Radiopaque intraluminal stents comprising cobalt-based alloys containing one or more platinum group metals, refractory metals, or combinations thereof
US-2017296365-A1 · Oct 19, 2017 · US
US11298251B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-11298251-B2 |
| Application number | US-201916601259-A |
| Country | US |
| Kind code | B2 |
| Filing date | Oct 14, 2019 |
| Priority date | Nov 17, 2010 |
| Publication date | Apr 12, 2022 |
| Grant date | Apr 12, 2022 |
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Embodiments are directed to radiopaque implantable structures (e.g., stents) formed of cobalt-based alloys that comprise cobalt, chromium, tungsten, and nickel. Tungsten is present above its solubility limit (about 15%), but is still only present as a super-saturated, primarily single-phase material exhibiting an FCC microcrystalline structure.
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The invention claimed is: 1. A radiopaque stent, comprising: a cylindrical main body comprising a cobalt-chromium alloy including cobalt and chromium, the cobalt-chromium alloy including tungsten as a radiopacity increasing element, the tungsten comprising about 20% to about 35% by weight of the cobalt-chromium alloy, the tungsten content being super-saturated, above the solubility limit of tungsten in the cobalt-chromium alloy; wherein the cobalt-chromium alloy further comprises nickel, the nickel being present in a concentration of 5% to about 15% by weight; and wherein the cobalt-chromium alloy exhibits a primarily single-phase FCC solid solution, wherein a second phase of the tungsten is present and makes up no more than 10% volume fraction in the cobalt-chromium alloy, the second phase having an average particle size of less than 5 μm, even with the super-saturated tungsten content. 2. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy comprises cobalt in an amount from about 30% to about 50% by weight of the cobalt-chromium alloy. 3. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy comprises chromium in an amount of about 20% by weight of the cobalt-chromium alloy. 4. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy comprises nickel in an amount of about 10% by weight of the cobalt-chromium alloy. 5. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy is entirely free of molybdenum. 6. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy comprises no more than 1% of silicon, phosphorus, and/or sulfur by weight. 7. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy further comprises manganese in a concentration of up to 5% by weight of the cobalt-chromium alloy. 8. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy further comprises iron in a concentration of up to 5% by weight of the cobalt-chromium alloy. 9. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy further comprises both manganese and iron in a concentration of about 1.5% each, by weight. 10. The radiopaque stent of claim 1 , wherein cobalt comprises from about 66 to 68% by weight of the cobalt-chromium alloy. 11. The radiopaque stent of claim 1 , wherein a weight percent ratio of tungsten to cobalt is at least 0.4. 12. The radiopaque stent of claim 1 , wherein a ratio of tungsten to cobalt is from 0.4 to 1.2. 13. The radiopaque stent of claim 1 , wherein a ratio of tungsten to cobalt is from 0.40 to 0.45. 14. The radiopaque stent of claim 1 , wherein a ratio of tungsten to cobalt is from 0.57 to 0.63. 15. The radiopaque stent of claim 1 , wherein a ratio of tungsten to cobalt is from 1.07 to 1.13. 16. The radiopaque stent of claim 1 , wherein the cobalt-chromium alloy is substantially free of carbon. 17. A radiopaque stent, comprising: a cylindrical main body formed from a single homogenous cobalt-chromium alloy including cobalt, chromium, nickel, and tungsten, the cobalt-chromium alloy not including any other alloying elements in amounts greater than 3% by weight; the cobalt-chromium alloy including tungsten as a radiopacity increasing element, the tungsten comprising about 20% to about 35% by weight of the cobalt-chromium alloy, the tungsten content being super-saturated, above the solubility limit of tungsten in the cobalt-chromium alloy at ambient temperature; wherein the cobalt-chromium alloy comprises about 10% by weight nickel; and wherein the cobalt-chromium alloy exhibits a primarily single-phase FCC solid solution structure, a second phase of the tungsten is present in the cobalt-chromium alloy having a maximum particle size of less than 15 μm, even with the super-saturated tungsten content. 18. The radiopaque stent of claim 17 , wherein the cobalt-chromium alloy is entirely free of molybdenum. 19. The radiopaque stent of claim 17 , wherein the cobalt-chromium alloy is substantially free of carbon. 20. The radiopaque stent of claim 17 , wherein the cobalt-chromium alloy is entirely free of carbon. 21. A radiopaque stent, comprising: a cylindrical main body comprising a cobalt-chromium alloy including cobalt and chromium, the cobalt-chromium alloy including tungsten as a radiopacity increasing element, the tungsten comprising about 20% to about 35% by weight of the cobalt-chromium alloy, the tungsten content being super-saturated, above the solubility limit of tungsten in the cobalt-chromium alloy; wherein the cobalt-chromium alloy further comprises nickel, the nickel being present in a concentration of 5% to about 15% by weight; wherein the cobalt-chromium alloy exhibits a primarily single-phase FCC solid solution, wherein no more than 10% volume fraction of a second phase of the tungsten is present in the cobalt-chromium alloy, the second phase having an average particle size of less than 5 μm, even with the super-saturated tungsten content; and at least one of (i) or (ii): (i) wherein a ratio of tungsten to cobalt is from 1.07 to 1.13; (ii) wherein the cobalt-chromium alloy further comprises both manganese and iron in a concentration of about 1.5% each, by weight. 22. The radiopaque stent of claim 1 , wherein the tungsten comprises 25% to about 30% by weight of the cobalt-chromium alloy.
based on cobalt · CPC title
Alloys based on tungsten or molybdenum · CPC title
Metals or alloys · CPC title
Materials at least partially X-ray or laser opaque · CPC title
Alloys based on chromium · CPC title
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