Glass substrates having carbon nanotubes grown thereon and methods for production thereof

• US 8,784,937 B2
• Filed: 09/12/2011
• Issued: 07/22/2014
• Est. Priority Date: 09/14/2010
• Status: Active Grant

• Current Assignee: Applied NanoStructured Solutions, LLC (Cabot Corporation)
• Original Assignee: Applied NanoStructured Solutions, LLC (Cabot Corporation)
• Inventors: Malet, Brandon K., Shah, Tushar K.
• Primary Examiner(s): TUROCY, DAVID P
• Application Number:
  US13/230,751
• Publication Number:
  US 20120064332A1
• Time in Patent Office: 1,044 Days
• Field of Search: 427/249.1
• US Class Current: 427/249.3
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 35/58 Fabrics or filaments
• CPC Class Codes: B01J 37/0213 Preparation of the impregnating solution
• CPC Class Codes: B05D 2203/35 Glass
• CPC Class Codes: B05D 2256/00 Wires or fibres
• CPC Class Codes: B05D 3/10 by other chemical means
• 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 2202/34 Length
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: C01B 32/164 involving continuous processes
• CPC Class Codes: C03C 17/28 with organic material C03C17/34, C03C17/44 take precedence
• CPC Class Codes: C03C 25/1095 to obtain coated fabrics
• CPC Class Codes: C03C 25/223 by chemical vapour deposition or pyrolysis
• CPC Class Codes: C03C 25/24 Coatings containing organic materials
• CPC Class Codes: C03C 25/44 Carbon, e.g. graphite
• CPC Class Codes: C23C 16/26 Deposition of carbon only
• CPC Class Codes: C23C 16/458 characterised by the method used for supporting substrates in the reaction chamber
• CPC Class Codes: C23C 16/545 for coating elongated substrates
• CPC Class Codes: D01F 9/127 : by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
• CPC Class Codes: Y10S 977/843 : Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/891 : Vapor phase deposition
• CPC Class Codes: Y10T 428/25 : Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Abstract

Methods for growing carbon nanotubes on glass substrates, particularly glass fiber substrates, are described herein. The methods can include depositing a catalytic material or a catalyst precursor on a glass substrate; depositing a non-catalytic material on the glass substrate prior to, after, or concurrently with the catalytic material or catalyst precursor; and exposing the glass substrate to carbon nanotube growth conditions so as to grow carbon nanotubes thereon. The glass substrate, particularly a glass fiber substrate, can be transported while the carbon nanotubes are being grown thereon. Catalyst precursors can be converted into a catalyst when exposed to carbon nanotube growth conditions. The catalytic material or catalyst precursor and the non-catalytic material can be deposited from a solution containing water as a solvent. Illustrative deposition techniques include, for example, spray coating and dip coating.

Claims

1. A carbon nanotube growth process comprising:

depositing a catalyst precursor on a glass substrate, the catalyst precursor being deposited from a solution comprising water as a solvent;

wherein the catalyst precursor is formed from a reaction between at least one transition metal salt and hydrogen peroxide in the solution from which the catalyst precursor is deposited; and

after depositing the catalyst precursor, exposing the glass substrate to carbon nanotube growth conditions so as to grow carbon nanotubes thereon;

wherein the catalyst precursor is converted into a catalyst that is operable for forming carbon nanotubes when exposed to the carbon nanotube growth conditions.

2. The carbon nanotube growth process of claim 1, further comprising:

transporting the glass substrate while the carbon nanotubes are being grown thereon.

3. The carbon nanotube growth process of claim 1, wherein the catalyst precursor comprises a transition metal salt selected from the group consisting of a transition metal nitrate, a transition metal acetate, a transition metal citrate, a transition metal chloride, hydrates thereof, and combinations thereof.

4. The carbon nanotube growth process of claim 3, wherein the transition metal salt is selected from the group consisting of iron (II) nitrate, iron (III) nitrate, cobalt (II) nitrate, nickel (II) nitrate, copper (II) nitrate, iron (II) acetate, iron (III) acetate, cobalt (II) acetate, nickel (II) acetate, copper (II) acetate, iron (II) citrate, iron (III) citrate, iron (III) ammonium citrate, cobalt (II) citrate, nickel (II) citrate, copper (II) citrate, iron (II) chloride, iron (III) chloride, cobalt (II) chloride, nickel (II) chloride, copper (II) chloride, hydrates thereof, and combinations thereof.

5. The carbon nanotube growth process of claim 1, wherein the at least one transition metal salt comprises an iron (II) salt or a hydrate thereof and a cobalt (II) salt or a hydrate thereof.

6. A carbon nanotube growth process comprising:

depositing a catalyst precursor on a glass fiber substrate, the catalyst precursor being deposited from a solution comprising water as a solvent;

wherein the catalyst precursor is formed from a reaction between at least one transition metal salt and hydrogen peroxide in the solution from which the catalyst precursor is deposited;

converting the catalyst precursor into a catalyst that is operable for forming carbon nanotubes when exposed to carbon nanotube growth conditions; and

exposing the glass fiber substrate to carbon nanotube growth conditions while the glass fiber substrate is being transported so as to grow carbon nanotubes thereon.

7. The carbon nanotube growth process of claim 6, wherein the at least one transition metal salt comprises iron (II) acetate or a hydrate thereof and cobalt (II) acetate or a hydrate thereof.

8. The carbon nanotube growth process of claim 6, wherein the catalyst precursor comprises a transition metal salt selected from the group consisting of a transition metal nitrate, a transition metal acetate, a transition metal citrate, a transition metal chloride, hydrates thereof, and combinations thereof.

9. The carbon nanotube growth process of claim 8, wherein the transition metal salt is selected from the group consisting of iron (II) nitrate, iron (III) nitrate, cobalt (II) nitrate, nickel (II) nitrate, copper (II) nitrate, iron (II) acetate, iron (III) acetate, cobalt (II) acetate, nickel (II) acetate, copper (II) acetate, iron (II) citrate, iron (III) citrate, iron (III) ammonium citrate, cobalt (II) citrate, nickel (II) citrate, copper (II) citrate, iron (II) chloride, iron (III) chloride, cobalt (II) chloride, nickel (II) chloride, copper (II) chloride, hydrates thereof, and combinations thereof.

10. A carbon nanotube growth process comprising:

allowing a solution comprising water, hydrogen peroxide, an iron (II) salt or a hydrate thereof, and a cobalt (II) salt or a hydrate thereof to form a catalyst precursor in the solution, the solution comprising water as a solvent;

depositing the solution with the catalyst precursor therein onto a glass fiber substrate;

converting the catalyst precursor into a catalyst that is operable for forming carbon nanotubes upon exposure to carbon nanotube growth conditions; and

exposing the glass fiber substrate to carbon nanotube growth conditions so as to grow carbon nanotubes thereon.

11. The carbon nanotube growth process of claim 10, further comprising:

transporting the glass fiber substrate while the carbon nanotubes are being grown thereon.

12. The carbon nanotube growth process of claim 10, wherein the iron (II) salt comprises iron (II) acetate or a hydrate thereof and the cobalt (II) salt comprises cobalt (II) acetate or a hydrate thereof.

13. The carbon nanotube growth process of claim 10, wherein the catalyst comprises at least an iron-cobalt alloy.

14. The carbon nanotube growth process of claim 10, wherein converting comprises heating the catalyst precursor to form an intermediate catalyst state and exposing the intermediate catalyst state to the carbon nanotube growth conditions to form the catalyst.

15. The carbon nanotube growth process of claim 10, wherein a molar ratio of iron to cobalt ranges from about 5:

1 to about 6;

1.