Compositions, methods and devices for generating nanotubes on a surface

• US 9,376,759 B2
• Filed: 03/13/2013
• Issued: 06/28/2016
• Est. Priority Date: 09/14/2010
• Status: Active Grant

• Current Assignee: Michigan Technological University
• Original Assignee: Michigan Technological University
• Inventors: Friedrich, Craig Richard, Shokuhfar, Tolou
• Primary Examiner(s): Azpuru, Carlos
• Assistant Examiner(s): HAGOPIAN, CASEY SHEA
• Application Number:
  US13/798,287
• Publication Number:
  US 20130196128A1
• Time in Patent Office: 1,203 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C25D 11/005 Apparatus specially adapted for electrolytic conversion coating apparatus in general for electrolytic coating C25D17/00
• CPC Class Codes: C25D 11/022 Anodisation on selected surface areas
• CPC Class Codes: C25D 11/26 of refractory metals or alloys based thereon
• CPC Class Codes: C25D 7/00 Electroplating characterised by the article coated
• CPC Class Codes: Y10T 428/24917 including metal layer

Abstract

A method for modifying a surface by generating nanotubes at one or more selected sites on the surface, the surface including a first metal. The method includes the steps of positioning at least one cathode and at least one anode relative to the surface in an electrolyte solution including a fluoride salt of a second metal, and applying a voltage between the at least one anode and the at least one cathode sufficient to generate nanotubes at one or more selected sites on the surface and to inhibit nanotube formation at one or more of the other selected sites, wherein the nanotubes include the first metal and the second metal.

Claims

1. A method for modifying a surface by generating nanotubes at one or more selected sites on the surface, the surface comprising a first metal, the method comprising:

positioning at least one cathode and at least one anode relative to the surface in an electrolyte solution comprising a fluoride salt of a second metal; and

applying a voltage between the at least one anode and the at least one cathode sufficient to generate nanotubes at one or more selected sites on the surface by removing a portion of the first metal from the surface by etching, and to inhibit nanotube formation at one or more of the other selected sites, wherein the nanotubes comprise the first metal and the second metal;

wherein the electrolyte solution comprises AgF or CaF₂.

2. The method of claim 1, further comprising applying a voltage of reverse polarity to the at least one cathode and the at least one anode sufficient to deposit the second metal onto the surface.

3. The method of claim 1, wherein the first metal comprises titanium.

4. The method of claim 3, wherein the second metal comprises silver.

5. The method of claim 4, further comprising varying a level of silver in the electrolyte solution to vary an amount of silver associated with the surface.

6. The method of claim 5, wherein varying a level of silver in the electrolyte solution comprises adjusting a level of silver in a range from 0.1 to 2.25 grams per 100 mL of electrolyte solution.

7. The method of claim 6, wherein the electrolyte solution comprises ethylene glycol and water.

8. The method of claim 1, wherein the at least one cathode and the at least one anode comprise graphite.

9. The method of claim 1, wherein the second metal reduces the propensity of the surface to support bacterial cell growth.

10. The method of claim 1, wherein the voltage is approximately 60 VDC.

11. The method of claim 1, wherein the surface comprises titanium.

12. The method of claim 1, further comprising coating the surface with at least one of an anti-bacterial agent, a growth factor, and an anti-inflammatory agent.

13. The method of claim 1, further comprising loading the nanotubes with an effective amount of a biologically active agent.

14. The method of claim 1, wherein the surface is present on a biomedical implant or medical device.

15. The method of claim 1, wherein the surface is present on a biomedical implant which is selected from the group consisting of a dental implant, a cardiovascular implant, a neurological implant, a neurovascular implant, a gastrointestinal implant, a muscular implant, an orthopedic implant, a cochlear implant, and an ocular implant.

16. The method of claim 1, wherein the surface is present on an orthopedic implant which is selected from the group consisting of joint implants, spinal implants, screws, pins, rods, and plates.

17. A method for modifying a surface by generating nanotubes at one or more selected sites on the surface, the surface comprising a first metal, the method comprising:

positioning at least one cathode and at least one anode relative to the surface in an electrolyte solution comprising a fluoride salt of a second metal; and

applying a voltage between the at least one anode and the at least one cathode sufficient to generate nanotubes at one or more selected sites on the surface by removing a portion of the first metal from the surface by etching, and to inhibit nanotube formation at one or more of the other selected sites, wherein the nanotubes comprise the first metal and the second metal; and

applying a voltage of reverse polarity to the at least one cathode and the at least one anode sufficient to deposit the second metal onto the surface.

18. A method for modifying a surface by generating nanotubes at one or more selected sites on the surface, the surface comprising a first metal, the method comprising:

positioning at least one cathode and at least one anode relative to the surface in an electrolyte solution comprising a fluoride salt of a second metal; and

applying a voltage between the at least one anode and the at least one cathode sufficient to generate nanotubes at one or more selected sites on the surface by removing a portion of the first metal from the surface by etching, and to inhibit nanotube formation at one or more of the other selected sites, wherein the nanotubes comprise the first metal and the second metal;

wherein the first metal comprises titanium, and the second metal comprises silver.

19. The method of claim 18, further comprising varying a level of silver in the electrolyte solution to vary an amount of silver associated with the surface.

20. The method of claim 19, wherein varying a level of silver in the electrolyte solution comprises adjusting a level of silver in a range from 0.1 to 2.25 grams per 100 mL of electrolyte solution.

21. The method of claim 20, wherein the electrolyte solution comprises ethylene glycol and water.

22. A method for modifying a surface by generating nanotubes at one or more selected sites on the surface, the surface comprising a first metal, the method comprising:

positioning at least one cathode and at least one anode relative to the surface in an electrolyte solution comprising a fluoride salt of a second metal; and

applying a voltage between the at least one anode and the at least one cathode sufficient to generate nanotubes at one or more selected sites on the surface by removing a portion of the first metal from the surface by etching, and to inhibit nanotube formation at one or more of the other selected sites, wherein the nanotubes comprise the first metal and the second metal;

wherein the at least one cathode and the at least one anode comprise graphite.