Process for forming an improved metal alloy stent

• US 7,540,995 B2
• Filed: 12/01/2006
• Issued: 06/02/2009
• Est. Priority Date: 03/03/2005
• Status: Active Grant

• Current Assignee: Mirus LLC
• Original Assignee: Icon Medical Corp. (ICON Interventional Systems, Inc.)
• Inventors: Furst, Joseph G., Patel, Udayan, Buckman, Raymond W. Jr.
• Primary Examiner(s): Wyszomierski; George
• Assistant Examiner(s): Zhu; Weiping
• Application Number:
  US11/635,158
• Publication Number:
  US 20070077163A1
• Time in Patent Office: 914 Days
• Field of Search: 623/1.15, 623/1.39, 419/28, 294/551, 148/513
• US Class Current: 419/28
• CPC Class Codes: A61F 2/91 made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
• CPC Class Codes: A61F 2/915 with bands having a meander structure, adjacent bands being connected to each other
• CPC Class Codes: A61F 2002/91575 connected peak to trough
• CPC Class Codes: A61F 2230/0054 V-shaped
• CPC Class Codes: A61L 31/022 Metals or alloys
• CPC Class Codes: B22F 1/00 Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
• CPC Class Codes: B22F 2003/241 Chemical after-treatment on the surface
• CPC Class Codes: B22F 2003/248 Thermal after-treatment
• CPC Class Codes: B22F 2201/01 Reducing atmosphere
• CPC Class Codes: B22F 2201/013 Hydrogen
• CPC Class Codes: B22F 2201/02 Nitrogen
• CPC Class Codes: B22F 2201/10 Inert gases
• CPC Class Codes: B22F 2201/20 Use of vacuum
• CPC Class Codes: B22F 2998/00 Supplementary information concerning processes or compositions relating to powder metallurgy
• CPC Class Codes: B22F 2998/10 Processes characterised by the sequence of their steps
• CPC Class Codes: B22F 2999/00 Aspects linked to processes or compositions used in powder metallurgy
• CPC Class Codes: B22F 3/04 by applying fluid pressure , e.g. by cold isostatic pressing [CIP]
• CPC Class Codes: B22F 3/10 Sintering only
• CPC Class Codes: B22F 3/1007 Atmosphere B22F3/1021 takes precedence
• CPC Class Codes: B22F 3/16 in successive or repeated steps
• CPC Class Codes: B22F 3/20 : by extruding
• CPC Class Codes: B22F 3/24 : After-treatment of workpieces or articles B22F3/1146 takes precedence
• CPC Class Codes: B22F 5/003 : Articles made for being fractured or separated into parts
• CPC Class Codes: B22F 5/10 : of articles with cavities or holes, not otherwise provided for in the preceding subgroups
• CPC Class Codes: B22F 5/106 : Tube or ring forms
• CPC Class Codes: C22C 27/00 : Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
• CPC Class Codes: C22C 27/04 : Alloys based on tungsten or molybdenum
• CPC Class Codes: C22C 30/00 : Alloys containing less than 50% by weight of each constituent
• CPC Class Codes: C22F 1/18 : High-melting or refractory metals or alloys based thereon

Abstract

A method and process for at least partially forming a medical device that is at least partially formed of a novel metal alloy which improves the physical properties of the medical device.

Claims

1. A method for forming a medical device comprising the steps of:

a) forming a rod or tube having a surface and an outer cross-sectional area, said rod or tube is formed of a metal alloy that is at least about 99 weight percent of a solid solution of molybdenum and rhenium;

b) drawing down said outer cross-sectional area of said rod or tube to a first drawn down cross-sectional area by a reducing mechanism, said rod or tube being drawn down at least once to obtain said first drawn down cross-sectional area, said outer cross-sectional area being reduced by no more than about 25% during each drawing down process;

c) annealing said rod or tube prior to said rod or tube having said outer cross-sectional area drawn down by more than about 50% at a first annealing temperature in a low oxygen environment after said rod or tube has been drawn down to said first drawn down cross-sectional area;

d) drawing down said cross-sectional area of said rod or tube to a second drawn down cross-sectional area by the reducing mechanism after said rod or tube has been annealed, said second drawn down cross-sectional area smaller than said first drawn down cross-sectional area, said rod or tube being drawn down at least once to obtain said second drawn down cross-sectional area, said outer cross-sectional area reduced by no more than about 25% during each drawing down process;

e) annealing said rod or tube that is at said second drawn down cross-sectional area at least one additional time at a second annealing temperature prior to said rod or tube having said outer cross-sectional area drawn down by more than about 50%, said second anneal temperature lower temperature than said first annealing; and

,

f) controlling an atmosphere about said rod or tube during said steps of drawing and annealing so that said metal alloy of said rod or tube after final drawing and annealing steps includes less than about 20 ppm nitrogen, less than about 150 ppm carbon, and less than about 50 ppm oxygen and a carbon to oxygen atomic ratio of at least about 2;

1.

2. The method as defined in claim 1, wherein said step of forming said rod or tube includes a process of isostatically pressing metal powder together and subsequently sintering said metal power to form said rod or tube in a controlled atmosphere, said rod or tube having an average density of about 0.7-0.95 a minimum theoretical density of said metal alloy, said rod or tube have an average density of about 12-14 gm/cc, said controlled atmosphere including an inert atmosphere, an oxygen reducing atmosphere, or a vacuum.

3. The method as defined in claim 1, wherein said step of forming said rod or tube includes a) forming an ingot of metal, b) extruding said ingot through a die to form a rod, c) hollowing out said rod to form a passageway at least partially through a longitudinal length of said rod, and d) polishing a surface of said passageway.

4. The method as defined in claim 2, wherein said tube is formed by gun drilling, EDM cutting, and combinations thereof a passageway at least partially through a longitudinal length of said rod.

5. The method as defined in claim 3, wherein said step of hollowing includes gun drilling, EDM cutting, and combinations thereof said rod to form said passageway.

6. The method as defined in claim 1, wherein said metal alloy includes about 46-49 weight percent rhenium, about 51-54 weight percent molybdenum, and up to about 1 weight percent additional metal, said additional metal including a metal selected from the group consisting of titanium, yttrium, zirconium, and mixtures thereof.

7. The method as defined in claim 1, including the step of nitriding said rod or tube to form a nitride layer on said rod or tube prior to at least one drawing down step, said step of nitriding including a) exposing at least a portion of said rod or tube to a nitriding gas that includes nitrogen, nitrogen and hydrogen, and combinations thereof, and b) exposing at least a portion of said rod or tube to a nitriding gas at a temperature of at least about 400°

C. for at least about 1 minute.

8. The method as defined in claim 7, including the step of nitriding said rod or tube to form a nitride layer on said rod or tube prior to at least one drawing down step, said step of nitriding including a) exposing at least a portion of said rod or tube to a nitriding gas that includes nitrogen, nitrogen and hydrogen, and combinations thereof, and b) exposing at least a portion of said rod or tube to a nitriding gas at a temperature of at least about 400°

C. for at least about 1 minute.

9. The method as defined in claim 7, including the step of removing said nitride layer on said rod or tube prior to annealing said rod or tube.

10. The method as defined in claim 8, including the step of removing said nitride layer on said rod or tube prior to annealing said rod or tube.

11. The method as defined in claim 1, including the step of protecting said rod or tube from oxygen when said rod or tube is exposed to temperatures of greater than about 400-500°

C.

12. The method as defined in claim 10, including the step of protecting said rod or tube from oxygen when said rod or tube is exposed to temperatures of greater than about 400-500°

C.

13. The method as defined in claim 1, wherein said step of drawing down said cross-sectional area of said rod or tube by a reducing mechanism that reduces said cross-sectional area by less than about 20% each time said rod or tube is processed by said reducing mechanism.

14. The method as defined in claim 12, wherein said step of drawing down said cross-sectional area of said rod or tube by a reducing mechanism that reduces said cross-sectional area by less than about 20% each time said rod or tube is processed by said reducing mechanism.

15. The method as defined in claim 3, wherein said step of drawing down includes the step of inserting a close-fitting rod in said passageway of said tube prior to using said reducing mechanism on said tube, said close-fitting rod formed of tantalum and niobium.

16. The method as defined in claim 4, wherein said step of drawing down includes the step of inserting a close-fitting rod in said passageway of said tube prior to using said reducing mechanism on said tube, said close-fitting rod formed of tantalum and niobium.

17. The method as defined in claim 1, wherein said step of annealing said rod or tube includes the steps of a) annealing the rod or tube at an annealing temperature of at least about 1480°

C. for a time period of at least about 5 minutes when said rod or tube has wall thickness of greater than about 0.015 inch, b) annealing the rod or tube at an annealing temperature of about 1450-1480°

C. for a time period of at least about 5 minutes when said rod or tube has wall thickness of about 0.008-0.015 inch, and c) annealing the rod or tube at an annealing temperature of less than about 1450°

C. for a time period of at least about 5 minutes when said rod or tube has wall thickness of less than about 0.00 8 inch.

18. The method as defined in claim 14, wherein said step of annealing said rod or tube includes the steps of a) annealing the rod or tube at an annealing temperature of at least about 1480°

C. for a time period of at least about 5 minutes when said rod or tube has wall thickness of greater than about 0.015 inch, b) annealing the rod or tube at an annealing temperature of about 1450-1480°

C. for a time period of at least about 5 minutes when said rod or tube has wall thickness of about 0.008-0.015 inch, and c) annealing the rod or tube at an annealing temperature of less than about 1450°

C. for a time period of at least about 5 minutes when said rod or tube has wall thickness of less than about 0.008 inch.

19. The method as defined in claim 1, wherein said medical device is a stent.

20. The method as defined in claim 18, wherein said medical device is a stent.

21. A method for forming a stent comprising the steps of:

a) forming a tube having a surface and an outer cross-sectional area, said tube is formed of a metal alloy that is at least about 99 weight percent of a solid solution of molybdenum and rhenium, said metal alloy including about 46-49 weight percent rhenium and about 51-54 weight percent molybdenum;

b) drawing down said outer cross-sectional area of said tube to a first drawn down cross-sectional area by a reducing mechanism, said tube being drawn down at least once to obtain said first drawn down cross-sectional area, said outer cross-sectional area being reduced by no more than about 25% during each drawing down process, said tube heated to about 400-800°

C. at least partially during said drawing down of said tube, said step of drawing down including the inserting of a close-fitting rod in a passageway of said tube prior to drawing down said tube, said close-fitting rod formed of tantalum and niobium, said tube having a grain size after said drawing down of up to 5 ASTM;

c) annealing said tube prior to said rod or tube having said outer cross-sectional area drawn down by more than about 50% at a first annealing temperature in a low oxygen environment after said tube has been drawn down to said first drawn down cross-sectional area, said step of annealing said tube includes the steps of a) annealing said tube at an annealing temperature ofat least about 1480°

C. for a time period of at least about 5 minutes for a time period of at least about 5 minutes when said tube has wall thickness of greater than about 0.015 inch, b) annealing said tube at an annealing temperature of about 1450-1480°

C. for a time period of at least about 5 minutes when said tube has wall thickness of about 0.008-0.015 inch, and c) annealing said tube at an annealing temperature of less than about 1450°

C. for a time period of at least about 5 minutes when said tube has wall thickness of less than about 0.008 inch;

d) drawing down said cross-sectional area of said tube to a second drawn down cross-sectional area by the reducing mechanism after said tube has been annealed, said tube heated to about 400-800°

C. at least partially during said drawing down of said tube, said step of drawing down including the insertion a close-fitting rod in said passageway of said tube prior to said second drawing down of said tube, said close-fitting rod formed of tantalum and niobium, said second drawn down cross-sectional area smaller than said first drawn down cross-sectional area, said tube having a grain size after said drawing down of up to 5 ASTM, said tube being drawn down at least once to obtain said second drawn down cross-sectional area, said outer cross-sectional area reduced by no more than about 25% during each drawing down process;

e) annealing said tube that is at said second drawn down cross-sectional area at least one additional time at a second annealing temperature, said annealing occurring prior to said tube having said outer cross-sectional area drawn down by more than about 50%, said second anneal temperature lower temperature than said first annealing temperature, said step of annealing said tube includes the steps of a) annealing said tube at an annealing temperature of at least about 1480°

C. for a time period of at least about 5 minutes for a time period of at least about 5 minutes when said tube has wall thickness of greater than about 0.015 inch, b) annealing said tube at an annealing temperature of about 1450-1480°

C. for a time period of at least about 5 minutes when said tube has wall thickness of about 0.008-0.015 inch, and c) annealing said tube at an annealing temperature of less than about 1450°

C. for a time period of at least about 5 minutes when said tube has wall thickness of less than about 0.008 inch;

f) repeating steps d and e until said tube is at a desired thickness and a grain size of 5-14 ASTM, an atmosphere about said rod or tube is controlled during said steps of drawing and annealing so that said metal alloy of said rod or tube after final drawing and annealing steps includes less than about 20 ppm nitrogen. less than about 150 ppm carbon, and less than about 50 ppm oxygen and a carbon to oxygen atomic ratio of at least about 2;

1; and

,

g) cutting said tube to at least partially for said stent.

22. The method as defined in claim 21, wherein said metal alloy includes an additional metal selected from the group consisting of titanium, yttrium, zirconium, and mixtures thereof.

23. The method as defined in claim 21, including the step of nitriding said tube to form a nitride layer on said tube prior to at least one drawing down step, said step of nitriding including a) exposing at least a portion of said tube to a nitriding gas that includes nitrogen, nitrogen and hydrogen, and combinations thereof, and b) exposing at least a portion of said tube to a nitriding gas at a temperature of at least about 400°

C. for at least about 1 minute.

24. The method as defined in claim 22, including the step of nitriding said tube to form a nitride layer on said tube prior to at least one drawing down step, said step of nitriding including a) exposing at least a portion of said tube to a nitriding gas that includes nitrogen, nitrogen and hydrogen, and combinations thereof, and b) exposing at least a portion of said tube to a nitriding gas at a temperature of at least about 400°

C. for at least about 1 minute.

25. The method as defined in claim 23, including the step of removing said nitride layer on said tube prior to annealing said tube.

26. The method as defined in claim 24, including the step of removing said nitride layer on said tube prior to annealing said tube.

27. The method as defined in claim 21, including the step of protecting said tube from oxygen when said tube is exposed to temperatures of greater than about 400-500°

C.

28. The method as defined in claim 22, including the step of protecting said tube from oxygen when said tube is exposed to temperatures of greater than about 400-500°

C.

29. The method as defined in claim 21, wherein said step of drawing down said cross-sectional area of said tube by a reducing mechanism that reduces said cross-sectional area by less than about 20% each time said tube is processed by said reducing mechanism.

30. The method as defined in claim 22, wherein said step of drawing down said cross-sectional area of said tube by a reducing mechanism that reduces said cross-sectional area by less than about 20% each time said tube is processed by said reducing mechanism.

31. The method as defined in claim 21, wherein said step of cutting is at least partially by a laser, said laser cutting of said tube at least partially conducted in a vacuum or an inert atmosphere.

32. The method as defined in claim 22, wherein said step of cutting is at least partially by a laser, said laser cutting of said tube at least partially conducted in a vacuum or an inert atmosphere.

33. The method as defined in claim 31, including the step of electropolishing said stent after said cutting step.

34. The method as defined in claim 32, including the step of electropolishing said stent after said cutting step.

35. The method as defined in claim 21, include the step of using a lubricant during said drawing down of said tube, said lubricant including a molybdenum containing lubricant.

36. The method as defined in claim 22, include the step of using a lubricant during said drawing down of said tube, said lubricant including a molybdenum containing lubricant.