Surface modification of medical implants

• US 6,033,582 A
• Filed: 01/16/1998
• Issued: 03/07/2000
• Est. Priority Date: 01/22/1996
• Status: Expired due to Term

• Current Assignee: Etex Corporation (Zimmer Biomet Holdings, Inc.)
• Original Assignee: Etex Corporation (Zimmer Biomet Holdings, Inc.)
• Inventors: Lee, Dosuk D., Nagras, Atul, Majahad, Anthony M., Chakravarthy, Pramod
• Primary Examiner(s): Gulakowski, Randy
• Assistant Examiner(s): Ahmed, Shamim
• Application Number:
  US09/008,650
• Time in Patent Office: 781 Days
• Field of Search: 216/75, 216/77, 216/78, 216/67, 216/37, 204/192.32, 204/192.35
• US Class Current: 216/37
• CPC Class Codes: A61L 2400/18 Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
• CPC Class Codes: A61L 27/02 Inorganic materials
• CPC Class Codes: A61L 27/14 Macromolecular materials
• CPC Class Codes: A61L 27/32 Phosphorus-containing materials, e.g. apatite
• CPC Class Codes: A61L 27/3839 characterised by the site of application in the body materials for artificial blood vessels A61L27/507; materials for use in artificial skin A61L27/60
• CPC Class Codes: A61L 27/50 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: A61L 27/56 Porous materials, e.g. foams or sponges
• CPC Class Codes: C23C 14/34 Sputtering
• CPC Class Codes: C23F 4/00 Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00

Abstract

An irregularly etched medical implant device is provided having random non-uniform relief patterns on the surface ranging from about 0.3 μm to less than about 20 μm in depth. The random, irregular surface as defined by the etch micromorphology and respective dimensional properties are obtained by exposing a surface to a reactive plasma in a chamber wherein said reactive plasma produces a reaction product with the surface to thereby etch the surface, said reaction product or a complex thereof having a vapor pressure lower than a pressure in the chamber; providing a dynamic masking agent during the etching process; and removing the reaction products.

Claims

1. A method for the production of a random, irregular surface on an article, comprising:

exposing an article having a polymer surface to a plasma comprised of a reactive etching species that etches the surface by producing a volatile reaction product with the substrate and a second species selected to promote dynamic masking of the substrate, said dynamic masking comprising in situ deposition and removal of a species having etching properties different than the substrate, to obtain non-uniform etching of the substrate.

2. The method of claim 1, wherein said second species comprises a plasma species capable of producing a sputtering effect.

3. The method of claim 2, wherein the plasma species is selected from the group consisting of argon, helium and nitrogen.

4. The method of claim 2, further comprising redeposition of ions sputtered from the surface of the substrate.

5. The method of claim 2, further comprising redeposition of said volatile reaction product.

6. The method of claim 2, further comprising deposition of ions onto the surface sputtered from a sputtering target.

7. The method of claim 6, wherein the sputtering target comprises a form of calcium phosphate.

8. The method of claim 1, wherein the second species is a contaminant selected from the group consisting of water vapor, carbon dioxide, dust, particulates and sputtered ions from impurities of the substrate, a holder supporting the article or walls from a chamber housing the article.

9. The method of claim 2 wherein the plasma further comprises a noble gas.

16. The method of claim 1 or 10, wherein the method produces etching features on the surface having a relief depth of greater than about 1 micron.

17. The method of claim 16, wherein the method produces shallow etching features on the surface having a relief depth in the range of about 1-5 microns and deep etching features in the range of about 5-20 microns.

18. The method of claim 1 or 10, further comprising:

chemically modifying the surface of the article to increase adhesion or improve biocompatibility of the article.

19. The method of claim 1 or 10, further comprising:

physical abrasion of the surface after exposure to the plasma.

20. The method of claim 1 or 10, further comprising:

applying a coating to the irregular surface.

21. The method of claim 19, wherein the coating is selected from the group consisting of organic polymers and forms of calcium phosphate.

22. The method of claim 1, wherein the reactive etching species comprises water vapor.

23. The method of claim 1 or 10, wherein the surface comprises a polymer selected from the group consisting of poly(L-lactic acid), poly(glycolic acid) [PGA], polyethylene, polypropylene, polyurethane, polysulphone, poly(tetrafluoroethylene), poly(methyl methacrylate), polyacrylonitrile, polyamide, poly(vinyl chloride), polyacetal and polyester resins.

24. The method of claim 1 or 10, wherein pressure of a chamber housing the article is in the range of 0.01 Torr to about 1 Torr.

25. The method of claim 1 or 10, wherein power levels of the plasma are modulated over fixed intervals.

26. The method of claim 25, wherein the plasma power level is at radio frequencies at 13.56 MHz and harmonic multiples thereof.

27. The method of claim 1 or 10, wherein the article is isothermally or incrementally cooled.

28. The method of claim 1 or 10, wherein the article is isothermally or incrementally heated.

29. The method of claim 1 or 10, wherein the surface is sonicated in situ.

10. A method of preparing an article for use as a medical device having a roughened surface amenable to bioadhesion, comprising;

exposing a polymeric surface of a medical device to a plasma comprised of a reactive etching species that etches the surface by producing a reaction product with the substrate; and

removing the reaction products to obtain a surface having random and irregular etched features of greater than about 0.1 μ

m in depth.

11. The method of claim 10, wherein the reactive species comprises a species selected from the group consisting of water vapor, oxygen and hydrogen.

12. The method of claim 10, wherein the reactive species comprises a fluorine-containing compound.

13. The method of claim 10, wherein the plasma fuirther comprises ions sputtered from a sputtering target material.

14. The method of claim 13, wherein the sputtering target material comprises a calcium phosphate.

15. The method of claim 10, wherein the medical device is selected from the group consisting of artificial organs, artificial blood vessels and vascular grafts, heart valves, blood oxygenators, catheters, electrodes, and implant wires.