Pyrocarbon and process for depositing pyrocarbon coatings

• US 5,514,410 A
• Filed: 09/08/1994
• Issued: 05/07/1996
• Est. Priority Date: 09/08/1994
• Status: Expired due to Term

• Current Assignee: Medtronic Carbon Implants Incorporated (Medtronic Plc)
• Original Assignee: Carbon Implants Inc. (Medtronic Plc)
• Inventors: Accuntius, James A., Emken, Michael R., Ely, John L., Haubold, Axel D.
• Primary Examiner(s): DUDASH, DIANA L
• Application Number:
  US08/303,064
• Time in Patent Office: 607 Days
• Field of Search: 427/2.24, 427/249, 427/213, 427/228, 427/378, 427/255.1, 427/255.5
• US Class Current: 427/2.24
• CPC Class Codes: A61F 2310/00574 Coating or prosthesis-covering structure made of carbon, e.g. of pyrocarbon
• CPC Class Codes: A61L 27/303 Carbon
• CPC Class Codes: C23C 16/26 Deposition of carbon only
• CPC Class Codes: C23C 16/442 using fluidised bed process
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

Pure unalloyed pyrocarbons having wear resistance suitable for use in pyrocarbon-coated heart valve components and having mechanical properties, such as flexural strength and toughness, superior to commercial silicon-alloyed pyrocarbons are deposited in fluidized bed coaters. Coating conditions are carefully controlled so as to maintain a precise bed size within a defined coating enclosure which will assure a substantially constant surface deposition temperature that in turn assures deposition of homogenous unalloyed pyrocarbons having these improved mechanical properties.

Claims

1. A process for coating prosthetic heart valve components with pyrocarbon having high fracture toughness, high flexural strength and high strain-to-failure without including 5 or more weight percent of silicon in such pyrocarbon, which process comprises,

establishing a bed of particles in a coating enclosure by levitating said particles so as to create a region within said enclosure wherein coating with pyrocarbon will occur and levitating a plurality of substrates for heart valve bodies or occluders along with said particles in said coating region, said particles providing sufficient surface area that the ratio of surface area of said bed of particles measured in square centimeters to the volume of the coating region measured in cubic centimeters is at least 10 to 1,

maintaining said particles and said substrates at a temperature between about 1350°

C. and about 1425°

C.,

employing a levitating gas stream which includes a hydrocarbon that will pyrolytically decompose at said temperature and may also include an inert gas but which is substantially devoid of any alloying agent and maintaining a continuous upward flow of said gas stream through said coating region at a rate of between about 0.1 and about 0.5 liter per minute per sq. cm. of cross section of said coating region, said hydrocarbon having a carbon chain length not greater than about 5 carbon atoms,

continuing said continuous upward flow of said gas stream through said coating region for a length of time sufficient to deposit a uniform coating having a thickness of at least about 0.2 mm of substantially unalloyed pyrocarbon upon each of said substrates, and

maintaining a substantially constant bed surface area within said coating region by adding additional particles thereto while removing therefrom pyrocarbon-coated particles which have grown in particle size as a result of deposition of pyrocarbon so that the actual bed temperature at surfaces where deposition is occurring remains within a temperature range of about 50°

C.,

whereby said substrates remain in said enclosure and are coated with unalloyed pyrocarbon having a density of about 1.8 to about 2.0 g/cm³, a K_IC of at least about 1.2, a modulus of rupture for bending of at least about 58, a strain-to-failure of at least about 1.3%, and a Young'"'"'s modulus of about 4.0×

10⁶ psi or below.

2. A process according to claim 1 wherein said pyrocarbon has a K_IC of at least about 1.54.

3. A process according to claim 1 wherein said substrates are made of isotropic artificial graphite.

4. A process according to claim 1 wherein an inert gas is present and constitutes at least about 40 volume percent of said stream.

5. A process for making unalloyed isotropic pyrocarbon having high fracture toughness, high flexural strength and high strain-to-failure, which process comprises,

establishing a bed of particles in a coating enclosure by levitating said particles so as to create a region within said enclosure wherein coating with pyrocarbon will occur and levitating a plurality of substrates to be coated along with said particles in said coating region, said particles providing sufficient surface area that the ratio of surface area of said bed of particles measured in square centimeters to the volume of the coating region measured in cubic centimeters is at least 10 to 1,

maintaining said coating region at a set temperature above about 1325°

C. and at or below about 1450°

C.,

employing a levitating gas stream which includes a hydrocarbon that will pyrolytically decompose at said temperature and maintaining a continuous upward flow of said gas stream through said coating region at a rate of between about 0.1 and about 0.5 liter per minute per sq. cm. of cross section of said coating region, said hydrocarbon having a carbon chain length not greater than about 5 carbon atoms,

continuing said continuous upward flow of said gas stream through said coating region for a length of time sufficient to deposit a uniform coating of a desired thickness of at least about 0.1 mm of pure unalloyed pyrocarbon upon each of said substrates, and

maintaining a substantially constant bed surface area within said coating region by adding additional particles thereto while removing therefrom pyrocarbon-coated particles which have grown in particle size as a result of deposition of pyrocarbon, so that the surface temperature of said particles and said substrates remains substantially constant during said length of time,

whereby said substrates remain in said enclosure and are coated with unalloyed pyrocarbon having such properties with a density of between about 1.7 and about 2.1 g/cm³, a K_IC of at least about 1.2, a modulus of rupture for bending of at least about 58, a strain-to-failure of at least about 1.3%, and a Diamond Pyramid Hardness (DPH) of between about 200 and 250.

6. A process according to claim 5 wherein the amount of said particles is selected so that the ratio of the surface area of said bed of particles measured in square centimeters to the volume of said coating region measured in cubic centimeters is at least about 20 to 1.

7. A process according to claim 6 wherein said ratio is between about 20 to 1 and about 40 to 1.

8. A process according to claim 5 wherein said hydrocarbon is selected from the group consisting of propane, propylene, ethane, methane, butane and mixtures thereof.

9. A process according to claim 5 wherein said gas stream is a mixture of said hydrocarbon and an inert gas devoid of any alloying agent, which inert gas constitutes at least about 40 volume percent of said mixture, and said flow rate is between about 0.2 and about 0.4 L/min/sq.cm.

10. A process according to claim 9 wherein said hydrocarbon and the volume percent of said hydrocarbon are selected so that said pyrocarbon deposited is isotropic and has a hardness of at least about 220 (DPH), and an apparent crystalline size of at least about 30 Å

.

11. A process according to claim 10 wherein said isotropic pyrocarbon which is deposited has a Bacon Aniosotropy Factor (BAF) between 1.0 and about 1.1.

12. A process according to claim 11 wherein said deposited pyrocarbon has a density of between about 1.8 and about 1.95 gm/cm³.

13. A process according to claim 5 wherein said temperature is maintained between about 1350°

C. and about 1425°

C.

14. A process for making substantially unalloyed pyrocarbon having high fracture toughness, high flexural strength and high strain-to-failure, which process comprises,

establishing a bed of particles in a coating enclosure by levitating said particles so as to create a region within said enclosure wherein coating with pyrocarbon will occur and levitating a plurality of substrates to be coated along with said particles in said coating region, said particles providing sufficient surface area that the ratio of surface area of said bed of particles measured in square centimeters to the volume of the coating region measured in cubic centimeters is at least 10 to 1,

maintaining said particles and said substrates at a temperature between about 1325°

C. and about 1425°

C.,

employing a levitating gas stream which is a mixture of a hydrocarbon that will pyrolytically decompose at said temperature and an inert gas and is substantially devoid of any alloying agent, which inert gas constitutes at least about 40 volume percent of said mixture, and maintaining a continuous upward flow of said gas stream through said coating region at a rate of between about 0.1 and about 0.5 liter per minute per sq. cm. of cross section of said coating region, said hydrocarbon having a carbon chain length not greater than about 5 carbon atoms,

continuing said continuous upward flow of said gas stream through said coating region for a length of time sufficient to deposit a uniform coating having a thickness of at least about 0.1 mm of substantially unalloyed pyrocarbon upon each of said substrates

maintaining a substantially constant bed surface area within said coating region by adding additional particles thereto while removing therefrom pyrocarbon-coated particles which have grown in particle size as a result of deposition of pyrocarbon so that the actual bed temperature at surfaces where deposition is occurring remains within a temperature range of about 50°

C., and

whereby said substrates remain in said enclosure and are coated with unalloyed pyrocarbon having a density of about 1.8 to about 2.0 g/cm³, a K_IC of at least about 1.2, a modulus of rupture for bending of at least about 58, a strain-to-failure of at least about 1.3%, and a Young'"'"'s modulus of about 4.0×

10⁶ psi or below.

15. A process according to claim 14 wherein said pyrocarbon has a K_IC of at least about 1.54.

16. A process according to claim 14 wherein said temperature is maintained at between about 1375°

C. and about 1425°

C.

17. A process according to claim 14 wherein the amount of said particles is selected so that the ratio of the surface area of said bed of particles measured in square centimeters to the volume of said coating region measured in cubic centimeters is at least about 20 to 1.

18. A process according to claim 17 wherein said hydrocarbon is propane, said levitating gas stream upward flow rate is between about 0.2 and about 0.4 liters per sq.cm. per minute, and said coating is continued to deposit a uniform coating of a thickness of at least about 0.2 mm on said substrates.

19. A process according to claim 14 wherein highly isotropic pyrocarbon is deposited having a BAF not greater than 1.075 and a hardness of at least about 230 (DPH).