Stent coating for eluting medication

• US 8,066,764 B2
• Filed: 12/23/2009
• Issued: 11/29/2011
• Est. Priority Date: 01/28/2005
• Status: Expired due to Fees

• Current Assignee: Greatbatch Limited (Greatbatch Incorporated)
• Original Assignee: Greatbatch Limited (Greatbatch Incorporated)
• Inventors: O'Brien, Robert C., Frysz, Christine A.
• Primary Examiner(s): Sweet; Thomas J
• Assistant Examiner(s): STEWART, JASON-DENNIS NEILKEN
• Application Number:
  US12/646,096
• Publication Number:
  US 20100100172A1
• Time in Patent Office: 706 Days
• Field of Search: 623 142- 146, 427/2.24
• US Class Current: 623/1.46
• 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 2250/0067 Means for introducing or releasing pharmaceutical products into the body
• CPC Class Codes: A61F 2250/0068 the pharmaceutical product being in a reservoir
• CPC Class Codes: A61L 2300/108 Elemental carbon, e.g. charcoal
• CPC Class Codes: A61L 31/084 Carbon; Graphite
• CPC Class Codes: A61L 31/146 Porous materials, e.g. foams or sponges
• CPC Class Codes: A61L 31/16 Biologically active materials, e.g. therapeutic substances A61L31/047 takes precedence
• CPC Class Codes: Y10T 29/49885 with coating before or during assembling

Abstract

A vascular stent comprising a drug-eluting outer layer of a porous sputtered columnar metal having each column capped with a biocompatible carbon-containing material is described. This is done by placing the stent over a close-fitting mandrel and rotating the assembly in a sputter flux. The result is a coating that is evenly distributed over the outward-facing side of the stent'"'"'s wire mesh while preventing the sputtered columnar coating from reaching the inward facing side where a smooth hemocompatible surface is required. The stent is then removed from the mandrel, exposing all surfaces, and finally coated with a layer of carbon such as amorphous carbon or diamond-like carbon. The carbonaceous coating enhances biocompatibility without preventing elutriation of a therapeutic drug provided in the porosity formed between the columnar structures. The result is a stent that is adapted to both the hemodynamic and the immune response requirements of its vascular environment.

Claims

1. A method for providing a stent suitable for insertion and expansion into a vasculature to support an adjacent vasculature region, comprising the steps of:

a) providing a plurality of wires forming an elongated and selectively expandable and constrictable hollow tube, each wire providing a substrate having a cross-section comprising an outside-facing surface portion and an inside-facing surface portion, wherein in an expanded condition, a lumen formed by the hollow tube has a diameter that is greater than when in the constricted condition such that in the expanded condition at least the outside-facing surface portions of the plurality of substrate wires are subjected to both tension forces (+σ

e) and compression forces (−

σ

e) within an elastic limit of the wires;

b) providing the hollow tube in the expanded condition;

c) adhering an intermediate coating to at least some of the outside-facing surface portions of the substrate wires of the expanded hollow tube, the thusly adhered intermediate coating being in a zero stress state within the elastic limits of the wires and comprising a plurality of columnar structures, each of the columns having a sidewall extending between a proximal end adhered to the outside-facing surface portion of the substrate wires and a distal end spaced therefrom with the sidewalls of immediately adjacent columns not contacting each other to thereby provide an area of the substrate wires between adjacent columns that is not contacted by the intermediate coating serving as porosity between the columns; and

d) capping the distal end of each of the plurality of columnar structures with a carbon-containing material.

2. The method of claim 1 including providing the stent comprising a nickel titanium shape memory alloy heated to less than an elastic stress limit of the plurality of wires prior to providing the intermediate coating thereon.

3. The method of claim 2 including heating the nickel titanium shape memory alloy to less than its elastic stress limit in a sputter chamber.

4. The method of claim 1 including providing a polymeric material covering the carbonaceous caps.

5. The method of claim 1 including adhering the intermediate coating to the substrate wires and capping the distal end of each of the plurality of columnar structures with the carbon-containing coating by one of the deposition techniques selected from the group consisting of sputtering, chemical vapor deposition, pulsed laser deposition, reactive evaporation, and as a thermal spray.

6. The method of claim 1 including providing the wires of a material selected from the group consisting of platinum, Nitinol, and medical grade 316L, stainless steel containing about 16% nickel.

7. The method of claim 1 including providing a. polymer in the porosity between the columnar structures, the polymer being selected from the group consisting of polyurethane, silicone, polyesters, polycarbonate, polyethylene, polyvinyl chloride, polypropylene methylacrylate, para-xylylene, and mixtures thereof.

8. The method of claim 1 including filling an elutable material into the porosity provided between each of the plurality of columnar structures.

9. The method of claim 8 including providing the elutable material as a medication filled into the porosity between the columnar structures.

10. A method for providing a stent suitable for insertion and expansion into a vasculature to support an adjacent vasculature region, comprising the steps of:

a) providing a plurality of wires comprising a shape memory alloy forming an elongated and selectively expandable and constrictable hollow tube, each wire providing a substrate having a cross-section comprising an outside-facing surface portion and an inside-facing surface portion, wherein in an expanded condition, a lumen formed by the hollow tube has a diameter that is greater than when in the constricted condition such that in the expanded condition at least the outside-facing surface portions of the plurality of substrate wires are subjected to both tension forces (+σ

e) and compression forces (−

σ

e) within an elastic limit of the wires;

b) heating the shape memory alloy to less than its elastic stress limit to thereby provide the hollow tube in the expanded condition;

c) adhering an intermediate coating to at least some of the outside-facing surface portions of the substrate wires of the expanded hollow tube, the thusly adhered intermediate coating being in a zero stress state within the elastic limits of the wires and comprising a plurality of columnar structures, each of the columns having a sidewall extending between a proximal end adhered on the outside-facing surface portion of the substrate wires and a distal end spaced therefrom with the sidewalls of immediately adjacent columns not contacting each other to thereby provide an area of the substrate wires between adjacent columns that is not contacted by the intermediate coating serving as porosity between the columns; and

d) capping the distal end of each of the plurality of columnar structures with a carbon-containing material formed thereon.

11. The method of claim 10 including providing the stent comprising a nickel titanium shaped memory alloy.

12. The method of claim 10 including heating the shape memory alloy to less than its elastic stress limit in a sputter chamber.

13. The method of claim 10 including selecting the intermediate coating from the group consisting of carbides, oxides, nitrides, oxynitrides, and carbonitrides of titanium, boron, aluminum, calcium, gold, hafnium, iridium, molybdenum, niobium, platinum, rhenium, ruthenium, silicon, silver, tantalum, titanium, tungsten, yttrium, zirconium.

14. The method of claim 10 including providing a polymer in the porosity between the columnar structures, the polymer being selected from the group consisting of polyurethane, silicone, polyesters, polycarbonate, polyethylene, polyvinyl chloride, polypropylene methylacrylate, para-xylylene, and mixtures thereof.

15. The method of claim 10 including providing a polymeric material covering the carbonaceous caps.

16. The method of claim 10 including adhering the intermediate coating to the substrate wires and capping the distal end of each of the plurality of columnar structures with the carbon-containing coating by one of the deposition techniques selected from the group consisting of sputtering, chemical vapor deposition, pulsed laser deposition, reactive evaporation, and as a thermal spray.

17. The method of claim 10 including filling an elutable material into the porosity provided between each of the plurality of columnar structures.

18. The method of claim 17 including providing the elutable material as a medication filled into the porosity between the columnar structures.

19. A method for providing a stent suitable for insertion and expansion into a vasculature to support an adjacent vasculature region, comprising the steps of:

a) providing a plurality of nickel titanium wires forming an elongated and selectively expandable and constrictable hollow tube, each wire providing a substrate having a cross-section comprising an outside-facing surface portion and an inside-facing surface portion, wherein in an expanded condition, a lumen formed by the hollow tube has a diameter that is greater than when in the constricted condition such that in the expanded condition at least the outside-facing surface portions of the plurality of substrate wires are subjected to both tension forces (+σ

e) and compression forces (−

σ

e) within an elastic limit of the wires;

b) providing the hollow tube in the expanded condition;

c) adhering an intermediate coating of titanium nitride to at least some of the outside-facing surface portions of the substrate wires of the expanded hollow tube, the thusly adhered titanium nitride coating being in a zero stress state within the elastic limits of the wires and comprising a plurality of columnar titanium nitride structures, each of the columns having a sidewall extending between a proximal end adhered to the outside-facing surface portion of the substrate wires and a distal end spaced therefrom with the sidewalls of immediately adjacent titanium nitride columns not contacting each other to thereby provide an area of the substrate wires between adjacent columns that is not contacted by the intermediate coating serving as porosity between the columns;

d) capping the distal end of each of the plurality of columnar titanium nitride structures with a carbon-containing material.

20. The method of claim 19 including filling an elutable material into the porosity provided between each of the plurality of columnar titanium nitride structures.