Process and apparatus for producing composite material that includes carbon nanotubes

• US 8,709,539 B2
• Filed: 02/02/2010
• Issued: 04/29/2014
• Est. Priority Date: 02/17/2009
• Status: Active Grant

• Current Assignee: Masuoka Ceramic Materials Co., Ltd., Meijo Nano Carbon Co., Ltd.
• Original Assignee: Masuoka Ceramic Materials Co., Ltd., Meijo Nano Carbon Co., Ltd., Meijo University
• Inventors: Hashimoto, Takeshi, Ando, Yoshinori, Kumar, Mukul, Kurauchi, Norio, Masuoka, Hirotaka, Kagohashi, Akira
• Primary Examiner(s): CHEN, BRET P
• Application Number:
  US13/201,747
• Publication Number:
  US 20120009344A1
• Time in Patent Office: 1,547 Days
• Field of Search: 427/249.1, 427/255.5, 118/724, 118/729
• US Class Current: 427/249.1
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/462 Ruthenium
• CPC Class Codes: B01J 23/70 of the iron group metals or copper
• CPC Class Codes: B01J 23/745 Iron
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 29/064 containing iron group metals, noble metals or copper
• CPC Class Codes: B01J 29/072 Iron group metals or copper
• CPC Class Codes: B01J 29/146 Y-type faujasite
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/393 Metal or metal oxide crystallite size
• CPC Class Codes: B01J 35/651 50-500 nm
• CPC Class Codes: B01J 35/653 500-1000 nm
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A process and an apparatus for producing a composite material utilize a rotatable hollow body that is inclined with an upstream side being higher than a downstream side. A reaction zone is defined within an elongated chamber in the hollow body. Protrusions inwardly extend from an inner peripheral wall of the hollow body adjacent to the reaction zone. Base material is input into the chamber via a base material introduction port and a carbon source vapor is input into the chamber via a carbon source supply port. A heater heats the reaction zone to a temperature at which carbon nanotubes form on the base material from the carbon source vapor. The protrusions catch base material disposed on the inner peripheral wall of the hollow body when the hollow body rotates and then drop the base material through the reaction zone so that the base material contacts the carbon source vapor.

Claims

1. A process for producing a composite material having carbon nanotubes present on a surface of a base material using an apparatus that comprises:

a hollow body defining an elongated chamber that is configured to have a gas flow through it and is heatable, wherein the hollow body is rotatable about a major axis and is inclined such that an upstream side on one end of the hollow body in the direction of the major axis is higher than a downstream side of the hollow body on the other end,

an introduction site configured to input the base material into the chamber,

a supply site configured to input a carbon source vapor into the chamber, the introduction site and the supply site being arranged so that contact between the base material and the carbon source vapor occurs in a reaction zone disposed in at least one upstream portion of the elongated chamber in the direction of the major axis, and

a plurality of ribs disposed on at least one inner peripheral wall of the hollow body at least within a portion of the elongated chamber adjacent to the reaction zone,

wherein the process comprises;

inputting the base material, which already has a catalyst disposed on its surface, into the chamber of the hollow body via the introduction site;

supplying the carbon source vapor, which is comprised of a carbon source capable of forming the carbon nanotubes on the base material, via the supply site, and

moving the base material from the upstream side to the downstream side by rotating the hollow body about the major axis, wherein base material disposed on the at least one inner peripheral wall is caught on the ribs and is lifted up and then is dropped such that the base material and the carbon source vapor make contact in the reaction zone.

2. The process according to claim 1, further comprising:

supplying the carbon source vapor directly into the reaction zone, and

preventing the carbon source vapor from flowing out to an upstream side or to a downstream side of the reaction zone by supplying a non-oxidizing gas into the chamber from locations upstream and downstream of the reaction zone and by discharging gas from the reaction zone or from a location in close proximity thereto.

3. The process according to claim 1, wherein the base material comprises an inorganic base material.

4. The process according to claim 3, wherein the inorganic base material comprises an inorganic porous material.

5. The process according to claim 1, wherein the base material comprises a carbonaceous base material comprised of a carbonaceous material.

6. The process according to claim 5, wherein the base material further comprises an inorganic base material.

7. The process according to claim 5, wherein the carbonaceous base material comprises carbon fibers having a mean diameter of 100 μ

m or less, and wherein the process produces a composite carbonaceous fiber material having carbon nanotubes present on the surface of the carbon fibers.

8. The process according to claim 5, wherein the carbonaceous base material comprises carbon black having a mean particle diameter of 1 μ

m or less, and wherein the process produces a composite carbonaceous powder material having carbon nanotubes are present on the surface of the carbon black.

9. The process according to claim 5, wherein the catalyst comprises iron and cobalt as a catalyst metal component, and the catalyst metal component comprises 1-30% by weight of a total weight of the carbonaceous base material and the catalyst metal component disposed the surface of the carbonaceous base material.

10. The process according to claim 9, further comprising:

supplying the carbon source vapor directly into the reaction zone, and

preventing the carbon source vapor from flowing out to an upstream side or to a downstream side of the reaction zone by supplying a non-oxidizing gas into the chamber from locations upstream and downstream of the reaction zone and by discharging gas from the reaction zone or from a location in close proximity thereto,

wherein the base material comprises at least one of an inorganic base material and a carbonaceous base material comprised of a carbonaceous material,

the carbon source is a liquid comprising camphor dissolved in an alcohol-based solvent, and

the carbon source vapor comprises camphor vapor.

11. The process according to claim 1, wherein the carbon source comprises a carbon-containing material in a form that is capable of producing carbon nanotubes in a chemical vapor deposition process, the carbon-containing material being a solid at room temperature.

12. The process according to claim 11, wherein the carbon-containing material comprises camphor.

13. The process according to claim 12, wherein the carbon source is a liquid comprising camphor dissolved in an alcohol-based solvent, and wherein the carbon source vapor comprises camphor vapor.

14. The method according to claim 1, wherein the ribs extend in the direction of the major axis of the hollow body and are disposed at intervals in a circumferential direction of the hollow body.

15. The method according to claim 1, wherein the ribs project from the at least one inner peripheral wall of the hollow body and have a first end spaced from a second end in the direction of the major axis.

16. A process for producing a composite material having carbon nanotubes present on a surface of a base material, the base material having a catalyst on a surface, the process comprising:

providing an apparatus that includes a hollow body defining an elongated chamber configured to have a gas flow therethrough and being heatable, the hollow body being mounted for rotation about a major axis and being inclined, the apparatus including an introduction site configured for inputting the base material into the chamber and a supply site configured for inputting a carbon source vapor into the chamber, the introduction site and the supply site being arranged so that contact between the base material and the carbon source vapor occurs in a reaction zone, and the apparatus having a plurality of ribs disposed on at least one inner peripheral wall of the hollow body at least within a portion of the elongated chamber adjacent to the reaction zone,

inputting the base material into the chamber of the hollow body via the introduction site;

supplying the carbon source vapor via the supply site, and

rotating the hollow body about the major axis to move the base material along the inclined hollow body, to lift the base material on the ribs and to drop the base material from the ribs such that the base material and the carbon source vapor make contact in the reaction zone.

17. An apparatus capable of producing a composite material having carbon nanotubes present on a surface of a base material, comprising:

a hollow body rotatable about a major axis and disposed such that the major axis is inclined with an upstream side of the hollow body on one end of the major axis being higher than a downstream side of the hollow body on the other end,

an elongated chamber comprising a reaction zone defined within the hollow body over at least one longitudinal section of the elongated chamber along the major axis,

a plurality of ribs disposed on at least one inner peripheral wall of the hollow body in at least a portion of the elongated chamber that is adjacent to the reaction zone,

an input device configured to input the base material into the chamber via a base material introduction port,

a carbon source vapor supply device configured to supply a carbon source vapor into the chamber via a carbon source supply port, and

a heater configured to heat at least the reaction zone to a temperature at which carbon nanotubes form from the carbon source vapor,

wherein the ribs are configured to catch base material disposed on the inner peripheral wall of the hollow body when the hollow body rotates and then drop the base material through the reaction zone so that the base material contacts the carbon source vapor.

18. The apparatus according to claim 17, wherein the ribs extend in the direction of the major axis of the hollow body, and are disposed at intervals in a circumferential direction of the hollow body.

19. The apparatus according to claim 17, wherein the carbon source supply port is disposed in the reaction zone or in close proximity thereto.

20. The apparatus according to claim 17, wherein the carbon source vapor supply device comprises a carbon source introduction pipe that at least partially extends through the reaction zone and is continuous with the carbon source supply port.

21. The apparatus according to claim 17, further comprising:

a gas supply unit configured to supply non-oxidizing gas into the chamber from a first gas supply port disposed upstream of the reaction zone and from a second gas supply port disposed downstream of the reaction zone, and

a gas exhaust unit configured to discharge gas in the chamber from a gas venting port disposed in the reaction zone or in close proximity thereto.

22. The apparatus according to claim 21, wherein the carbon source supply port and the base material introduction port are each disposed in an upstream region of the reaction zone or in proximity to the upstream side thereof, and

the gas venting port is disposed in a downstream region of the reaction zone or in proximity to the downstream side thereof.

23. The apparatus according to claim 17, wherein the carbon source vapor supply device comprises:

a storage tank that stores a liquid carbon source for forming the carbon source vapor, and

a vaporization chamber configured to vaporize the liquid carbon source supplied from the storage tank.

24. The apparatus according to claim 17, wherein the ribs project from the at least one inner peripheral wall of the hollow body and have a first end spaced from a second end in the direction of the major axis.