IP Library Granted Patent US 8,709,374
Granted Patent B2
US 8,709,374 · App. 12/026,868 · Granted Apr 29, 2014

Methods for the production of aligned carbon nanotubes and nanostructured material containing the same

Inventors: Christopher H. Cooper (Windsor, VT); Hai-Feng Zhang (Winchester, MA); Richard Czerw (Clemmons, NC)
Assignee: Seldon Technologies, LLC
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Quick Facts
Patent No.
US 8,709,374
App. No.
12/026,868
Granted
Apr 29, 2014
Kind
B2
Abstract

Disclosed herein is a scaled method for producing substantially aligned carbon nanotubes by depositing onto a continuously moving substrate, (1) a catalyst to initiate and maintain the growth of carbon nanotubes, and (2) a carbon-bearing precursor. Products made from the disclosed method, such as monolayers of substantially aligned carbon nanotubes, and methods of using them are also disclosed.

Claims (59)

1. A method for producing substantially aligned carbon nanotubes, said method comprising:

depositing onto a continuously moving substrate,

(1) a catalyst support,

(2) a catalyst on the catalyst support to form a catalyst layer and to initiate and maintain the growth of carbon nanotubes, and

(3) a carbon-bearing precursor on the catalyst layer, wherein the carbon-bearing precursor is preheated by a delivery manifold prior to being introduced into the CVD reactor; and

growing nanotubes inside of a chemical vapor deposition (CVD) reactor at conditions that promote the growth of substantially aligned carbon nanotubes on the moving substrate, wherein said catalyst support is treated prior to depositing said catalyst thereon.

2. The method of claim 1 , wherein the moving substrate is a flexible ribbon, ridged cylindrical, or ring.

3. The method of claim 1 , wherein the moving substrate comprises platinum, palladium, iridium, iron, cobalt, nickel, chromium, carbon, silicon, aluminum, magnesium, carbon, and combinations, alloys and oxides thereof.

4. The method of claim 1 , wherein the moving substrate comprises at least one of fibers, fabrics, mesh, sheets, wafers, cylinders, or ring plates.

5. The method of claim 1 , further comprising depositing a catalyst promotion material prior to depositing said catalyst material.

6. The method of claim 5 , wherein the catalyst promotion material comprises sulfur, water vapor, hydrogen gas, deuterium gas, oxygen, fluorine, helium, argon, ammonium, nitrogen or combinations thereof.

7. The method of claim 1 , wherein the depositing at least one of (2) or (3) is performed using laminar flow conditions.

8. The method of claim 1 , wherein the carbon-bearing precursor comprises CH 4 , C 2 H 4 , C 2 H 2 , CO 2 , CO, or combinations thereof.

9. The method of claim 1 , wherein the depositing of at least one of (2) or (3) in the CVD reactor is performed using at least one technique chosen from chemical vapor deposition, plasma enhanced chemical vapor deposition, physical vapor deposition, plasma enhanced physical vapor deposition, or combinations thereof.

10. The method of claim 1 , wherein the substantially aligned carbon nanotubes comprise hollow multi-walled nanotubes, bamboo multi-walled nanotubes, double-walled nanotubes, single-walled nanotubes, nano-spirals, or any combination thereof.

11. The method of claim 1 , wherein the substantially aligned carbon nanotubes form at least a monolayer of carbon nanotubes.

12. The method of claim 1 , wherein the conditions that promote the growth of substantially aligned carbon nanotubes include a temperature ranging from 600 to 1,100 degrees Celsius.

13. The method of claim 1 , wherein the conditions that promote the growth of substantially aligned carbon nanotubes include the deposition of carbon bearing precursor at a flow rate per unit substrate surface ranging from 10 ml/(cm 2 min) to 400 ml/(cm 2 min).

14. The method of claim 1 , wherein the catalyst comprises iron, cobalt, nickel, platinum, lead, palladium, copper, gold, or any combination or alloy thereof.

15. The method of claim 1 , wherein the catalyst comprises a particle having diameter ranging from 0.7 nm to 50 nm.

16. The method of claim 1 , wherein the moving substrate is moving at a speed sufficient to grow said carbon nanotubes to a length ranging from 100 um to 20 cm.

17. The method of claim 1 , wherein the catalyst support comprises a compound selected from aluminum oxides, silicon oxides, titanium oxides, and combinations thereof.

18. The method of claim 1 , wherein the catalyst support is treated with a plasma etch or chemical clean prior to depositing said catalyst.

19. A method for producing substantially aligned carbon nanotubes, said method comprising depositing onto a semi-continuous or continuously moving substrate:

(1) a catalyst support,

(2) a catalyst on the catalyst support to form a catalyst layer and to initiate and maintain the growth of carbon nanotubes, said catalyst comprising iron, cobalt, nickel, platinum, lead, palladium, copper, gold, or any combination or alloy thereof; and

(3) a carbon-bearing precursor on the catalyst layer at a flow rate per unit substrate surface ranging from 10 ml/(cm 2 min) to 400 ml/(cm 2 min); and

growing nanotubes inside of a chemical vapor deposition (CVD) reactor at a temperature ranging from 600 to 1,100 degrees Celsius, wherein said substrate comprises a flexible or rigid tape, wire, ribbon, cylindrical, or ring substrate of platinum, palladium, iridium, iron, cobalt, nickel, chromium, carbon, silicon, aluminum, magnesium carbon, combinations, alloys or oxides thereof.

20. The method of claim 19 , wherein the catalyst support comprises a compound selected from aluminum oxides, silicon oxides, titanium oxides, and combinations thereof, wherein said catalyst support is treated with a plasma etch or chemical clean prior to depositing said catalyst.

21. A method for producing substantially aligned carbon nanotubes, said method comprising:

depositing onto a continuously moving substrate,

(1) a catalyst support,

(2) a catalyst on the catalyst support to form a catalyst layer and to initiate and maintain the growth of carbon nanotubes, and

(3) a carbon-bearing precursor on the catalyst layer; and

growing nanotubes inside of a chemical vapor deposition (CVD) reactor at conditions that promote the growth of substantially aligned carbon nanotubes on the moving substrate, wherein said catalyst support is treated prior to depositing said catalyst thereon and the depositing of at least one of (2) or (3) in the CVD reactor is performed using at least one technique chosen from chemical vapor deposition, plasma enhanced chemical vapor deposition, physical vapor deposition, plasma enhanced physical vapor deposition, or combinations thereof.

22. A method for producing substantially aligned carbon nanotubes, said method comprising:

depositing onto a continuously moving substrate,

(1) a catalyst support,

(2) a catalyst on the catalyst support to form a catalyst layer and to initiate and maintain the growth of carbon nanotubes, and

(3) a carbon-bearing precursor on the catalyst layer; and

growing nanotubes inside of a chemical vapor deposition (CVD) reactor at conditions that promote the growth of substantially aligned carbon nanotubes on the moving substrate include the deposition of carbon bearing precursor at a flow rate per unit substrate surface ranging from 10 ml/(cm 2 min) to 400 ml/(cm 2 min), wherein said catalyst support is treated prior to depositing said catalyst thereon.

23. The method of claim 22 , further comprising depositing a catalyst promotion material prior to depositing said catalyst material.

24. The method of claim 22 , wherein the depositing at least one of (2) or (3) is performed using laminar flow conditions.

25. The method of claim 22 , wherein the carbon-bearing precursor comprises CH 4 , C 2 H 4 , C 2 H 2 , CO 2 , CO, or combinations thereof.

26. The method of claim 22 , wherein the substantially aligned carbon nanotubes comprise hollow multi-walled nanotubes, bamboo multi-walled nanotubes, double-walled nanotubes, single-walled nanotubes, nano-spirals, or any combination thereof.

27. The method of claim 22 , wherein the substantially aligned carbon nanotubes form at least a monolayer of carbon nanotubes.

28. The method of claim 22 , wherein the carbon-bearing precursor is preheated by a delivery manifold prior to being introduced into the CVD reactor.

29. A method for producing substantially aligned carbon nanotubes, said method comprising:

depositing onto a continuously moving substrate,

(1) a catalyst support,

(2) a catalyst on the catalyst support to form a catalyst layer and to initiate and maintain the growth of carbon nanotubes, wherein the catalyst comprises a particle having diameter ranging from 0.7 nm to 50 nm, and

(3) a carbon-bearing precursor on the catalyst layer; and

growing nanotubes inside of a chemical vapor deposition (CVD) reactor at conditions that promote the growth of substantially aligned carbon nanotubes on the moving substrate, wherein said catalyst support is treated prior to depositing said catalyst thereon.

30. A method for producing substantially aligned carbon nanotubes, said method comprising:

depositing onto a continuously moving substrate, wherein the moving substrate is moving at a speed sufficient to grow said carbon nanotubes to a length ranging from 100 um to 20 cm,

(1) a catalyst support,

(2) a catalyst on the catalyst support to form a catalyst layer and to initiate and maintain the growth of carbon nanotubes, and

(3) a carbon-bearing precursor on the catalyst layer; and

growing nanotubes inside of a chemical vapor deposition (CVD) reactor at conditions that promote the growth of substantially aligned carbon nanotubes on the moving substrate, wherein said catalyst support is treated prior to depositing said catalyst thereon.

Assignments (5)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 23, 2016
From: SELDON TECHNOLOGIES, INC.
To: MULTIPURE INTERNATIONAL
Reel/Frame 037801/0715 →
SECURITY AGREEMENT Recorded Apr 24, 2013
From: SELDON TECHNOLOGIES, INC.
To: ECOGLOBAL HOLDINGS, INC.
Reel/Frame 030291/0160 →
RELEASE OF SECURITY INTEREST Recorded Nov 7, 2012
From: ECOGLOBAL HOLDINGS, INC.
To: SELDON TECHNOLOGIES, INC.
Reel/Frame 029254/0193 →
SECURITY AGREEMENT Recorded Apr 11, 2012
From: SELDON TECHNOLOGIES, INC.
To: ECOGLOBAL HOLDINGS, INC.
Reel/Frame 028024/0766 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 8, 2008
From: COOPER, CHRISTOPHER H.; ZHANG, HAI-FENG; CZERW, RICHARD
To: SELDON TECHNOLOGIES, LLC
Reel/Frame 020949/0434 →
Continuity (2)
Provisional Application 60899868 · Feb 7, 2007
Related Publication 20120251432A1 · Oct 4, 2012