, wherein the homogeneous mixture comprises a plurality of individual nanostructures, wherein a nanostructure is an individual nanostructure if the nanostructure is physically separated from other nanostructures.

56. The method of claim 55, wherein from 20% to 50% of the nanostructures are individual nano structures.

57. The method of claim 56, further comprising non-individual nano structures, wherein at least 80% of the non-individual nanostructures are comprised in a plurality of nanostructure bundles.

58. The method of claim 57, wherein the plurality of nanostructure bundles comprises a plurality of nanotube bundles.

59. The method of claim 57, wherein each of the nanostructure bundles comprises an average of 30 or fewer nano structures.

60. The method of claim 57, wherein each of the nanostructure bundles comprises an average of 15 or fewer nanostructures.

61. The method of claim 57, wherein the nanostructure bundles have an average diameter of 1-50 nm.

62. The method of claim 1, wherein the aerosol of nanostructures comprises carbon nanotubes or carbon fibers.

63. The method of claim 62, wherein the carbon nanotubes are single walled carbon nanotubes or multi walled carbon nanotubes.

64. The method of claim 1, wherein the nano structure dispersion is continuously produced.

65. The method of claim 5, further comprising:

continuously transferring the aerosol of nano structures from the reactor to the mixing chamber; and

continuously transferring the matrix material into the mixing chamber from the matrix tank.

66. The method of claim 5, further comprising:

continuously producing an aerosol of matrix particles from the matrix material; and

continuously transferring the matrix material comprising the aerosol of matrix particles into the mixing chamber from the matrix tank.

67. The method of claim 65, further comprising:

continuously producing an aerosol of matrix particles from the matrix material; and

continuously transferring the matrix material comprising the aerosol of matrix particles into the mixing chamber from the matrix tank.

68. The method of claim 1, further comprising:

continuously producing an aerosol of matrix particles from the matrix material;

continuously providing the aerosol of matrix particles in the mixing chamber; and

dispersing the aerosol of nano structures into the matrix material comprising the aerosol of matrix particles.

69. The method of claim 1, wherein the matrix material comprises a material selected from a carbon allotrope, a metal, an alloy, a metal oxide, a metal carbonate, silicon carbide, a ceramic, a polymer, a cement, or a combination thereof.

70. The method of claim 1, wherein the matrix material comprises a liquid matrix material selected from:

a melted polymer selected from melted polyester, epoxy, polyimide, organosilicone, bismaleimide, phenol-formaldehyde, polysulfone (PSU), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyamide-imide (PAI), nylon, teflon, polystyrene, or polyethylene;

a resin or a solution thereof;

a molten metal selected from molten aluminum, magnesium, titanium, nickel, copper, niobium, cobalt, lead, steel, or beryllium;

a metal alloy;

a carbon pitch;

a solution of dispersed graphene or graphene oxide sheets;

a tar;

a cement;

an asphalt;

an ionic liquid selected from an imidazolium-based liquid;

an organic solvent selected from N,N-dimethylformamide or n-methylpyrrolidone;

or

a combination thereof.

71. The method of claim 1, wherein producing the aerosol of nanostructures is performed at a temperature selected from 950°

C. to 1300°

C.

72. The method of claim 1, wherein the reactor is held at a temperature of 950°

C. to 1300°

C.

73. The method of claim 10, wherein the rate of flow of the second carrier gas into the mixing chamber has a rate selected from 1000 sccm to 2500 sccm.

74. The method of claim 10, wherein the rate of flow of the second carrier gas into the mixing chamber has a rate selected from 1500 sccm to 2500 sccm.

75. The method of claim 1, wherein the rate of production of the aerosol of nanostructures is constant and wherein the mass percent of the nanostructures in the nanostructure dispersion is controlled by modulating the quantity of matrix material in the mixing chamber.

76. The method of claim 75, wherein the nanostructures in the nanostructure dispersion are produced at a rate of 0.1 g/hr to 10 g/hr.

77. The method of claim 1, wherein the rate of production of the aerosol of nanostructures is constant and wherein the mass percent of the nanostructures in the nanostructure dispersion is controlled by modulating the duration of the production of the aerosol of nano structures.

78. The method of claim 77, wherein the nanostructures in the nanostructure dispersion are produced at a rate of 0.1 g/hr to 10 g/hr.

79. The method of claim 1, wherein the aerosol of nanostructures comprises boron nitride nanotubes (BNNTs).