Nanotube solutions with high concentration and low contamination and methods for purifiying nanotube solutions

• US 10,069,072 B2
• Filed: 09/20/2011
• Issued: 09/04/2018
• Est. Priority Date: 09/20/2010
• Status: Active Grant

• Current Assignee: Sally Smith, ZEON Corporation
• Original Assignee: Nantero Incorporated
• Inventors: Roberts, David A., Sen, Rahul, Kocab, J. Thomas, Smith, Billy, Gu, Feng
• Primary Examiner(s): Jolley, Kirsten
• Application Number:
  US13/825,070
• Publication Number:
  US 20130243954A1
• Time in Patent Office: 2,541 Days
• Field of Search: 427240, 4274211, 252502
• CPC Class Codes: B01D 21/262 by using a centrifuge
• CPC Class Codes: B01D 2251/90 Chelants
• CPC Class Codes: B01D 2251/902 EDTA
• CPC Class Codes: B01D 37/00 Processes of filtration processes specially adapted for filtering gases B01D46/00
• CPC Class Codes: B05D 1/005 Spin coating
• CPC Class Codes: B05D 1/02 performed by spraying
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C02F 1/36 ultrasonic vibrations
• CPC Class Codes: C02F 1/38 by centrifugal separation
• CPC Class Codes: C02F 1/444 by ultrafiltration or microfiltration
• CPC Class Codes: C02F 1/5236 using inorganic agents
• CPC Class Codes: C02F 1/683 by addition of complex-forming compounds
• CPC Class Codes: C02F 2101/20 Heavy metals or heavy metal compounds
• CPC Class Codes: H10K 85/221 Carbon nanotubes

Abstract

Solutions of carbon nanotubes and methods for purifying the solutions are provided. The methods include mixing, for example, at least one complexing agents, at least one ionic species, and/or at least one buffer oxide etch (BOE) with a liquid medium containing carbon nanotubes and different types of contaminants, such as metal impurities, amorphous carbon, and/or silica particles, and performing a filtration process to the liquid medium so as to remove or reduce the contaminants in the liquid medium. As a result, carbon nanotube solutions of low contaminants are produced. In some embodiments, the solutions of this disclosure include a high concentration of carbon nanotubes and are substantially free from metal, amorphous carbon, and/or silica impurities.

Claims

1. A method for producing a nanotube solution, comprising:

dispersing functionalized nanotube;

materials in a liquid medium in a first operation, wherein at least a portion of said functionalized nanotube materials have surface carboxylic acid functional groups bound with binary metal counter ions;

mixing at least one complexing agent with the liquid medium to complex and remove said binary metal counter ions from said functional groups of said functionalized nanotube materials in a second operation; and

performing a filtration process to the liquid medium so as to remove the complexed binary metal ions in the liquid medium in a third operation;

wherein said second operation is performed subsequent to said first operation and prior to said third operation.

2. The method of claim 1, further comprising sonicating the liquid medium after mixing the at least one complexing agent with the liquid medium.

3. The method of claim 2, wherein sonicating the liquid medium comprises sonicating the liquid medium in a chilled sonication bath having a temperature of about 5-25°

C.

4. The method of claim 1, wherein the filtration process is a cross flow filtration process using a filtration membrane having a pore size of about 0.2 to 2 microns.

5. The method of claim 1, further comprising repeating the cross flow filtration process until concentrations of individual metal impurities are below a predetermined concentration.

6. The method of claim 5, wherein the predetermined concentration is 25 parts per billion (ppb).

7. The method of claim 1, further comprising repeating the mixing step and the performing step until a concentration of individual metal impurities is below a predetermined concentration.

8. The method of claim 7, wherein the predetermined concentration is 25 part per billion.

9. The method of claim 1, further comprising performing a centrifugation process to the liquid medium so as to remove amorphous carbon and larger particles.

10. The method of claim 1, wherein mixing the at least one complexing agent with the liquid medium includes adding a chelating agent in the liquid medium.

11. The method of claim 10, wherein adding the chelating agent comprises adding in the liquid medium one or more of a first amount of ethylenediaminetetraacetic acid (EDTA), a second amount of diethylene triamine pentaacetic acid (DTPA), and a third amount of etidronic acid.

12. A solution, comprising:

a liquid medium; and

a plurality of functionalized nanotubes dispersed in the liquid medium, wherein at least a portion of said functionalized nanotubes have surface carboxylic acid functional groups, whereby binary metal counter ions on said functional groups have been complexed with a complexing agent and removed from the functional groups;

wherein the liquid medium comprises composite molecules of said complexed binary metals complexed with said complexing agent.

13. The solution of claim 12, wherein the liquid medium is one selected from the group consisting of an aqueous solvent, a non-aqueous solvent, and a mixture of the aqueous solvent and the non-aqueous solvent.

14. The solution of claim 12, wherein a first concentration of metal impurities is equal to or less than about 25 parts per billion.

15. The solution of claim 12, wherein the metal ions comprise ionic iron or ionic calcium.

16. The solution of claim 15, wherein a second concentration of residual complexing agent is equal to or less than 25 parts per billion.

17. The solution of claim 12, wherein the solution has a nanotube concentration of about 333 mg/L or more.

18. A method for using a nanotube solution, comprising applying the solution of claim 12 on a substrate so as to form a nanotube fabric layer on the substrate.

19. The method of claim 18, wherein applying the solution comprises spin coating the solution on the substrate.

20. The method of claim 18, wherein applying the solution comprises spraying the solution on the substrate.