WO2023048840A1 - Coating for refractory metal alloy - Google Patents
Coating for refractory metal alloy Download PDFInfo
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- WO2023048840A1 WO2023048840A1 PCT/US2022/039576 US2022039576W WO2023048840A1 WO 2023048840 A1 WO2023048840 A1 WO 2023048840A1 US 2022039576 W US2022039576 W US 2022039576W WO 2023048840 A1 WO2023048840 A1 WO 2023048840A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal alloy
- refractory metal
- medical device
- values
- alloy
- Prior art date
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- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 467
- 239000003870 refractory metal Substances 0.000 title claims abstract description 459
- 238000000576 coating method Methods 0.000 title claims abstract description 126
- 239000011248 coating agent Substances 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 claims abstract description 114
- 229910052751 metal Inorganic materials 0.000 claims description 172
- 239000002184 metal Substances 0.000 claims description 172
- 238000000034 method Methods 0.000 claims description 161
- 230000008569 process Effects 0.000 claims description 126
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 116
- 239000011651 chromium Substances 0.000 claims description 111
- 229910052702 rhenium Inorganic materials 0.000 claims description 111
- 229920000642 polymer Polymers 0.000 claims description 105
- 239000010936 titanium Substances 0.000 claims description 94
- 229910052799 carbon Inorganic materials 0.000 claims description 93
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 93
- 229910052804 chromium Inorganic materials 0.000 claims description 90
- 239000010955 niobium Substances 0.000 claims description 88
- 229910052726 zirconium Inorganic materials 0.000 claims description 88
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 86
- 239000003795 chemical substances by application Substances 0.000 claims description 84
- 229910052750 molybdenum Inorganic materials 0.000 claims description 80
- 229910052715 tantalum Inorganic materials 0.000 claims description 79
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 78
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 76
- 239000011733 molybdenum Substances 0.000 claims description 76
- 229910052757 nitrogen Inorganic materials 0.000 claims description 76
- 229910052719 titanium Inorganic materials 0.000 claims description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 73
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 72
- 229910052758 niobium Inorganic materials 0.000 claims description 70
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 69
- 229910052760 oxygen Inorganic materials 0.000 claims description 68
- 229910052721 tungsten Inorganic materials 0.000 claims description 68
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 67
- 239000010937 tungsten Substances 0.000 claims description 66
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 62
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 62
- 239000000956 alloy Substances 0.000 claims description 61
- 229910045601 alloy Inorganic materials 0.000 claims description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 55
- 229910052741 iridium Inorganic materials 0.000 claims description 55
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 55
- 239000010949 copper Substances 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 54
- 229910052727 yttrium Inorganic materials 0.000 claims description 52
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 49
- 229910052735 hafnium Inorganic materials 0.000 claims description 49
- 229910052762 osmium Inorganic materials 0.000 claims description 49
- 239000001301 oxygen Substances 0.000 claims description 49
- 229910052713 technetium Inorganic materials 0.000 claims description 48
- 229910052720 vanadium Inorganic materials 0.000 claims description 48
- 229910052802 copper Inorganic materials 0.000 claims description 46
- 150000002739 metals Chemical class 0.000 claims description 45
- 239000010948 rhodium Substances 0.000 claims description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 44
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 42
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 42
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 42
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims description 42
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 42
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 41
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 41
- 229910052703 rhodium Inorganic materials 0.000 claims description 41
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 41
- 229910052707 ruthenium Inorganic materials 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 38
- 229910052697 platinum Inorganic materials 0.000 claims description 34
- 239000010941 cobalt Substances 0.000 claims description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 33
- 229910017052 cobalt Inorganic materials 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 31
- 230000002829 reductive effect Effects 0.000 claims description 31
- 239000012535 impurity Substances 0.000 claims description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 28
- 229910052791 calcium Inorganic materials 0.000 claims description 28
- 239000011575 calcium Substances 0.000 claims description 28
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 28
- 239000010931 gold Substances 0.000 claims description 28
- 229910052737 gold Inorganic materials 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 229910052709 silver Inorganic materials 0.000 claims description 28
- 239000004332 silver Substances 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011133 lead Substances 0.000 claims description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 27
- 150000002910 rare earth metals Chemical class 0.000 claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims description 27
- 239000011701 zinc Substances 0.000 claims description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 26
- 229910052749 magnesium Inorganic materials 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 26
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 25
- 229910052746 lanthanum Inorganic materials 0.000 claims description 25
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 25
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 25
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 25
- 238000005240 physical vapour deposition Methods 0.000 claims description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims description 16
- 238000000231 atomic layer deposition Methods 0.000 claims description 15
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 14
- 238000005275 alloying Methods 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 13
- 150000004767 nitrides Chemical class 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 238000005336 cracking Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 6
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003124 biologic agent Substances 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- 238000002788 crimping Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 230000001988 toxicity Effects 0.000 claims description 5
- 231100000419 toxicity Toxicity 0.000 claims description 5
- VKTRRMAGOGCOHX-UHFFFAOYSA-N [C].[N].[Zr] Chemical compound [C].[N].[Zr] VKTRRMAGOGCOHX-UHFFFAOYSA-N 0.000 claims description 3
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012255 powdered metal Substances 0.000 claims 6
- 238000010285 flame spraying Methods 0.000 claims 4
- 239000000446 fuel Substances 0.000 claims 4
- 238000005468 ion implantation Methods 0.000 claims 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 3
- 239000002356 single layer Substances 0.000 claims 1
- 230000000670 limiting effect Effects 0.000 description 263
- -1 pacemaker Substances 0.000 description 67
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 40
- 238000005498 polishing Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- 238000000137 annealing Methods 0.000 description 27
- 229910052797 bismuth Inorganic materials 0.000 description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 26
- 229910052739 hydrogen Inorganic materials 0.000 description 24
- 239000003550 marker Substances 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 238000005121 nitriding Methods 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
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- 239000001257 hydrogen Substances 0.000 description 18
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- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 11
- 230000002411 adverse Effects 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 11
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 11
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- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 10
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- A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
Definitions
- the disclosure relates generally to refractory metal alloy such as, but not limited to a refractory metal alloys, particularly to a protective coating for a refractory metal alloy, and even more particularly to a medical device that is at least partially formed of a refractory metal alloy.
- Stainless steel, cobalt-chromium alloys, and TiAIV alloys are some of the more common metal alloys used for medical devices. Although these alloys have been successful in forming a variety of medical devices, these alloys have several deficiencies.
- the present disclosure is directed to a refractory metal alloy, and in particular to a refractory metal alloy that include rhenium, and wherein in the refractory metal alloy is partially or fully coated with material that improves one or more properties of the refractory metal alloy.
- the medical device can include, but is not limited to, an orthopedic device, PFO (patent foramen ovale) device, stent, valve (e.g., heart valve, TAVR valve, mitral valve replacement, tricuspid valve replacement, pulmonary valve replacement, etc.), spinal implant, spinal discs, frame and other structures for use with a spinal implant, vascular implant, graft, guide wire, sheath, catheter, needle, stent catheter, electrophysiology catheter, hypotube, staple, cutting device, any type of implant, pacemaker, dental implant, dental crown, dental braces, wire used in medical procedures, bone implant, artificial disk, artificial spinal disk, prosthetic implant or device to repair, replace and/or support a bone (e.g., acromion, atlas, axis, calcaneus, carpus, clavicle, coccyx, epicondyle, epitrochlea, femur, fibula, front
- a bone e.g., acromion
- a medical device partially or fully formed of a refractory metal alloy.
- 50-100% (and all values and ranges therebetween) of the medical device is formed of the refractory metal alloy.
- at least 30 wt.% (e.g., 30-100 wt.% and all values and ranges therebetween) of the medical device is formed of a refractory metal alloy that includes rhenium (e.g., MoRe alloy, ReW alloy, MoReCr alloy, MoReTa alloy, MoReTi alloy, or ReCr alloy, etc.).
- rhenium e.g., MoRe alloy, ReW alloy, MoReCr alloy, MoReTa alloy, MoReTi alloy, or ReCr alloy, etc.
- the refractory metal alloy that is used to form at least a portion of the medical device has one or more improved properties (e.g., strength, durability, hardness, biostability, bendability, coefficient of friction, radial strength, flexibility, tensile strength, tensile elongation, longitudinal lengthening, stress-strain properties, reduced recoil, radiopacity, heat sensitivity, biocompatibility, improved fatigue life, crack resistance, crack propagation resistance, reduced magnetic susceptibility, etc.), improved conformity when bent, less recoil, increase yield strength, improved fatigue ductility, improved durability, improved fatigue life, reduced adverse tissue reactions, reduced metal ion release, reduced corrosion, reduced allergic reaction, improved hydrophilicity, reduced toxicity, reduced thickness of metal component, improved bone fusion, and/or lower ion release into tissue.
- improved properties e.g., strength, durability, hardness, biostability, bendability, coefficient of friction, radial strength, flexibility, tensile strength, tensile elongation,
- These one or more improved physical properties of the refractory metal alloy can be achieved in the medical device without having to increase the bulk, volume, and/or weight of the medical device, and in some instances these improved physical properties can be obtained even when the volume, bulk, and/or weight of the medical device is reduced as compared to medical devices that are at least partially formed from traditional stainless steel, titanium alloy, or cobalt and chromium alloy materials.
- the refractory metal alloy used to at least partially form the medical device can thus 1) increase the radiopacity of the medical device, 2) increase the radial strength of the medical device, 3) increase the yield strength and/or ultimate tensile strength of the medical device, 4) improve the stress-strain properties of the medical device, 5) improve the crimping and/or expansion properties of the medical device, 6) improve the bendability and/or flexibility of the medical device, 7) improve the strength and/or durability of the medical device, 8) increase the hardness of the medical device, 9) improve the recoil properties of the medical device, 10) improve the biostability and/or biocompatibility properties of the medical device, 11) increase fatigue resistance of the medical device, 12) resist cracking in the medical device and resist propagation of cracks, 13) enable smaller, thinner, and/or lighter weight medical device to be made, 14) reduce the outer diameter of a crimped medical device, 15) improve the conformity
- the medical device is optionally subjected to one or more manufacturing processes.
- These manufacturing processes can include, but are not limited to, expansion, laser cutting, etching, crimping, annealing, drawing, pilgering, electroplating, electro-polishing, machining, plasma coating, 3D printing, 3D printed coatings, chemical vapor deposition, chemical polishing, cleaning, pickling, ion beam deposition or implantation, sputter coating, vacuum deposition, etc.
- a portion or all of the medical device is formed by a 3D printing process.
- the refractory metal alloy that is used to at least partially form the medical device optionally has a generally uniform density throughout the refractory metal alloy, and also results in the desired yield and ultimate tensile strengths of the refractory metal alloy.
- the density of the refractory metal alloy is generally at least about 5 gm/cc (e.g., 5 gm/cc-21 gm/cc and all values and ranges therebetween; 10-20 gm/cc; etc.), and typically at least about 11-19 gm/cc. This substantially uniform high density of the refractory metal alloy can optionally improve the radiopacity of the refractory metal alloy.
- the refractory metal alloy optionally includes a certain amount of carbon and oxygen; however, this is not required. These two elements have been found to affect the forming properties and brittleness of the refractory metal alloy.
- the controlled atomic ratio of carbon and oxygen of the refractory metal alloy also can be used to minimize the tendency of the refractory metal alloy to form micro-cracks during the forming of the refractory metal alloy at least partially into a medical device, and/or during the use and/or expansion of the medical device in a body passageway.
- the control of the atomic ratio of carbon to oxygen in the refractory metal alloy allows for the redistribution of oxygen in the refractory metal alloy to minimize the tendency of micro-cracking in the refractory metal alloy during the forming of the refractory metal alloy at least partially into a medical device, and/or during the use and/or expansion of the medical device in a body passageway.
- the atomic ratio of carbon to oxygen in the refractory metal alloy is believed to facilitate in minimizing the tendency of micro-cracking in the refractory metal alloy and improve the degree of elongation of the refractory metal alloy, both of which can affect one or more physical properties of the refractory metal alloy that are useful or desired in forming and/or using the medical device.
- the carbon to oxygen atomic ratio can be as low as about 0.2: 1 (e.g., 0.2:1 to 50: 1 and all values and ranges therebetween).
- the carbon to oxygen atomic ratio in the refractory metal alloy is generally at least about 0.3: 1.
- the carbon content of the refractory metal alloy is less than about 0.2 wt.% (e.g., 0 wt.% to 0.1999999 wt.% and all values and ranges therebetween). Carbon contents that are too large can adversely affect the physical properties of the refractory metal alloy.
- the oxygen content is to be maintained at very low level.
- the oxygen content is less than about 0.1 wt.% of the refractory metal alloy (e.g., 0 wt. to 0.0999999 wt.% and all values and ranges therebetween). It is believed that the refractory metal alloy will have a very low tendency to form micro-cracks during the formation of the medical device and after the medical device has been inserted into a patient by closely controlling the carbon to oxygen ration when the oxygen content exceeds a certain amount in the refractory metal alloy. In one non-limiting arrangement, the carbon to oxygen atomic ratio in the refractory metal alloy is at least about 2.5: 1 when the oxygen content is greater than about 100 ppm in the refractory metal alloy.
- the refractory metal alloy optionally includes a controlled amount of nitrogen; however, this is not required.
- Large amounts of nitrogen in the refractory metal alloy can adversely affect the ductility of the refractory metal alloy. This can in turn adversely affect the elongation properties of the refractory metal alloy.
- a too high nitrogen content in the refractory metal alloy can begin to cause the ductility of the refractory metal alloy to unacceptably decrease, thus adversely affect one or more physical properties of the refractory metal alloy that are useful or desired in forming and/or using the medical device.
- the refractory metal alloy includes less than about 0.001 wt.% nitrogen (e.g., 0 wt.% to -0.0009999 wt.% and all values and ranges therebetween). It is believed that the nitrogen content should be less than the content of carbon or oxygen in the refractory metal alloy.
- the atomic ratio of carbon to nitrogen is at least about 1.5: 1 (e.g., 1.5: 1 to 400: 1 and all values and ranges therebetween).
- the atomic ratio of oxygen to nitrogen is at least about 1.2: 1 (e.g., 1.2: 1 to 150: 1 and all value and ranges therebetween).
- the medical device is generally designed to include at least about 5 wt.% of the refractory metal alloy (e.g., 5 -100 wt.% and all values and ranges therebetween). In one non-limiting embodiment of the disclosure, the medical device includes at least about 50 wt.% of the refractory metal alloy. In another non-limiting embodiment of the disclosure, the medical device includes at least about 95 wt.% of the refractory metal alloy.
- the expandable frame when the medical device includes an expandable frame, is formed of 50-100 wt.% (and all values and ranges therebetween) of the refractory metal alloy, and typically 75-100 wt.% of the refractory metal alloy.
- the refractory metal alloy used to form all or part of the medical device 1) is optionally not clad, metal sprayed, plated, and/or formed (e.g., cold worked, hot worked, etc.) onto another metal, or 2) optionally does not have another metal or metal alloy metal sprayed, plated, clad, and/or formed onto the refractory metal alloy.
- the medical device can optionally be at least partially or fully formed from a tube or rod of refractory metal alloy, or be formed into shape that is at least 80% of the final net shape of the medical device.
- the medical device can be at least partially or fully formed from by 3D printing.
- the average grain size of the refractory metal alloy of the present disclosure used to at least partially form the medical device is optionally no greater than about 4 ASTM (e.g., 4 ASTM to 20 ASTM using ASTM El 12 and all values and ranges therebetween, e.g., 0.35 micron to 90 micron, and all values and ranges therebetween).
- 4 ASTM e.g., 4 ASTM to 20 ASTM using ASTM El 12 and all values and ranges therebetween, e.g., 0.35 micron to 90 micron, and all values and ranges therebetween.
- the unique combination of the metals in the refractory metal alloy of the present disclosure in combination with achieving the desired purity and composition of the refractory metal alloy and the desired grain size of the refractory metal alloy results in 1) a medical device having the desired high ductility at about room temperature, 2) a medical device having the desired amount of tensile elongation, 3) a homogeneous or solid solution of a refractory metal alloy having high radi opacity, 4) a reduction or prevention of micro-crack formation and/or breaking of the refractory metal alloy of the present disclosure tube when the tube is sized and/or cut to form the medical device, 5) a reduction or prevention of micro-crack formation and/or breaking of the medical device when the medical device is crimped, 6) a reduction or prevention of micro-crack formation and/or breaking of the medical device when the medical device is bent and/or expanded in a body passageway, 7)
- At least 50 wt.% (e.g., 50-100 wt.% and all values and ranges therebetween) of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten, and 0-40 wt.% (and all values and ranges therebetween) of the refractory alloy includes one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, nickel, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, technetium, titanium, vanadium, yttrium, yttrium oxide, zinc, zirconium, or zirconium oxide.
- At least 50 wt.% (e.g., 50-99.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten, and 0.1-40 wt.% (and all values and ranges therebetween) of the refractory alloy includes one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, nickel, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, technetium, titanium, vanadium, yttrium, yttrium oxide, zinc, zirconium, or zirconium oxide, and the refractory alloy includes 0-2 wt.% (and all values and ranges therebetween) of
- At least 55 wt.% of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten, and 0-40 wt.% of the refractory alloy includes one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, nickel, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, technetium, titanium, vanadium, yttrium, yttrium oxide, zinc, zirconium, or zirconium oxide, and the refractory alloy includes 0-0.1 wt.% of a combination of other metals, carbon, oxygen and nitrogen.
- At least 55 wt.% of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten, and 0.1-40 wt.% of the refractory alloy includes one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, nickel, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, technetium, titanium, vanadium, yttrium, yttrium oxide, zinc, zirconium, or zirconium oxide, and the refractory alloy includes 0-0.1 wt.% of a combination of other metals, carbon, oxygen and nitrogen.
- the refractory metal alloy includes at least 30 wt.% (e.g., 30-99 wt.% and all values and ranges therebetween) rhenium and one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, tantalum, technetium, titanium, tungsten, vanadium, yttrium, yttrium oxide, zinc, zirconium, or zirconium oxide.
- rhenium e.g., 30-99 wt.% and all values and ranges therebetween
- the refractory metal alloy includes at least 35 wt.% (e.g., 35-99 wt.% and all values and ranges therebetween) rhenium and 0.1-65 wt.% (and all values and ranges therebetween) of one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, tantalum, technetium, titanium, tungsten, vanadium, yttrium, yttrium oxide, zinc, zirconium, or zirconium oxide.
- 35 wt.% e.g., 35-99 wt.% and all values and ranges therebetween
- rhenium and 0.1-65 wt.% and all values
- the refractory metal alloy includes at least 35 wt.% (e.g., 35-99 wt.% and all values and ranges therebetween) rhenium and 0.1-65 wt.% (and all values and ranges therebetween) of one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, tantalum, technetium, titanium, tungsten, vanadium, yttrium, yttrium oxide, zinc, zirconium, or zirconium oxide, and the refractory metal alloy includes 0-2 wt.% (and all values and ranges therebetween) of a combination of other metals, carbon, oxygen, and nitrogen.
- the refractory metal alloy includes at least 40 wt.% (e.g., 40-99.9 wt.% and all values and ranges therebetween) rhenium and 0.1-60 wt.% (and all values and ranges therebetween) of one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, tantalum, technetium, titanium, tungsten, vanadium, yttrium, yttrium oxide, zinc, zirconium, or zirconium oxide, and the refractory metal alloy includes 0-0.1 wt.% (and all values and ranges therebetween) of a combination of other metals, carbon, oxygen, and nitrogen
- a refractory metal alloy wherein at least 20 wt.% (e.g., 20-99 wt.% and all values and ranges therebetween) of the refractory metal alloy includes rhenium.
- the refractory metal alloy includes at least 20 wt.% (e.g., 30-99.9 wt.% and all values and ranges therebetween) rhenium, and 0.1-80 wt.% (and all values and ranges therebetween) of one or more of copper, chromium, hafnium, iridium, manganese, molybdenum, niobium, osmium, rhodium, ruthenium, tantalum, technetium, titanium, tungsten, vanadium, zirconium, and and/or alloys of one or more of such components.
- the refractory metal alloy includes at least 30 wt.% (e.g., 30- 99.9 wt.% and all values and ranges therebetween) rhenium, and 0.1-70 wt.% (and all values and ranges therebetween) of one or more of copper, chromium, hafnium, iridium, manganese, molybdenum, niobium, osmium, rhodium, ruthenium, tantalum, technetium, titanium, tungsten, vanadium, zirconium, and and/or alloys of one or more of such components.
- the refractory metal alloy includes at least 35 wt.% (e.g., 35-99.9 wt.% and all values and ranges therebetween) rhenium, and 0.1-65 wt.% (and all values and ranges therebetween) of one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, tantalum, technetium, titanium, tungsten, vanadium, yttrium, yttrium oxide, zinc, zirconium, zirconium oxide, and/or alloys of one or more of such components.
- 35 wt.% e.g., 35-99.9 wt.% and all values and ranges therebetween
- the refractory metal alloy includes at least 35 wt.% (e.g., 35-99.9 wt.% and all values and ranges therebetween) rhenium, and 0.1-65 wt.% (and all values and ranges therebetween) of one or more of copper, chromium, hafnium, iridium, manganese, molybdenum, niobium, osmium, rhodium, ruthenium, tantalum, technetium, titanium, tungsten, vanadium, zirconium, and and/or alloys of one or more of such components.
- the refractory metal alloy includes 35-60 wt.% (and all values and ranges therebetween) rhenium, and 40-65 wt.% (and all values and ranges therebetween) of one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, tantalum, technetium, titanium, tungsten, vanadium, yttrium, yttrium oxide, zinc, zirconium, zirconium oxide, and/or alloys of one or more of such components.
- the refractory metal alloy includes at least 40 wt.% (e.g., 40-99.9 wt.% and all values and ranges therebetween) rhenium, and 0.1-60 wt.% (and all values and ranges therebetween) of one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, tantalum, technetium, titanium, tungsten, vanadium, yttrium, yttrium oxide, zinc, zirconium, zirconium oxide, and/or alloys of one or more of such components.
- wt.% e.g., 40-99.9 wt.% and all values and ranges therebetween
- the refractory metal alloy includes at least 50 wt.% (e.g., 50-99.9 wt.% and all values and ranges therebetween) rhenium, and 0.1-50 wt.% (and all values and ranges therebetween) of one or more of calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iridium, iron, lanthanum, lanthanum oxide, lead, magnesium, manganese, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhodium, ruthenium, silver, tantalum, technetium, titanium, tungsten, vanadium, yttrium, yttrium oxide, zinc, zirconium, zirconium oxide, and/or alloys of one or more of such components.
- wt.% e.g., 50-99.9 wt.% and all values and ranges therebetween
- the refractory metal alloy includes at least 50 wt.% (e.g., SO- 99.9 wt.% and all values and ranges therebetween) rhenium, and 0.1-50 wt.% (and all values and ranges therebetween) of one or more of copper, chromium, hafnium, iridium, manganese, molybdenum, niobium, osmium, rhodium, ruthenium, tantalum, technetium, titanium, tungsten, vanadium, zirconium, and and/or alloys of one or more of such components.
- wt.% e.g., SO- 99.9 wt.% and all values and ranges therebetween
- rhenium e.g., SO- 99.9 wt.% and all values and ranges therebetween
- 0.1-50 wt.% and all values and ranges therebetween
- the metals used to form the refractory metal alloy includes rhenium and tungsten and optionally one or more alloying agents such as, but not limited to, calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iron, lanthanum oxide, lead, magnesium, molybdenum, nickel, niobium, osmium, platinum, rare earth metals, rhenium, silver, tantalum, technetium, titanium, vanadium, yttrium, yttrium oxide, zinc, zirconium, zirconium oxide, and/or alloys of one or more of such components (e.g., WRe, WReMo, etc.).
- alloying agents such as, but not limited to, calcium, carbon, cerium oxide, chromium, cobalt, copper, gold, hafnium, iron, lanthanum oxide, lead, magnesium, molybdenum, nickel, niobium, osmium, platinum, rare
- the refractory metal alloy is described as including one or more metals and/or metal oxides, it can be appreciated that some of the metals and/or metal oxides in the refractory metal alloy can be substituted for one or more materials selected from the group of ceramics, plastics, thermoplastics, thermosets, rubbers, laminates, non-wovens, etc.
- the refractory metal alloy includes 1-40 wt.% rhenium (and all values and ranges therebetween) and 60-99 wt.% tungsten (and all values and ranges therebetween).
- the total weight percent of the tungsten and rhenium in the tungstenrhenium alloy is at least about 95 wt.%, typically at least about 99 wt.%, more typically at least about 99.5 wt.%, yet more typically at least about 99.9 wt.%, and still more typically at least about 99.99 wt.%.
- the refractory metal alloy includes 1-47.5 wt.% rhenium (and all values and ranges therebetween) and 20-80 wt.% tungsten (and all values and ranges therebetween) and 1-47.5 wt.% molybdenum (and all values and ranges therebetween).
- the total weight percent of the tungsten, rhenium, and molybdenum in the tungsten-rhenium- molybdenum alloy is at least about 95 wt.%, typically at least about 99 wt.%, more typically at least about 99.5 wt.%, yet more typically at least about 99.9 wt.%, and still more typically at least about 99.99 wt.%.
- the weight percent of the tungsten is greater than a weight percent of rhenium and also greater than the weight percent of molybdenum.
- the weight percent of the tungsten is greater than 50 wt.% of the tungsten-rhenium-molybdenum alloy. In another non-limiting specific tungsten-rhenium-molybdenum alloy, the weight percent of the tungsten is greater than a weight percent of rhenium, but less than a weigh percent of molybdenum. In another non-limiting specific tungsten-rhenium-molybdenum alloy, the weight percent of the tungsten is greater than a weight percent of molybdenum, but less than a weigh percent of rhenium. In another non-limiting specific tungsten-rhenium-molybdenum alloy, the weight percent of the tungsten is less than a weight percent of rhenium and also less than the weight percent of molybdenum.
- a combined weight percentage of rhenium and alloy metals in the refractory metal alloy is greater than the weight percent of molybdenum in the refractory metal alloy.
- a weight percent of molybdenum in the refractory metal alloy is at least 10 wt.% and less than 60 wt.% (and all values and ranges therebetween).
- a weight percent of rhenium in the refractory metal alloy is 35-60 wt.% (and all values and ranges therebetween).
- a combined weight percent of the alloying metals is 5-45 wt.% (and all values and ranges therebetween) of the refractory metal alloy.
- a weight percent of the rhenium in the refractory metal alloy is greater than a combined weight percent of the alloying metals. In another non-limiting embodiment, a combined weight percent of the rhenium, molybdenum, and the one or more alloying metals in the refractory metal alloy is at least 99.9 wt.%.
- alloy metal includes chromium. In another non-limiting embodiment, the alloying metal includes chromium and one or more metals selected from the group consisting of bismuth, zirconium, iridium, niobium, tantalum, titanium, and yttrium.
- the alloying metal includes chromium and one or more metals selected from the group consisting of bismuth, zirconium, iridium, niobium, tantalum, titanium, and yttrium; and wherein an atomic ratio of chromium to an atomic ratio of each or all of the metals selected from the group consisting of bismuth, chromium, iridium, niobium, tantalum, titanium, and yttrium is 0.4: 1 to 2.5: 1 (and all values and ranges therebetween).
- the alloying metal includes chromium and one or more metals selected from the group consisting of zirconium, niobium, and tantalum.
- the alloying metal includes a first metal selected from the group consisting of bismuth, chromium, iridium, niobium, tantalum, titanium, yttrium and zirconium, and a second metal selected from the group consisting of bismuth, chromium, iridium, niobium, tantalum, titanium, yttrium and zirconium; and wherein the first and second metals are different; and wherein an atomic ratio of the first metal to the second metal is 0.4: 1 to 2.5: 1 (and all values and ranges therebetween).
- the weight percent of molybdenum in the refractory metal alloy is at least 10 wt.% and less than 50 wt.% (and all values and ranges therebetween). In another non-limiting specific non-limiting formulation, the weight percent of rhenium in the refractory metal alloy is 41-58.5 wt.% (and all values and ranges therebetween), the weight percent of molybdenum in the refractory metal alloy is at least 15-45 wt.% (and all values and ranges therebetween), and the combined weight percent of bismuth, niobium, tantalum, tungsten, titanium, vanadium, chromium, manganese, yttrium, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and iridium in the refractory metal alloy is 11-41 wt.% (and all values and ranges therebetween).
- the weight percent of rhenium in the refractory metal alloy is 41-58.5 wt.% (and all values and ranges therebetween)
- the weight percent of molybdenum in the refractory metal alloy is at least 15-45 wt.% (and all values and ranges therebetween)
- the combined weight percent of bismuth, chromium, iridium, niobium, tantalum, titanium, yttrium, and zirconium in the refractory metal alloy is 11-41 wt.% (and all values and ranges therebetween).
- the weight percent of rhenium in the refractory metal alloy is 41-58.5 wt.% (and all values and ranges therebetween)
- the weight percent of molybdenum in the refractory metal alloy is at least 15-45 wt.% (and all values and ranges therebetween)
- the combined weight percent of chromium, niobium, tantalum, and zirconium in the refractory metal alloy is 11-41 wt.% (and all values and ranges therebetween).
- the weight percent of rhenium in the refractory metal alloy is greater than the combined weight percent of bismuth, chromium, iridium, niobium, tantalum, titanium, yttrium, and zirconium in the refractory metal alloy. In another non-limiting specific non-limiting formulation, the weight percent of rhenium in the refractory metal alloy is greater than the combined weight percent of chromium, niobium, tantalum, and zirconium in the refractory metal alloy.
- the atomic weight percent of rhenium to the atomic weight percent of the combination of bismuth, niobium, tantalum, tungsten, titanium, vanadium, chromium, manganese, yttrium, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and iridium in the refractory metal alloy is 0.7: 1 to 1.5: 1 (and all values and ranges therebetween), typically 0.8: 1 to 1.4:1, more typically 0.8: 1 to 1.25: 1, and still more typically about 0.9: 1 to 1.1 : 1 (e.g., 1 : 1).
- the atomic weight percent of rhenium to the atomic weight percent of the combination of chromium, niobium, tantalum, and zirconium is 0.7: 1 to 5.1 : 1 (and all values and ranges therebetween), typically 0.8: 1 to 1.5: 1, more typically 0.8: 1 to 1.25: 1, and still more typically about 0.9: 1 to 1.1 : 1 (e.g., 1 : 1).
- At least 33 wt.% of the refractory metal alloy includes chromium.
- at least 50 wt.% (e.g., 50-74.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes rhenium
- at least 25 wt.% (e.g., 25-49.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes chromium
- 0.1- 25 wt.% (and all values and ranges therebetween) of the refractory metal alloy includes one or more of molybdenum, bismuth, niobium, tantalum, titanium, vanadium, tungsten, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, yttrium, zirconium, and/or iridium.
- At least 60 wt.% (e.g., 60-69.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes rhenium, at least 30 wt.% (e.g., 30-39.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes chromium, and 0.1-10 wt.% (and all values and ranges therebetween) of the refractory metal alloy includes one or more of molybdenum, bismuth, niobium, tantalum, titanium, vanadium, tungsten, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, yttrium, zirconium, and/or iridium.
- the refractory metal alloy can optionally be nitrided; however, this is not required.
- the nitride layer on the refractory metal alloy can function as a lubricating surface during the optional drawing of the refractory metal alloy when partially or fully forming the medical device.
- the refractory metal alloy is typically cleaned; however, this is not required.
- the surface of the refractory metal alloy is modified by the presence of nitrogen.
- the nitriding process can be by gas nitriding, salt bath nitriding, or plasma nitriding.
- the nitrided surface layer on a MoRe alloy e.g., 40-99 wt.% Mo, 1-40 wt.% Re
- the nitrided surface layer comprises 40-99 wt.% molybdenum (and all values and ranges therebetween), 1-40 wt.% rhenium (and all values and ranges therebetween), and 0.0001-5 wt.% nitrogen (and all values and ranges therebetween).
- the nitride surface layer comprises 40-99 wt.% molybdenum, 1-40 wt.% rhenium, and 0.001-1 wt.% nitrogen.
- the refractory metal alloy after the refractory metal alloy has been annealed, the refractory metal alloy is optionally nitrided prior to being drawn.
- the refractory metal alloy can optionally be nitrided only at selected portions of the outer surface of the refractory metal alloy to obtain different surface characteristics of the refractory metal alloy; however, this is not required.
- the one or more agents can be coated on and/or impregnated in medical device by a variety of mechanisms such as, but not limited to, spraying (e.g., atomizing spray techniques, etc.), flame spray coating, powder deposition, dip coating, flow coating, dip-spin coating, roll coating (direct and reverse), sonication, brushing, plasma deposition, depositing by vapor deposition, MEMS technology, and rotating mold deposition.
- spraying e.g., atomizing spray techniques, etc.
- flame spray coating powder deposition
- dip coating dip coating
- flow coating dip-spin coating
- roll coating direct and reverse
- sonication sonication
- brushing plasma deposition
- depositing by vapor deposition MEMS technology
- rotating mold deposition rotating mold deposition
- polyvinyl chloride polyacrylic acid; ethylene acrylic acid copolymer; ethylene vinyl acetate copolymer; polyvinyl alcohol; poly(hydroxyl alkylmethacrylate); polyvinyl esters (e.g. polyvinyl acetate); and/or copolymers, blends, and/or composites of above.
- the flexible marker material includes one or more metal powders in combinations with parylene, PLGA, POE, PGA, PLLA, PAA, PEG, chitosan and/or derivatives of one or more of these polymers.
- the protective material includes, but is not limited to, sugar (e.g., glucose, fructose, sucrose, etc.), carbohydrate compound, salt (e.g., NaCl, etc.), parylene, PLGA, POE, PGA, PLLA, PAA, PEG, chitosan and/or derivatives of one or more of these materials; however, other and/or additional materials can be used.
- the thickness of the protective material is generally less than about 300 microns (e.g., 0.01 microns to 299.9999 microns and all values and ranges therebetween), and typically less than about 150 microns; however, other thicknesses can be used.
- the protective material can be coated by one or more mechanisms previously described herein.
- cold working occurs at a temperature of no more than 150°C (e.g., 10-150°C and all values and ranges therebetween).
- the change in the shape of the repressed post-sintered part needs to be determined so the final part (pressed, sintered, and re-pressed) meets the dimensional requirements of the final formed part.
- a prepress pressure of 1-300 tsi (1 ton per square inch) (and all values and ranges therebetween) can be used followed by a sintering process of at least 1600°C (e.g., 1600-2600°C and all values and ranges therebetween) and a post sintering press at a pressure of 1-300 tsi (and all values and ranges therebetween) at a temperature of at least 20°C (e.g., 20-100°C and all values and ranges therebetween; 20-40°C, etc.).
- the formed metal part or medical device is to have one or more channels, passageways, and/or voids on the outer surface and/or within the formed part or medical device
- at least a portion of the polymer is not uniformly distributed with the metal powder, but instead is concentrated or forms all of the region that is to be the one or more channels, passageways, and/or voids on the outer surface and/or within the formed part or medical device such that when the polymer and metal powder is sintered, some or all of the polymer is degraded and removed from the part or medical device thereby forming such one or more channels, passageways, and/or voids on the outer surface and/or within the formed part or medical device.
- the part could include up to about 5 vol.% cavities and/or passageways in the medical device.
- the refractory metal alloy near net part, blank, rod, tube, etc. can be formed by various techniques such as, but not limited to, 1) melting the refractory metal alloy and/or metals that form the refractory metal alloy (e.g., vacuum arc melting, etc.) and then extruding and/or casting the refractory metal alloy into a near net part, blank, rod, tube, etc., 2) melting the refractory metal alloy and/or metals that form the refractory metal alloy, forming a metal strip and then rolling and welding the strip into a near net part, blank, rod, tube, etc., 3) consolidating (pressing, pressing and sintering, etc.) the metal powder of the refractory metal alloy and/or metal powder of metals that form the refractory metal alloy into a near net part, blank, rod, tube, etc., and/or 4) 3D print the metal alloy into a
- the tube of the refractory metal alloy can be formed from a strip or sheet of refractory metal alloy.
- the strip or sheet of refractory metal alloy can be formed into a tube by rolling the edges of the sheet or strip and then welding together the edges of the sheet or strip.
- the average particle size of the metal powders is about 2-63 microns, and more particularly about 5-40 microns. As can be appreciated, smaller average particle sizes can be used.
- the purity of the metal powders should be selected so the metal powders contain very low levels of carbon, oxygen, and nitrogen. Typically, the carbon content of the metal powder used to form the refractory metal alloy is less than about 100 ppm, the oxygen content is less than about 50 ppm, and the nitrogen content is less than about 20 ppm. Typically, metal powder used to form the refractory metal alloy has a purity grade of at least 99.9 and more typically at least about 99.95.
- the near net medical device, blank, rod, tube, etc. can be protected from oxygen by use of a vacuum environment, a non-oxygen environment (e.g., hydrogen, argon and hydrogen mixture, nitrogen, nitrogen and hydrogen, etc.) or an inert environment.
- a non-oxygen environment e.g., hydrogen, argon and hydrogen mixture, nitrogen, nitrogen and hydrogen, etc.
- One non-limiting protective environment includes argon, hydrogen or argon and hydrogen; however, other or additional inert gasses can be used.
- the near net medical device, blank, rod, tube, etc. is typically cleaned after each drawing process to remove impurities and/or other undesired materials from the surface of the near net medical device, blank, rod, tube, etc.; however, this is not required.
- the near net medical device, blank, rod, tube, etc. is cooled after being annealed; however, this is not required.
- the near net medical device, blank, rod, tube, etc. is cooled at a fairly quick rate after being annealed so as to inhibit or prevent the formation of a sigma phase in the refractory metal alloy; however, this is not required.
- the near net medical device, blank, rod, tube, etc. is cooled after being annealed; however, this is not required.
- a rate of at least about 50°C per minute (e.g., 50-500°C per minute and all values and ranges therebetween) after being annealed typically at least about 75°C per minute after being annealed, more typically at least about 100°C per minute after being annealed, even more typically about 100-400°C per minute after being annealed, still even more typically about 150-350°C per minute after being annealed, and yet still more typically about 200-300°C per minute after being annealed, and still yet even more typically about 250-280°C per minute after being annealed; however, this is not required.
- 50°C per minute e.g., 50-500°C per minute and all values and ranges therebetween
- the near net medical device, blank, rod, tube, etc. is annealed after one or more drawing processes.
- the refractory metal alloy blank, rod, tube, etc. can be annealed after each drawing process or after a plurality of drawing processes.
- the refractory metal alloy blank, rod, tube, etc. is typically annealed prior to about a 60% cross-sectional area size reduction of the refractory metal alloy blank, rod, tube, etc.
- the near net medical device, blank, rod, tube, etc. should not be reduced in cross-sectional area by more than 60% before being annealed (e.g., 0.1-60% reduction and all values and ranges therebetween).
- the refractory metal alloy blank, rod, tube, etc. is annealed prior to about a 5-15% cross-sectional area size reduction of the refractory metal alloy blank, rod, tube, etc.
- the annealing chamber typically is formed of a material that will not impart impurities to the near net medical device, blank, rod, tube, etc. as the near net medical device, blank, rod, tube, etc. is being annealed.
- Lubricants commonly include carbon compounds, nitride compounds, molybdenum paste, and other types of compounds that can adversely affect the refractory metal alloy if such compounds and/or elements in such compounds become associated and/or embedded with the refractory metal alloy during an annealing process.
- the refractory metal alloy that is used to partially or fully form the near net medical device, after being formed into its final or near final shape can optionally be cleaned, polished, sterilized, nitrided, etc.
- the medical device is electropolished.
- the medical device is cleaned prior to being exposed to the polishing solution; however, this is not required.
- Non-limiting enhancement coatings that can be applied to a portion of all of the outer surface of the refractory metal alloy includes chromium nitride (CrN), diamond-like carbon (DLC), titanium nitride (TiN), zirconium nitride (ZrN), zirconium oxide (ZrCh), zirconium-nitrogen-carbon (ZrNC), zirconium OxyCarbide (ZrOC), and combinations of such coatings.
- the one or more enhancement coatings are applied to a portion of all of the outer surface of the refractory metal alloy can be a vacuum process using an energy source to vaporize material and deposit a thin layer of enhancement coating material.
- the one or more enhancement coatings can be form various coating colors on the outer surface of the refractory metal alloy (e.g., gold, copper, brass, black, rose gold, chrome, blue, silver, yellow, green, etc.).
- the thickness of the enhancement coating is greater than 1 nanometer (e.g., 2 nanometers to 100 microns and all values and ranges therebetween), and typically 0.1-25 microns, and more typically 1-10 microns.
- the wear rate of the enhancement coating is 0.5 x 10' 7 mm 3 /N-m to 3 x 10' 7 mm 3 /N-m (an all values and ranges therebetween), and typically 1.2 x 10' 7 mm 3 /N-m to 2 x 10' 7 mm 3 /N-m.
- the Cr metal coating can be applied by PVD, CVD, ALD and PE-CVD in an inert environment.
- the coating thickness of Cr metal is 0.5- 15 microns.
- the Cr metal coating is exposed to nitrogen gas and/or a nitrogen containing gas compound to cause the nitrogen to react with the Cr metal coating to form a layer of CrN on the outer surface of the Cr metal coating and/or the outer surface of the refractory metal alloy.
- the enhancement coating composition generally includes 65-80 wt.% Cr, 15-30 wt.% N, 0-8 wt.% Re, 0-1 wt.% Si, 0-1 wt.% O, and 0-1 wt.% C.
- the enhancement coating composition generally includes 80-90 wt.% Zr, 10-20 wt.% N, 0-8 wt.% Re, 0-1 wt.% Si, 0-1 wt.% O, and 0-1 wt.% C.
- all or a portion of the outer surface of the refractory metal alloy is initially coated with Zr metal.
- the Zr metal coating can be applied by PVD, CVD, ALD and PE- CVD in an inert environment.
- the coating thickness of Zr metal is 0.5-15 microns.
- the Zr metal coating is exposed to a) both oxygen gas and/or oxygen containing gas compound and also to nitrogen gas and/or nitrogen containing gas compound, b) nitrogen gas and/or nitrogen containing gas compound and then to oxygen gas and/or oxygen containing gas compound, or c) oxygen gas and/or oxygen gas containing compound and then to nitrogen gas and/or nitrogen gas containing compound.
- the coating composition of the zirconium oxide (ZrO2) coating and the zirconium nitride coating (ZrN) are similar or the same as discussed above.
- the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy
- the enhancement coating composition generally includes a zirconium oxycarbide (ZrOC) coating.
- ZrOC zirconium oxycarbide
- a portion or all of the outer surface of the refractory metal alloy can include the zirconium oxycarbide (ZrOC) coating.
- the enhancement coating can be used to improve hardness, improve toughness, improve resistance to corrosion and oxidation, reduced friction, and/or form a reduced stick surface when in contact with many different materials.
- all or a portion of the outer surface of the refractory metal alloy is initially coated with Zr metal.
- the enhancement coating composition generally includes 40-80 wt.% Zr, 5-25 wt.% N, and 5-25 wt.% C, 0-1 wt.% O, 0-8 wt.% Re, and 0-1 wt.% Si.
- the refractory metal alloy has a reduced degree of recoil during the crimping and/or expansion of the medical device compared with stainless steel, chromium-cobalt alloys, or titanium alloys.
- the medical device formed of the refractory metal alloy better maintains its crimped form and/or better maintains its expanded form after expansion due to the use of the refractory metal alloy.
- the medical device when the medical device is to be mounted onto a delivery device when the medical device is crimped, the medical device better maintains its smaller profile during the insertion of the medical device in a body passageway. Also, the medical device better maintains its expanded profile after expansion to facilitate in the success of the medical device in the treatment area.
- the refractory metal alloy has improved radiopaque properties compared to standard materials such as stainless steel or cobalt-chromium alloy, thus reducing or eliminating the need for using marker materials on the medical device.
- the refractory metal alloy is at least about 10-20% more radiopaque than stainless steel or cobalt-chromium alloy.
- Another and/or alternative non-limiting object of the present disclosure is the provision of a method and process for forming the refractory metal alloy in accordance with the present disclosure that inhibits or prevents the formation of micro-cracks during the processing of the refractory metal alloy.
- Another and/or alternative non-limiting object of the present disclosure is the provision of a method and process for forming the refractory metal alloy in accordance with the present disclosure to inhibit or prevent the formation of micro-cracks during the processing of the refractory metal alloy into a medical device.
- Another and/or alternative non-limiting object of the present disclosure is the provision of a medical device that includes a refractory metal alloy wherein the medical device has a smaller crimped profile as compared to medical devices formed of different metals.
- a refractory metal alloy that includes an enhancement coating of chromium nitride (CrN), diamond-like carbon (DLC), titanium nitride (TiN), zirconium nitride (ZrN), zirconium oxide (ZrCh), or zirconium OxyCarbide (ZrOC), that can be used to improve one or more properties of the refractory metal alloy (e.g., change exterior color of metal alloy, increase hardness of coated surface, increase toughness of coated surface, reduced friction to coated surface, improve impact wear of coated surface, improve resistance to corrosion and oxidation, form a non-stick coated surface, improve biocompatibility of metal alloy having the coated surface, reduce toxicity of metal alloy having the coated surface, etc.).
- CrN chromium nitride
- DLC diamond-like carbon
- TiN titanium nitride
- ZrN zirconium nitride
- ZrCh zirconium oxide
- ZrOC zirconium Ox
- the term “comprising” may include the embodiments “consisting of’ and “consisting essentially of.”
- the terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients/ steps and permit the presence of other ingredients/steps.
- Medical devices such as expandable heart valves, that are at least partially formed of the refractory metal alloy in accordance with the present disclosure overcome several unmet needs that exist in expandable medical device formed of CoCr alloys, TiAIV alloys, and stainless steel.
- Such unmet needs addressed by the medical devices in accordance with the present disclosure include 1) not having to form a large hole in large arterial vessels or other blood vessels for initial insertion of the crimped medical device into the atrial vessel or other blood vessel, thereby reducing the incidence of lethal bleeding during a treatment; 2) enabling the medical device to be delivered and implanted in abnormally shaped heart valves or through an abnormally shaped arterial vessel due to calcination in the heart valve and/or calcination and/or plaque in the arterial vessel by creating a medical device (e.g., stent, prosthetic heart valve, etc.) having a reduced crimped profile that is smaller than medical devices formed of CoCr alloys, TiAIV alloys, and stainless steel; 3) reducing the incidence of a perivalvular leak and/or other types of leakage about the implanted medical device when the medical device is expanded in the treatment region by using a frame formed of the refractory metal alloy that better conforms to the shape of the abnormally shaped heart valve orifice upon expansion
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Abstract
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EP22873375.4A EP4404878A1 (en) | 2021-09-23 | 2022-08-05 | Coating for refractory metal alloy |
JP2024518408A JP2024537713A (en) | 2021-09-23 | 2022-08-05 | Metal alloys, medical devices and methods |
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US63/247,540 | 2021-09-23 | ||
US17/586,270 US20230040416A1 (en) | 2021-07-28 | 2022-01-27 | Medical Device That Includes a Rhenium Metal Alloy |
US17/586,270 | 2022-01-27 | ||
US202263316077P | 2022-03-03 | 2022-03-03 | |
US63/316,077 | 2022-03-03 | ||
US202263347337P | 2022-05-31 | 2022-05-31 | |
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WO2024205558A1 (en) * | 2023-03-24 | 2024-10-03 | Mirus Llc | Medical device metal alloy |
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US20060136051A1 (en) * | 1998-07-27 | 2006-06-22 | Icon Interventional Systems, Inc. | Coated medical device |
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US20130084322A1 (en) * | 2010-07-29 | 2013-04-04 | Tim Wu | Drug-impregnated biodegradable stent and methods of making the same |
US20190008995A1 (en) * | 2015-07-02 | 2019-01-10 | Mirus | Molybdenum Alloys for Medical Devices |
US20210251766A1 (en) * | 2020-02-19 | 2021-08-19 | DePuy Synthes Products, Inc. | Coated implant and method of making the same |
-
2022
- 2022-08-05 WO PCT/US2022/039576 patent/WO2023048840A1/en active Application Filing
- 2022-08-05 EP EP22873375.4A patent/EP4404878A1/en active Pending
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US20030159920A1 (en) * | 1998-07-17 | 2003-08-28 | Micro Therapeutics, Inc. | Thin film stent |
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US20060184251A1 (en) * | 2005-01-07 | 2006-08-17 | Zongtao Zhang | Coated medical devices and methods of making and using |
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WO2024205558A1 (en) * | 2023-03-24 | 2024-10-03 | Mirus Llc | Medical device metal alloy |
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