Method and apparatus for forming prosthetic device having a biocompatible carbon film thereon

• US 5,084,151 A
• Filed: 02/14/1990
• Issued: 01/28/1992
• Est. Priority Date: 11/26/1985
• Status: Expired due to Term

• Current Assignee: Sorin Biomedica Cardio Srl (LivaNova Plc)
• Original Assignee: Sorin Biomedica SpA (Snia SpA)
• Inventors: Vallana, Franco, Arru, Pietro
• Primary Examiner(s): Nguyen, Nam X.
• Application Number:
  US07/480,094
• Time in Patent Office: 713 Days
• Field of Search: 204/192.11, 204/192.14, 204/192.15, 204/192.38, 204/298.04, 204/298.06, 204/298.09, 204/298.27, 204/298.28, 204/298.29 , 204/298.41, 204/192.16, 204/298.15
• US Class Current: 204/192.11
• CPC Class Codes: A61F 2/30767 Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
• CPC Class Codes: A61F 2/3094 Designing or manufacturing processes
• CPC Class Codes: A61F 2310/00574 Coating or prosthesis-covering structure made of carbon, e.g. of pyrocarbon
• CPC Class Codes: C23C 14/0605 Carbon
• CPC Class Codes: C23C 14/205 by cathodic sputtering
• CPC Class Codes: C23C 14/355 using electrons, e.g. triode sputtering

Abstract

A prosthetic device which includes a biocompatible carbon film firmly adherent to a substrate. The carbon preferably is turbostratic and is preferably very thin, e.g., less than about one micron. The thin carbon biocompatible film is dense and covers at least that portion of the substrate which will be in contact with body tissue and/or fluids to insure against physiological rejection and degradation of the prosthetic device. The carbon can be deposited on a variety of substrates, including low temperature substrates, in situ, without adversely affecting the mechanical properties of the substrate. The prosthetic device of the invention is formed by triode sputtering vacuum deposition at a relatively low temperature to achieve the desired results with respect to the deposited carbon and the substrate and with respect to the required adherence therebetween.

Claims

1. The method of forming a prosthetic device having a substrate, comprising:

forming a plasma beam and directing the beam toward a carbon cathode circumscribed by an anode, the cathode and anode being remote from the site of formation of the plasma beam,

sputtering the carbon cathode by said beam while cooling the cathode and anode and operating the cathode at a high voltage and a low current;

directing said sputtered carbon onto a substrate at a temperature of below about 250°

C. without degradation to form a biocompatible carbon coating firmly adhered on the substrate, and

operating the method at a pressure of about 10^-4 mbar to about 10^-2 mbar.

2. The method of forming a prosthetic device according to claim 1, wherein the carbon cathode consists of graphite or pyrolytic carbon, and wherein the carbon deposited on the substrate is turbostratic.

3. The method of forming a prosthetic device according to claim 1, wherein the carbon cathode and anode are cooled by water conveyed through conduits contiguous therewith.

4. The method according to claim 1, wherein the substrate is flat and is rotated about the carbon cathode and about itself for uniform distribution of the sputtered carbon thereon.

5. The method according to claim 1, wherein the substrate is tubular and is rotated about its axis for uniform distribution of the sputtered carbon thereon.

6. The method according to claim 1, wherein the substrate is suture yarn and is rotated about a frame for uniform distribution of the sputtered carbon thereon.

7. The method according to claim 1, further comprising masking portions of the substrate so that the sputtered carbon only is deposited on unmasked portions.

8. The method according to claim 1, wherein the substrate is a polyester resin and the temperature at the substrate is maintained at about 80°

C. to enhance the adhesion of the sputtered carbon to the substrate.

9. The method according to claim 1, wherein the substrate is polytetrafluoroethylene and the temperature at the substrate is maintained at about 180°

C. for about one-sixth of the desired carbon coating thickness, and then at about 40°

C. for the balance of the coating of carbon, to thereby enhance the adhesion of the sputtered carbon to the substrate.

10. The method according to claim 1, wherein the carbon sputtered onto the substrate has a thickness of not more than about 1.0 micron.

11. The method according to claim 1, wherein the material of the substrate is selected from the group consisting of polyester resins, polytetrafluoroethylene, silicone, polyacetal resins, polyurethanes, polyethylene, cobalt-chromium alloys, titanium and titanium alloys, and wherein the carbon sputtered on the substrate is turbostratic.

12. The method according to claim 11, wherein the carbon cathode is sputtered in an atmosphere having a pressure of about 10^-3 mbar.

13. Apparatus for depositing a film of biocompatible carbon firmly adherent to a substrate of a prosthetic device, comprising:

(a) a first chamber for receiving an inert gas;

(b) means in said first chamber for ionizing the inert gas and issuing a plasma beam therefrom;

(c) a second chamber open and connected to said first chamber at one end thereof for receiving the plasma beam, and including a carbon cathode positioned at the other end of said second chamber remote from said one end, an annular anode circumscribing said carbon cathode, means about said second chamber for collimating the plasma beam and directing the collimated plasma beam toward said carbon cathode to sputter carbon atoms therefrom, and means mounted in said second chamber for holding a substrate and moving the substrate in the path of the sputtered carbon to form a firmly adherent carbon coating thereon;

(d) means within and about said second chamber for operating said second chamber at a low pressure;

(e) electrical means connected to said cathode for operating the cathode at a high voltage and low current;

(f) heating means positioned in said second chamber and in proximity of the substrate for heating the substrate to a desired level; and

(g) means for cooling the carbon cathode and anode.

14. The apparatus of claim 13, wherein said electrical means comprises an electrical source for maintaining the cathode and anode at a voltage of at least about 500 volts and at a current of not more than about 0.3 amps.

15. The apparatus of claim 13, wherein said means for cooling the carbon cathode and anode comprises:

(a) a first annular conduit contiguous with the outer perimeter of the anode;

(b) a second annular conduit in contact with the carbon cathode; and

(c) means for conveying cooling water through said conduits.

16. The apparatus of claim 13 wherein a plurality of substrates are simultaneously coated with sputtered biocompatible carbon, and wherein said means for holding and moving the substrates comprises:

rotatable means mounted at the bottom of the second chamber;

a housing removably mounted on and rotatable with said rotatable means which extends upwardly therefrom and about said carbon cathode,

support means for each substrate releasably connected to said housing for holding a substrate thereon during sputtering of the carbon, wherein said support means rotates with said housing about said carbon cathode and is rotatable, at the same time, about its own axis,

means connected to said rotatable means for rotation thereof, and

means positioned in said second chamber for frictionally engaging each of said support means to effect rotation thereof about its own axis as said housing rotates with said support means about said carbon cathode.

17. The apparatus of claim 16, wherein each of said support means for the substrate comprises:

(a) a disk having a convex rear wall and a concave front wall; and

(b) a frame mounted on the concave front wall of said disk for releasably connecting the substrate thereto; and

wherein

(c) said frictionally engaging means is an annular rail engaged by the bottom of each of said disks.

18. The apparatus of claim 17, wherein said substrates have a flat cross-sectional shape.

19. The apparatus of claim 13 for coating biocompatible carbon on a tubular substrate of a prosthetic device, wherein said holding and moving means for the substrate, comprises:

a rotatable spindle mounted in said second chamber in the path of the sputtered carbon for mounting the tubular substrate thereon, and

drive means positioned in said second chamber for rotating said spindle so that sputtered carbon is uniformly deposited on the exposed surface of the rotating tubular substrate.

20. The apparatus of claim 13 for coating biocompatible carbon on a substrate of suture yarn, wherein said holding and moving means for a substrate of suturing yarn comprises:

a frame mounted in said second chamber in the path of the sputtered carbon, including a pair of transversely spaced rods having a plurality of grooves therein for receiving the suture yarn as it is rotated on said rods, wherein said grooves are aligned between rods in such a manner that the yarn turns slightly as it continuously travels from one groove to another therebetween;

means connected to one of said rods for rotation thereof; and

means connected to said frame for transferring the suture yarn coming off one end of one of said transverse rods to thereby continuously rotate said suture yarn until it is coated to the desired thickness with firmly adherent biocompatible sputtered carbon.