HIGHLY-ORDERED TITANIA NANOTUBE ARRAYS

• US 20100187172A1
• Filed: 01/25/2010
• Published: 07/29/2010
• Est. Priority Date: 07/26/2007
• Status: Abandoned Application

• Current Assignee: Penn State Research Foundation
• Original Assignee: Penn State Research Foundation
• Inventors: VARGHESE, OOMMAN K., SHANKAR, KARTHIK, GRIMES, CRAIG A., PRAKASAM, HARIPRIYA E., PAULOSE, MAGGIE, YORIYA, SORACHON
• Application Number:
  US12/693,123
• Publication Number:
  US 20100187172A1
• Time in Patent Office: Days
• US Class Current: 210/506
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 23/047 Titanium dioxide
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• 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: C25D 11/26 of refractory metals or alloys based thereon
• CPC Class Codes: C25D 7/04 Tubes; Rings; Hollow bodies

Abstract

Fabrication of self-aligned closed packed titania nanotube arrays in excess of 10 μm in length and aspect ratio ≈10,000 by potentiostatic anodization of titanium is disclosed. Conditions for achieving complete anodization and absolute tailorability of Ti foil samples resulting in a self-standing mechanically robust titania membrane in excess of 1000 μm are also disclosed.

Claims

1. A method of forming a vertically oriented titania nanotube array using electrochemical oxidation, the method comprising:

providing a two-electrode configuration having a working electrode and a counter electrode; and

anodizing the working electrode in a polar organic electrolyte for providing fluoride ions, the polar organic electrolyte optimized to maintain dynamic equilibrium between growth and dissolution processes to promote growth of the nanotube array by providing sustained chemical oxidation of the working electrode and pore growth by dissolution of formed oxides.

2. The method of claim 1 wherein the polar organic electrolyte is ethylene glycol or a polar organic electrolyte consisting of a formamide, a dimethyl sulfoxide, a dimethylformamide or a N-methylformamide for providing fluoride ions.

3. The method of claim 1 wherein the working electrode is a titanium foil having a thickness sufficient to provide synthesis of self-aligned closely packed nanotube arrays of in excess of 10 μ

m in length.

4. The method of claim 1 wherein the working electrode is a titanium foil having a thickness sufficient to provide synthesis of self-aligned closely packed nanotube arrays of at least 134 μ

m in length.

5. The method of claim 1 wherein the working electrode is a titanium foil having a thickness sufficient to provide synthesis of self-aligned closely packed nanotube arrays in excess of 1000 μ

m in length.

6. The method of claim 5 wherein the thickness of the titanium foil being at least 2.0 mm.

7. The method of claim 3 wherein the thickness of the titanium foil being between 0.25 mm and 2.0 mm.

8. The method of claim 1 wherein the polar organic electrolyte is an aqueous electrolyte, an amide based electrolyte, or a non-aqueous electrolyte.

9. The method of claim 1 wherein the polar organic electrolyte is an ethylene glycol containing 0.3 wt % NH₄F and 2% H₂O.

10. The method of claim 1 wherein the polar organic electrolyte is a fluoride containing organic electrolyte of DMSO containing hydrofluoric acid, potassium fluoride, or ammonium fluoride.

11. The method of claim 10 further comprising the step of optimizing the electrolytic composition of the fluoride containing organic electrolyte and duration of oxidation to provide complete anodization of the working electrode and control of the length of the nanotube array.

12. The method of claim 1 further comprising the step of assisting in increasing length of the nanotube array by anodizing the working electrode in the polar organic electrolyte having 0.5 wt % NH₄F and 3.0% H₂O in ethylene glycol.

13. The method of claim 1 wherein the counter electrode comprises a platinum foil.

14. A method for forming a vertically oriented nanotube array using electrochemical oxidation, the method comprising:

providing a two-electrode configuration having a working electrode and a counter electrode;

anodizing the working electrode in an electrolyte having fluoride ions to assist in providing a formed oxide;

dissolving the formed oxide to form the nanotube array;

maintaining dynamic equilibrium between growth and dissolution processes by controlling one or more anodization variables; and

growing the nanotube array to a total length to form to the nanotube array by sustained oxidation of the working electrode.

15. The method of claim 14 wherein the electrolyte is a polar organic electrolyte to provide the fluoride ions, the polar organic electrolyte from a set consisting of:

a) formamide (FA);

b) dimethyl sulfoxide (DMSO);

c) dimethylformamide (DMF); and

d) N-methylformamide (NMF).

16. The method of claim 14 wherein the electrolyte is a polar organic electrolyte comprising ammonium fluoride (NH₄F).

17. The method of claim 14 wherein the working electrode comprises a titanium foil.

18. The method of claim 17 wherein the counter electrode comprises a platinum foil.

19. The method of claim 18 wherein the formed oxide comprises a titanium oxide.

20. The method of claim 19 wherein the electrolyte comprises a solution of ethylene glycol, wherein the ethylene glycol assists in minimizing lateral etching of the nanotubes.

21. The method of claim 20 further comprising completely anodizing a thickness of the titanium foil by optimizing the electrolyte comprising a weight % of NH₄F and H₂O in the solution of ethylene glycol.

22. The method of claim 21 wherein the anodization variables include at least:

a) an anodization voltage;

b) an anodization time;

c) a wt % of H₂O in the solution of ethylene glycol; and

d) a wt % of NH₄F.

23. The method of claim 22 further comprising the step of obtaining at least the total length of 1000 μ

m for the nanotube array using titanium foil of sufficient thickness and anodizing the titanium foil in the electrolyte having the wt % NH₄F and H₂O in the solution of ethylene glycol at sufficient anodization voltage and the time.

24. A method for forming a nanotube array using electro-chemical oxidation, the method comprising:

providing a two-electrode configuration having a titanium foil as a working electrode and a platinum foil as a counter electrode;

anodizing the titanium foil in a polar organic electrolyte solution to form a titanium dioxide;

dissolving the titanium dioxide to form the nanotube array of long range order exhibiting close-packing and high aspect ratios;

growing the nanotube array to an optimal length given the working electrode thickness by sustained oxidation of the titanium foil and pore growth; and

maintaining dynamic equilibrium between growth and dissolution processes.

25. The method of claim 24 further comprising the step of providing the nanotube array of at least 1000 μ

m in length from 0.5 mm thick titanium foil by anodizing the foil in the polar organic electrolyte having a wt % NH₄F and wt % H₂O in a solution of ethylene glycol.

26. A nanotube array, comprising:

a plurality of self-aligned vertically oriented titania nanotubes;

wherein the plurality of self-aligned vertically oriented titania nanotubes being formed by electrochemical oxidation using a polar organic electrolyte.

27. A solar cell, comprising;

a solar cell surface;

a nanotube array attached to the surface, the nanotube array comprising a plurality of self-aligned vertically oriented titania nanotubes;

wherein the titania nanotube array being formed by electrochemical oxidation using a polar organic electrolyte.

28. A biofilter, comprising:

a biofilter surface;

a nanotube array attached to the surface, the nanotube array comprising a plurality of self-aligned vertically oriented titania nanotubes;

wherein the titania nanotube array being formed by electrochemical oxidation using a polar organic electrolyte.