Functionalized boron nitride nanotubes

• US 8,703,023 B2
• Filed: 06/19/2012
• Issued: 04/22/2014
• Est. Priority Date: 11/22/2006
• Status: Active Grant

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Sainsbury, Toby, Ikuno, Takashi, Zettl, Alexander K.
• Primary Examiner(s): Buie-Hatcher, Nicole M
• Assistant Examiner(s): ASDJODI, MOHAMMADREZA
• Application Number:
  US13/527,369
• Publication Number:
  US 20120273733A1
• Time in Patent Office: 672 Days
• Field of Search: 252/500, 423/290
• US Class Current: 252/500
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 21/064 with boron
• CPC Class Codes: C01B 21/0648 After-treatment, e.g. grinding, purification transformation of hexagonal into cubic or wurtzitic boron nitride C04B35/5831
• CPC Class Codes: C01P 2002/82 by IR- or Raman-data
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/13 Nanotubes
• CPC Class Codes: C01P 2006/22 Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Abstract

A plasma treatment has been used to modify the surface of BNNTs. In one example, the surface of the BNNT has been modified using ammonia plasma to include amine functional groups. Amine functionalization allows BNNTs to be soluble in chloroform, which had not been possible previously. Further functionalization of amine-functionalized BNNTs with thiol-terminated organic molecules has also been demonstrated. Gold nanoparticles have been self-assembled at the surface of both amine- and thiol-functionalized boron nitride Nanotubes (BNNTs) in solution. This approach constitutes a basis for the preparation of highly functionalized BNNTs and for their utilization as nanoscale templates for assembly and integration with other nanoscale materials.

Claims

1. A method of modifying boron nitride nanotubes, comprising:

a) providing the boron nitride nanotubes;

b) placing the boron nitride nanotubes in a chamber equipped with a plasma generator; and

c) exposing the boron nitride nanotubes to an ammonia plasma in the chamber to form amine-functionalized boron nitride nanotubes; and

d) combining the amine-functionalized boron nitride nanotubes with a liquid 3-bromopropanoylchloride reagent to form a mixture.

2. The method of claim 1 wherein operation c) includes:

i) pumping the chamber to a pressure less than or approximately equal to 0.3 Pascals;

ii) flowing ammonia gas into the chamber;

iii) applying a bias voltage of between about −

50 volts and −

200 volts 1 to the boron nitride nanotubes; and

iv) applying power to the plasma generator.

3. The method of claim 2 wherein flowing the ammonia gas comprises flowing the ammonia gas at a rate of approximately 10 standard cubic centimeters per minute under a pressure of approximately 400 Pascals.

4. The method of claim 2 wherein the bias voltage is about −

100 volts.

5. The method of claim 2 wherein the power is between about 100 watts and 500 watts.

6. The method of claim 2 wherein the power is about 200 watts.

7. A method of modifying boron nitride nanotubes, comprising:

a) providing the boron nitride nanotubes;

b) placing the boron nitride nanotubes in a chamber equipped with a plasma generator;

c) exposing the boron nitride nanotubes to a plasma to form functionalized boron nitride nanotubes; and

d) combining the functionalized boron nitride nanotubes with a liquid 3-bromopropanoylchloride reagent to form a mixture.

8. The method of claim 7 wherein operation c) includes:

i) pumping the chamber to a pressure less than or approximately equal to 0.3 Pascals;

ii) flowing a gas into the chamber;

iii) applying a negative bias voltage to the boron nitride nanotubes; and

iv) applying power to the plasma generator.

9. The method of claim 8 wherein the gas is selected from the group consisting of ammonia, H₂+N₂, CH₄+O₂, CH₄+N₂, H₂O, and N₂+O₂.

10. The method of claim 9 wherein the ammonia or the H₂+N₂ forms amine-functionalized boron nitride nanotubes.

11. The method of claim 9 wherein the CH₄+O₂ forms carboxyl-functionalized boron nitride nanotubes.

12. The method of claim 9 wherein the CH₄+N₂ forms imine-functionalized boron nitride nanotubes.

13. The method of claim 9 wherein the H₂O forms hydroxyl-functionalized boron nitride nanotubes.

14. The method of claim 9 wherein the N₂+O₂ forms nitrile-functionalized boron nitride nanotubes.

15. The method of claim 7, further comprising:

combining the functionalized boron nitride nanotubes with nanoparticles after operation c).

16. A method comprising:

a) providing boron nitride nanotubes;

b) placing the boron nitride nanotubes in a chamber equipped with a plasma generator; and

c) exposing the boron nitride nanotubes to an ammonia plasma in the chamber to form amine-functionalized boron nitride nanotubes;

d) combining the amine-functionalized boron nitride nanotubes with de-ionized water to form a suspension; and

e) adding a solution of 3-mercaptopropionic acid, N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride, and 4-dimethylaminopyridine in de-ionized water to the suspension to form a mixture.

17. The method of claim 16 wherein operation c) includes:

i) pumping the chamber to a pressure less than or approximately equal to 0.3 Pascals;

ii) flowing ammonia gas into the chamber;

iii) applying a bias voltage of between about −

50 volts and −

200 volts to the boron nitride nanotubes; and

iv) applying power to the plasma generator.

18. The method of claim 17 wherein flowing the ammonia gas comprises flowing the ammonia gas at a rate of approximately 10 standard cubic centimeters per minute under a pressure of approximately 400 Pascals.

19. The method of claim 17 wherein the bias voltage is about −

100 volts.

20. The method of claim 17 wherein the power is between about 100 watts and 500 watts.

21. The method of claim 17 wherein the power is about 200 watts.

22. A method comprising:

a) providing boron nitride nanotubes;

b) placing the boron nitride nanotubes in a chamber equipped with a plasma generator;

c) exposing the boron nitride nanotubes to a plasma to form functionalized boron nitride nanotubes;

d) combining the functionalized boron nitride nanotubes with de-ionized water to form a suspension; and

e) adding a solution of 3-mercaptopropionic acid, N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride, and 4-dimethylaminopyridine in de-ionized water to the suspension to form a mixture.

23. The method of claim 22 wherein operation c) includes:

i) pumping the chamber to a pressure less than or approximately equal to 0.3 Pascals;

ii) flowing a gas into the chamber;

iii) applying a negative bias voltage to the boron nitride nanotubes; and

iv) applying power to the plasma generator.

24. The method of claim 23 wherein the gas is selected from the group consisting of ammonia, H₂+N₂, CH₄+O₂, CH₄+N₂, H₂O, and N₂+O₂.

25. The method of claim 22, further comprising:

combining the functionalized boron nitride nanotubes with nanoparticles after operation c).