WO2023048840A1 - Coating for refractory metal alloy - Google Patents

Coating for refractory metal alloy Download PDF

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Publication number
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
Application number
PCT/US2022/039576
Other languages
French (fr)
Inventor
Noah Roth
Ravi ENNETI
Jordan BAUMAN
Original Assignee
Mirus Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US17/586,270 external-priority patent/US20230040416A1/en
Application filed by Mirus Llc filed Critical Mirus Llc
Priority to EP22873375.4A priority Critical patent/EP4404878A1/en
Priority to JP2024518408A priority patent/JP2024537713A/en
Publication of WO2023048840A1 publication Critical patent/WO2023048840A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/86Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/86Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
    • A61F2/90Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/02Inorganic materials
    • A61L31/022Metals or alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/08Materials for coatings
    • A61L31/082Inorganic materials
    • A61L31/088Other specific inorganic materials not covered by A61L31/084 or A61L31/086
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2240/00Manufacturing or designing of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
    • A61F2240/001Designing or manufacturing processes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals 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

A refractory metal alloy and includes an enhancement coating material.

Description

COATING FOR REFRACTORY METAL ALLOY
[0001] The present disclosure is a continuation in part of United States Patent Application Serial No. 17/586,270 filed January 27, 2022, which in turn claims priority on United States Provisional Application Serial No. 63/226,270 filed July 28, 2021, which are both incorporated herein by reference.
[0002] The present disclosure claims priority on United States Provisional Application Serial No. 63/389,281 filed July 14, 2022, which is incorporated herein by reference.
[0003] The present disclosure claims priority on United States Provisional Application Serial No. 63/347,337 filed May 31, 2022, which is incorporated herein by reference.
[0004] The present disclosure claims priority on United States Provisional Application Serial No. 63/247,540 filed September 23, 2021, which is incorporated herein by reference.
[0005] The present disclosure claims priority on United States Provisional Application Serial No. 63/316,077 filed March 3, 2022, which is incorporated herein by reference.
[0006] 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.
BACKGROUND OF DISCLOSURE
[0007] 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.
[0008] 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.
SUMMARY OF THE DISCLOSURE
[0009] The present disclosure is direct to a protective coating for refractory metal alloy such as refractory metal alloys that include rhenium, and even more particularly to a medical device that is at least partially formed of a refractory metal alloy wherein the refractory metal alloy includes a protective coating. As defined herein, a refractory metal alloy is a metal alloy that includes at least 20 wt.% of one or more of Mo, Re, Nb, Ta or W. Non-limiting refractory metal alloys include MoRe alloy, ReW alloy, MoReCr alloy, MoReTa alloy, MoReTi alloy, WCu alloy, ReCr alloy, Mo alloy, Re alloy, W alloy, Ta alloy, Nb alloy, etc. In one non-limiting embodiment, the refractory metal alloy includes at least 20 wt.% of rhenium. Non-limiting refractory metal alloys that include rhenium include, but are not limited to, MoRe alloy, ReW alloy, MoReCr alloy, MoReTa alloy, MoReTi alloy, ReCr alloy, etc.
[0010] In accordance with one non-limiting aspect of the present disclosure, 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, frontal bone, greater trochanter, humerus, ilium, ischium, mandible, maxilla, metacarpus, metatarsus, occipital bone, olecranon, parietal bone, patella, phalanx, radius, ribs, sacrum, scapula, sternum, talus, tarsus, temporal bone, tibia, ulna, zygomatic bone, etc.) and/or cartilage, bone plate, knee replacement, hip replacement, shoulder replacement, ankle replacement, nail, rod, screw, post, cage, plate, pedicle screw, cap, hinge, joint system, anchor, spacer, shaft, anchor, disk, ball, tension band, locking connector other structural assembly that is used in a body to support a structure, mount a structure, and/or repair a structure in a body such as, but not limited to, a human body, animal body, etc.
[0011] In accordance with another and/or alternative non-limiting aspect of the present disclosure, there is provided a medical device partially or fully formed of a refractory metal alloy. In one non-limiting embodiment, 50-100% (and all values and ranges therebetween) of the medical device is formed of the refractory metal alloy. In another non-limiting embodiment, 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.). [0012] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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. 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.
[0013] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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 of the medical device to the shape of the treatment area when the medical device is used and/or expanded in the treatment area, 16) reduce the amount of recoil of the medical device to the shape of the treatment area when the medical device is expanded in the treatment area, 17) increase yield strength of the medical device, 18) improve fatigue ductility of the medical device, 18) improve durability of the medical device,
19) improve fatigue life of the medical device, 20) reduce adverse tissue reactions after implant of the medical device, 21) reduce metal ion release after implant of the medical device, 22) reduce corrosion of the medical device after implant of the medical device, 23) reduce allergic reaction after implant of the medical device, 24) improve hydrophilicity of the medical device, 25) reduce thickness of meta component of medical device, 26) improve bone fusion with medical device, and/or 27) lower ion release from medical device into tissue, 28) reduce magnetic susceptibility of the medical device when implanted in a patient, and/or 29) reduce toxicity of the medical device after implant of the medical device.
[0014] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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. In one non-limiting embodiment, a portion or all of the medical device is formed by a 3D printing process.
[0015] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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.
[0016] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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). In one non-limiting formulation of the refractory metal alloy, the carbon to oxygen atomic ratio in the refractory metal alloy is generally at least about 0.3: 1. Typically, 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. Generally, the oxygen content is to be maintained at very low level. In one non-limiting formulation of the refractory metal alloy, 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.
[0017] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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. In one non-limiting formulation, 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. In one non-limiting formulation of 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). In another non-limiting formulation of the refractory metal alloy, 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).
[0018] In another and/or alternative non-limiting aspect of the present disclosure, 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. In one specific configuration, when the medical device includes an expandable frame, the 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.
[0019] In another and/or alternative non-limiting aspect of the present disclosure, 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.
[0020] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy that is used to form all or part of the medical device 1) is clad, metal sprayed, plated and/or formed (e.g., cold worked, hot worked, etc.) onto another metal, or 2) has another metal or metal alloy metal sprayed, plated, clad and/or formed onto the refractory metal alloy.
[0021] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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. [0022] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device can be at least partially or fully formed from by 3D printing.
[0023] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy has several physical properties that positively affect the medical device when the medical device is at least partially formed of the refractory metal alloy of the present disclosure. In one non-limiting embodiment of the disclosure, the average Vickers hardness of refractory metal alloy of the present disclosure used to at least partially form the medical device is optionally at least about 150 Vickers (e.g., 150-300 Vickers and all values and ranges therebetween); and typically 160-240 Vickers; however, this is not required. The refractory metal alloy of the present disclosure generally has an average hardness that is greater than stainless steel (e.g., Grade 304, Grade 316). In another and/or alternative non-limiting embodiment of the disclosure, the average ultimate tensile strength of the refractory metal alloy of the present disclosure is optionally at least about 100 ksi (e.g., 100-350 ksi and all values and ranges therebetween); however, this is not required. In still another and/or alternative non-limiting embodiment of the disclosure, the average yield strength of the refractory metal alloy of the present disclosure is optionally at least about 80 ksi (e.g., 80-300 ksi and all values and ranges therebetween); however, this is not required. In yet another and/or alternative non-limiting embodiment of the disclosure, 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). The small grain size of the refractory metal alloy of the present disclosure enables the medical device to have the desired elongation and ductility properties that are useful in enabling the medical device to be formed, crimped, and/or expanded.
[0024] In another and/or alternative non-limiting embodiment of the disclosure, the average tensile elongation of the refractory metal alloy of the present disclosure used to at least partially form the medical device is optionally at least about 25% (e.g., 25%-50% average tensile elongation and all values and ranges therebetween). An average tensile elongation of at least 25% for the refractory metal alloy is useful to facilitate in the medical device being properly expanded when positioned in the treatment area of a body passageway. A medical device that does not have an average tensile elongation of at least about 25% may be more prone to the formation of microcracks and/or break during the forming, crimping, and/or expansion of the medical device.
[0025] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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) a medical device having the desired ultimate tensile strength and yield strength, 8) a medical device having very thin wall thicknesses and still having the desired radial forces needed to retain the medical device on an open state when expanded, 9) a medical device exhibiting less recoil when the medical device is crimped onto a delivery system and/or expanded in a body passageway, 10) a medical device exhibiting improved conformity to the shape of the treatment area in the body passageway when the medical device is expanded in a body passageway, 11) a medical device exhibiting improved fatigue ductility, and/or 12) a medical device that exhibits improved durability.
[0026] In accordance with another and/or alternative non-limiting aspect of the present disclosure, at least 30 wt.% (e.g., 30-100 wt.% and all values and ranges therebetween) of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten. In another non-limiting embodiment, at least 40 wt.% of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten. In another nonlimiting embodiment, at least 50 wt.% of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten.
[0027] In another non-limiting embodiment, 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. In another non-limiting embodiment, 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. In another non-limiting embodiment, 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, and the refractory alloy includes 0-2 wt.% (and all values and ranges therebetween) of a combination of other metals, carbon, oxygen and nitrogen. In another non-limiting embodiment, 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 a combination of other metals, carbon, oxygen and nitrogen. In another non-limiting embodiment, 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. In another non-limiting embodiment, 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.
[0028] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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. In another non-limiting embodiment, 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, 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. In another non-limiting embodiment, 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, 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. In another non-limiting embodiment, 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. In another nonlimiting embodiment, 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. In another non-limiting embodiment, 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, 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. In another non-limiting embodiment, 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. In another non-limiting embodiment, 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 0-2 wt.% (and all values and ranges therebetween) of a combination of other metals, carbon, oxygen, and nitrogen. In another non-limiting embodiment, 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.
[0029] In accordance with another and/or alternative non-limiting aspect of the present disclosure, there is provided 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. In one non-limiting embodiment, the refractory metal alloy includes at least 20 wt.% (e.g., 20-99.9 wt.% and all values and ranges therebetween) rhenium, and 0.1-80 wt.% (and all values and ranges therebetween) of one or more of 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. In another non-limiting embodiment, 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. In another non-limiting embodiment, 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 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. In another non-limiting embodiment, 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. In another nonlimiting embodiment, 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. In another non-limiting embodiment, 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. In another non-limiting embodiment, In another non-limiting embodiment, 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. In another non-limiting embodiment, 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 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. In another non-limiting embodiment, 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. In another non-limiting embodiment, 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 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. In one non-limiting embodiment, 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. In another non-limiting embodiment, 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.
[0030] In another non-limiting aspect of the present disclosure, 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.). Although 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. In one nonlimiting formulation, 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). In one non-limiting embodiment, 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.%. In another non-limiting formulation, 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.%. In one non-limiting specific tungsten-rhenium-molybdenum alloy, the weight percent of the tungsten is greater than a weight percent of rhenium and also greater than the weight percent of molybdenum. In another non-limiting specific tungsten-rhenium-molybdenum alloy, 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.
[0031] In another non-limiting aspect of the present disclosure, the metals used to form the refractory metal alloy include rhenium, molybdenum, and one or more alloying metals selected from the group consisting of bismuth, chromium, copper, hafnium, iridium, manganese, niobium, osmium, rhodium, ruthenium, tantalum, technetium, titanium, tungsten, vanadium, yttrium, and zirconium. In one non-limiting embodiment, a combined weight percentage of rhenium and alloy metals in the refractory metal alloy is greater than or equal to the weight percent of molybdenum in the refractory metal alloy. In another non-limiting embodiment, 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. In another non-limiting embodiment, 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). In another non-limiting embodiment, a weight percent of rhenium in the refractory metal alloy is 35-60 wt.% (and all values and ranges therebetween). In another non-limiting embodiment, a combined weight percent of the alloying metals is 5-45 wt.% (and all values and ranges therebetween) of the refractory metal alloy. In another non-limiting embodiment, 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.%. In another non-limiting embodiment, 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. 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; 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). In another non-limiting embodiment, the alloying metal includes chromium and one or more metals selected from the group consisting of zirconium, niobium, and tantalum. In another non-limiting embodiment, 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). In another non-limiting embodiment, the alloying metal a first metal selected from the group consisting of chromium, niobium, tantalum, and zirconium, and a second metal selected from the group consisting of chromium, niobium, tantalum, 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).
[0032] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the weight percent of rhenium plus the weigh percent of the combined weight percentage of bismuth, niobium, tantalum, tungsten, titanium, vanadium, chromium, manganese, yttrium, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and iridium is greater than the weight percent of molybdenum in the refractory metal alloy. In one specific nonlimiting formulation, the weight percent of rhenium plus the weigh percent of the combined weight percentage of bismuth, chromium, iridium, niobium, tantalum, titanium, yttrium, and zirconium is greater than the weight percent of molybdenum in the refractory metal alloy. In another specific non-limiting formulation, the weight percent of rhenium plus the weigh percent of the combined weight percentage of chromium, niobium, tantalum, and zirconium is greater than the weight percent of molybdenum in the refractory metal alloy. In another non-limiting specific non-limiting formulation, 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). 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, chromium, iridium, niobium, tantalum, titanium, yttrium, and zirconium in the refractory metal alloy is 11-41 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 chromium, niobium, tantalum, and zirconium in the refractory metal alloy is 11-41 wt.% (and all values and ranges therebetween). In another non-limiting embodiment of the invention, 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.
[0033] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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). In one specific non-limiting formulation, the atomic weight percent of rhenium to the atomic weight percent of the combination of bismuth, chromium, iridium, niobium, tantalum, titanium, yttrium, 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). In one specific non-limiting formulation, 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).
[0034] In accordance with another and/or alternative non-limiting aspect of the present disclosure, when the refractory metal alloy includes two of bismuth, niobium, tantalum, tungsten, titanium, vanadium, chromium, manganese, yttrium, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and iridium, the atomic ratio of the two metals is 0.4: 1 to 2.5: 1 (and all values and ranges therebetween), and typically 0.5: 1 to 2: 1. In one specific non-limiting formulation, when the refractory metal alloy includes two of bismuth, chromium, iridium, niobium, tantalum, titanium, yttrium, and zirconium, the atomic ratio of the two metals is 0.4: 1 to 2.5:1 (and all values and ranges therebetween), and typically 0.5: 1 to 2: 1. In another specific nonlimiting formulation, when the refractory metal alloy includes two of chromium, niobium, tantalum, and zirconium, the atomic ratio of the two metals is 0.4: 1 to 2.5: 1 (and all values and ranges therebetween), and typically 0.5: 1 to 2: 1.
[0035] In accordance with another and/or alternative non-limiting aspect of the present disclosure, at least 35 wt.% (e.g., 35-75 wt.% and all values and ranges therebetween) of the refractory metal alloy includes rhenium, and the refractory metal alloy also includes chromium. In one non-limiting embodiment, at least 25 wt.% (e.g., 25-49.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes chromium. In another non-limiting embodiment, at least 30 wt.% of the refractory metal alloy includes chromium. In another nonlimiting embodiment, at least 33 wt.% of the refractory metal alloy includes chromium. In another non-limiting embodiment, 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, and 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. In another non-limiting embodiment, at least 55 wt.% (e.g., 55-69.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes rhenium, at least 30 wt.% (e.g., 30-44.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes chromium, and 0.1-15 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. In another non-limiting embodiment, 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. In another non-limiting embodiment, at least 62 wt.% (e.g., 62-67.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes rhenium, at least 32 wt.% (e.g., 32-32.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes chromium, and 0.1-6 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.
[0036] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy includes less than about 5 wt.% (e.g., 0-4.999999 wt.% and all values and ranges therebetween) other metals and/or impurities. A high purity level of the refractory metal alloy results in the formation of a more homogeneous alloy, which in turn results in a more uniform density throughout the refractory metal alloy, and also results in the desired yield and ultimate tensile strengths of the refractory metal alloy. In one non-limiting embodiment, the refractory metal alloy includes less than about 0.5 wt.% other metals and/or impurities. In another non-limiting embodiment, the refractory metal alloy includes less than about 0.2 wt.% other metals and/or impurities. In another non-limiting embodiment, the refractory metal alloy includes less than about 0.1 wt.% other metals and/or impurities. In another non-limiting embodiment, the refractory metal alloy includes less than about 0.05 wt.% other metals and/or impurities. In another non-limiting embodiment, the refractory metal alloy includes less than about
0.01 wt.% other metals and/or impurities.
[0037] Several non-limiting examples of the refractory metal alloy in accordance with the present disclosure are set forth below:
Ex, 1 Ex, 2 Ex, 3 Ex, 4 40-80% 40-80% 40-80% 40-80% 0.01-0.3% 0-0.3% 0-0.3% 0-0.3% <0.002% <0.002% <0.002% <0.002% 0-0.2% 0-0.2% 0.01-0.2% 0-0.2% <0.02% <0.02% <0.02% <0.02% <0.002% <0.002% <0.002% <0.002% 0.1-2.5% 0-2.5% 0-2.5% 0-2.5% <0.06% <0.06% <0.06% <0.06% <1% <1% <1% <1% 0-2% 0.1-2% 0-2% 0-2% <20 ppm <20 ppm <20 ppm <20 ppm <0.01% <0.01% <0.01% <0.01% <1% <1% <1% <1% 20-49% 20-49% 20-49% 20-49% <0.008% <0.008% <0.008% <0.008% <0.002% <0.002% <0.002% <0.002% 0-50% 0-50% 0-50% 0-50% <1% <1% <1% <1% <1% <1% <1% <1% <1% <1% <1% <1% 0-50% 0-50% 0-50% 0.5-50% 0-1% 0-1% 0.1-1% 0-1% <1% <1% <1% <1% 0-3% 0-3% 0-3% 0-3%
Figure imgf000021_0001
0-10% 0-10% 0-10% 0-10% Ex, 5 Ex, 6 Ex, 7 40-80% 40-80% 40-80% 0-0.3% 0-0.3% 0-0.3% <0.002% <0.002% <0.002% 0-0.2% 0-0.2% 0-0.2% <0.002% <0.002% <0.002% 0-2.5% 0-2.5% 0-2.5% <0.06% <0.06% <0.06% <1% <1% <1% 0-2% 0-2% 0-2% <20 ppm <20 ppm <20 ppm <0.01% <0.01% <0.01% <1% <1% <1% 20-49% 20-49% 20-49% <0.008% <0.008% <0.008% <0.002% <0.002% <0.002% 0-50% 0.5-50% 0-50% <1% <1% <1% <1% <1% <1% <1% <1% <1% 0-50% 0-50% 0-50% 0-1% 0-1% 0-1% 0.1-3% 0-3% 0-3%
Figure imgf000022_0001
0-10% 0-10% 0-10%
Metal/Wt. % Ex, 8 Ex, 9 Ex, 10 Mo 45-78% 45-75% 45-70% C 0-0.3% 0-0.3% 0-0.3% Co <0.002% <0.002% <0.002% Cs2O 0-0.2% 0-0.2% 0-0.2% H <0.002% <0.002% <0.002% Hf 0-2.5% 0-2.5% 0-2.5% O <0.06% <0.06% <0.06% Os <1% <1% <1% La2O3 0-2% 0-2% 0-2% N <20 ppm <20 ppm <20 ppm Nb <0.01% <0.01% <0.01% Pt <1% <1% <1% Re 22-49% 25-49% 30-49% S <0.008% <0.008% <0.008% Sn <0.002% <0.002% <0.002% Ta 0-50% 0.5-50% 0-50% Tc <1% <1% <1% Ti <1% <1% <1% V <1% <1% <1% w 0-50% 0-50% 0-50% Y2O3 0-1% 0-1% 0-1%
ZrO2 0.1-3% 0-3% 0-3%
CNT 0-10% 0-10% 0-10%
Metal/Wt. % Ex, 12 Ex, 13 Ex, 14
Mo 35-80% 35-80% 35-70% 35-65%
C 0.05-0.15% 0-0.15% 0-0.15% 0-0.15%
Cs2O 0-0.2% 0-0.2% 0.04-0.1% 0-0.2%
Hf 0.8-1.4% 0-2% 0-2.5% 0-2.5%
La2O3 0-2% 0.3-0.7% 0-2% 0-2%
Re 20-49% 20-49% 30-49% 35-49%
Ta 0-2% 0-2% 0-50% 0-50%
W 0-2% 0-2% 0-50% 20-50%
Y2O3 0-1% 0-1% 0.3-0.5% 0-1%
ZrO2 0-3% 0-3% 0-3% 0-3%
Figure imgf000023_0001
Metal/Wt. % Ex, 18 Ex, 19 Ex, 20 W 20-80% 60-80% 20-78% Re 20-47.5% 20-40% 22-47.5% Mo 0-47.5% <0.5% 1-47.5% Cu <0.5% <0.5% <0.5% C <0.15% <0.15% <0.15% Co <0.002% <0.002% <0.002% Cs2O <0.2% <0.2% <0.2% Fe <0.02% <0.02% <0.02% H <0.002% <0.002% <0.002% Hf <0.5% <0.5% <0.5% La2O3 <0.5% <0.5% <0.5% O <0.06% <0.06% <0.06% Os <0.5% <0.5% <0.5% N <20 ppm <20 ppm <20 ppm Nb <0.01% <0.01% <0.01% Pt <0.5% <0.5% <0.5% S <0.008% <0.008% <0.008% Sn <0.002% <0.002% <0.002%
Ta <0.5% <0.5% <0.5%
Tc <0.5% <0.5% <0.5%
Ti <0.5% <0.5% <0.5%
V <0.5% <0.5% <0.5%
Y2O3 <0.5% <0.5% <0.5%
Zr <0.5% <0.5% <0.5%
ZrO2 <0.5% <0.5% <0.5%
CNT 0-10% 0-10% <0.5%.
Metal/Wt. % Ex, 21 Ex, 22 Ex, 23
W 20-80% 60-80% 20-75%
Re 20-47.5% 20-40% 25-47.5%
Mo 0-47.5% <0.5% 1-47.5%
Metal/Wt. % Ex, 24 Ex, 25 Ex, 26
W 50.1-80% 65-80% 50.1-79%
Re 20-40% 20-35% 20-40%
Mo 0-40% <0.5% 1-30%
Metal/Wt. % Ex, 27 Ex, 28 Ex, 29
W 20-49% 20-49% 20-49%
Re 20-60% 30-60% 40-60%
Mo 0-40% 0-40% 0-39%
Metal/Wt. % Ex, 30 Ex, 31 Ex, 32
Re 20-98% 60-95% 80-90%
Mo 0-80% 0-40% 0-20%
W 0-80% 0-40% 0-20%
Metal/Wt. % Ex, 33 Ex, 34 Ex, 35
W 20-49% 20-49% 20-49%
Re 20-40% 20-40% 22-39%
Mo 20-60% 30-60% 40-60%
Metal/Wt. % Ex, 36 Ex, 37 Ex, 38
W 20-40% 20-35% 20-30%
Re 20-40% 20-40% 31-40%
Mo 0-40% 10-40% 31-40%
Wt. % Ex, 39 Ex, 40 Ex, 41 Ex, 42
Re 35-60% 35-60% 35-60% 35-60%
Mo 10-55% 10-55% 10-55% 10-55%
Bi 1-42 0-32 0-32 0-32
Cr 0-32 1-42 0-32 0-32
Ir 0-32 0-32 1-42 0-32 Nb 0-32 0-32 0-32 1-42 Ta 0-32 0-32 0-32 0-32 Ti 0-32 0-32 0-32 0-32 Y 0-32 0-32 0-32 0-32
Zr 0-32 0-32 0-32 0-32 C <0.06 <0.06 <0.06 <0.06 N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Figure imgf000025_0001
Ta 1-42 0-32 0-32 0-32
Ti 0-32 1-42 0-32 0-32
Y 0-32 0-32 1-42 0-32
Zr 0-32 0-32 0-32 1-42
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06 wt. % Ex, 55 Ex, 56 Ex, 57 Ex, 58
Re 41-59% 41-59% 41-59% 41-59%
Mo 18-45% 18-45% 18-45% 18-45%
Bi 0-15 0-15 1-36 0-15
Cr 1-20 1-20 1-20 1-20
Ir 0-15 0-15 0-15 0-15
Nb 1-36 0-15 0-15 0-15
Ta 0-15 1-36 0-15 0-15
Ti 0-15 0-15 0-15 0-15
Y 0-15 0-15 0-15 0-15
Zr 0-15 0-15 0-15 1-36
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Wt. % Ex, 59 Ex, 60 Ex, 61 Ex, 62
Re 41-59% 41-59% 41-59% 41-59%
Mo 18-45% 18-45% 18-45% 18-45%
Bi 1-36 0-15 0-15 0-15
Cr 1-20 1-20 1-20 1-20
Ir 0-15 1-36 0-15 0-15
Nb 0-15 0-15 0-15 0-15
Ta 0-15 0-15 0-15 0-15
Ti 0-15 0-15 1-36 0-15
Y 0-15 0-15 0-15 1-36
Zr 0-15 0-15 0-15 0-15
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Wt. % Ex, 63 Ex, 64 Ex, 65 Ex, 66
Re 41-59% 41-59% 41-59% 41-59%
Mo 18-45% 18-45% 18-45% 18-45%
Bi 1-34 0-15 0-15 0-15
Cr 0-15 0-15 0-15 0-15
Ir 0-15 0-15 0-15 1-34
Nb 3-27 3-27 3-27 3-27
Ta 0-42 1-34 0-15 0-15 Ti 0-15 0-15 0-15 0-15
Y 0-15 0-15 0-15 0-15
Zr 0-15 0-15 3-27 0-15
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Wt. % Ex, 67 Ex, 68 Ex, 69 Ex, 70
Re 41-59% 41-59% 41-59% 41-59%
Mo 18-45% 18-45% 18-45% 18-45%
Bi 0-15 0-15 0-15 0-15
Cr 0-15 0-15 0-15 0-15
Ir 0-15 1-34 0-15 0-15
Nb 0-15 0-15 0-15 0-15
Ta 1-34 0-15 3-27 0-15
Ti 0-15 0-15 0-15 0-15
Y 0-15 0-15 0-15 3-27
Zr 3-27 3-27 3-27 3-27
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Wt. % Ex, 71 Ex, 72 Ex, 73 Ex, 74
Re 41-59% 41-59% 41-59% 41-59%
Mo 18-45% 18-45% 18-45% 18-45%
Bi 0-15 0-15 0-15 0-15
Cr 0-15 0-15 0-15 1-10
Ir 1-34 0-25 3-27 0-15
Nb 0-15 3-27 0-15 0-15
Ta 0-15 0-15 1-34 0-15
Ti 0-15 0-15 0-15 0-15
Y 3-27 3-27 0-15 0-15
Zr 0-15 0-15 3-27 1-12
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Element/Wt. % Ex, 75 Ex, 76 Ex, 77 Ex, 78
Re 50-75% 55-75% 60-75% 65-75%
Cr 25-50% 25-45% 25-40% 25-35%
Mo 0-25% 0-25% 0-25% 0-25%
Bi 0-25% 0-25% 0-25% 0-25%
Cr 0-25% 0-25% 0-25% 0-25%
Ir 0-25% 0-25% 0-25% 0-25%
Nb 0-25% 0-25% 0-25% 0-25%
Ta 0-25% 0-25% 0-25% 0-25% V 0-25% 0-25% 0-25% 0-25% w 0-25% 0-25% 0-25% 0-25%
Mn 0-25% 0-25% 0-25% 0-25%
Tc 0-25% 0-25% 0-25% 0-25%
Ru 0-25% 0-25% 0-25% 0-25%
Rh 0-25% 0-25% 0-25% 0-25%
Hf 0-25% 0-25% 0-25% 0-25%
Os 0-25% 0-25% 0-25% 0-25%
Cu 0-25% 0-25% 0-25% 0-25%
Ir 0-25% 0-25% 0-25% 0-25%
Ti 0-25% 0-25% 0-25% 0-25%
Y 0-25% 0-25% 0-25% 0-25%
Zr 0-25% 0-25% 0-25% 0-25%
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Element/Wt. % Ex, 79 Ex, 80 Ex, 81 Ex, 82
Re 50-72% 55-72% 60-72% 65-72%
Cr 28-50% 28-45% 28-40% 28-35%
Mo 0-25% 0-25% 0-25% 0-25%
Bi 0-10% 0-10% 0-10% 0-10%
Cr 0-10% 0-10% 0-10% 0-10%
Ir 0-10% 0-10% 0-10% 0-10%
Nb 0-10% 0-10% 0-10% 0-10%
Ta 0-10% 0-10% 0-10% 0-10%
V 0-10% 0-10% 0-10% 0-10% w 0-10% 0-10% 0-10% 0-10%
Mn 0-10% 0-10% 0-10% 0-10%
Tc 0-10% 0-10% 0-10% 0-10%
Ru 0-10% 0-10% 0-10% 0-10%
Rh 0-10% 0-10% 0-10% 0-10%
Hf 0-10% 0-10% 0-10% 0-10%
Os 0-10% 0-10% 0-10% 0-10%
Cu 0-10% 0-10% 0-10% 0-10%
Ir 0-10% 0-10% 0-10% 0-10%
Ti 0-10% 0-10% 0-10% 0-10%
Y 0-10% 0-10% 0-10% 0-10%
Zr 0-10% 0-10% 0-10% 0-10%
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Element/Wt. % Ex, 83 Ex, 84 Ex, 85 Ex, 86
Re 50-70% 55-70% 60-70% 65-70%
Cr 30-50% 30-45% 30-40% 30-35% Mo 0-10% 0-10% 0-10% 0-10%
Bi 0-10% 0-10% 0-10% 0-10%
Cr 0-10% 0-10% 0-10% 0-10%
Ir 0-10% 0-10% 0-10% 0-10%
Nb 0-10% 0-10% 0-10% 0-10%
Ta 0-10% 0-10% 0-10% 0-10%
V 0-10% 0-10% 0-10% 0-10% w 0-10% 0-10% 0-10% 0-10%
Mn 0-10% 0-10% 0-10% 0-10%
Tc 0-10% 0-10% 0-10% 0-10%
Ru 0-10% 0-10% 0-10% 0-10%
Rh 0-10% 0-10% 0-10% 0-10%
Hf 0-10% 0-10% 0-10% 0-10%
Os 0-10% 0-10% 0-10% 0-10%
Cu 0-10% 0-10% 0-10% 0-10%
Ir 0-10% 0-10% 0-10% 0-10%
Ti 0-10% 0-10% 0-10% 0-10%
Y 0-10% 0-10% 0-10% 0-10%
Zr 0-10% 0-10% 0-10% 0-10%
C <0.06 <0.06 <0.06 <0.06
N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Element/Wt. % Ex, 87 Ex, 88 Ex, 89 Ex, 90
Re 50-67.5% 55-67.5% 60-67.5% 65-67.5%
Cr 32.5-50% 32.5-45% 32.5-40% 32.5-35%
Mo 0-10% 0-10% 0-10% 0-10%
Bi 0-10% 0-10% 0-10% 0-10%
Cr 0-10% 0-10% 0-10% 0-10%
Ir 0-10% 0-10% 0-10% 0-10%
Nb 0-10% 0-10% 0-10% 0-10%
Ta 0-10% 0-10% 0-10% 0-10%
V 0-10% 0-10% 0-10% 0-10% w 0-10% 0-10% 0-10% 0-10%
Mn 0-10% 0-10% 0-10% 0-10%
Tc 0-10% 0-10% 0-10% 0-10%
Ru 0-10% 0-10% 0-10% 0-10%
Rh 0-10% 0-10% 0-10% 0-10%
Hf 0-10% 0-10% 0-10% 0-10%
Os 0-10% 0-10% 0-10% 0-10%
Cu 0-10% 0-10% 0-10% 0-10%
Ir 0-10% 0-10% 0-10% 0-10%
Ti 0-10% 0-10% 0-10% 0-10%
Y 0-10% 0-10% 0-10% 0-10%
Zr 0-10% 0-10% 0-10% 0-10%
C <0.06 <0.06 <0.06 <0.06 N <0.06 <0.06 <0.06 <0.06
O <0.06 <0.06 <0.06 <0.06
Figure imgf000030_0001
Metal/Wt. % Ex, 95 Ex, 96 Ex, 97 Ex, 98
Mo 40-99.98% 40-99.9% 40-99.8% 40-99.5%
C 0.01-0.3% 0-0.3% 0-0.3% 0-0.3%
Co <0.002% <0.002% <0.002% <0.002%
Cs2O 0-0.2% 0-0.2% 0.01-0.2% 0-0.2% Fe <0.02% <0.02% <0.02% <0.02%
H <0.002% <0.002% <0.002% <0.002% Hf 0.1-2.5% 0-2.5% 0-2.5% 0-2.5% O <0.06% <0.06% <0.06% <0.06% Os <1% <1% <1% <1% La2O3 0-2% 0.1-2% 0-2% 0-2% N <20 ppm <20 ppm <20 ppm <20 ppm Nb <0.01% <0.01% <0.01% <0.01% Pt <1% <1% <1% <1% Re 0-40% 0-40% 0-40% 0-40% S <0.008% <0.008% <0.008% <0.008% Sn <0.002% <0.002% <0.002% <0.002% Ta 0-50% 0-50% 0-50% 0-50% Tc <1% <1% <1% <1% Ti <1% <1% <1% <1% V <1% <1% <1% <1% w 0-50% 0-50% 0-50% 0.5-50% Y2O3 0-1% 0-1% 0.1-1% 0-1% Zr <1% <1% <1% <1% ZrO2 0-3% 0-3% 0-3% 0-3% CNT 0-10% 0-10% 0-10% 0-10%
Metal/Wt. % Ex, 99 Ex, 100 Ex, 101 Mo 40-99.9% 40-99.5% 40-99.5% C 0-0.3% 0-0.3% 0-0.3% Co <0.002% <0.002% <0.002% Cs2O 0-0.2% 0-0.2% 0-0.2% H <0.002% <0.002% <0.002% Hf 0-2.5% 0-2.5% 0-2.5% O <0.06% <0.06% <0.06% Os <1% <1% <1% La2O3 0-2% 0-2% 0-2% N <20 ppm <20 ppm <20 ppm Nb <0.01% <0.01% <0.01% Pt <1% <1% <1% Re 0-40% 0-40% 0.5-40% S <0.008% <0.008% <0.008% Sn <0.002% <0.002% <0.002% Ta 0-50% 0.5-50% 0-50% Tc <1% <1% <1% Ti <1% <1% <1%
V <1% <1% <1% w 0-50% 0-50% 0-50% Y2O3 0-1% 0-1% 0-1% ZrO2 0.1-3% 0-3% 0-3% CNT 0-10% 0-10% 0-10%
Metal/Wt. % Ex, 102 Ex, 103 Ex, 104 Mo 60-99% 60-95% 60-90% C 0-0.3% 0-0.3% 0-0.3% Co <0.002% <0.002% <0.002% Cs2O 0-0.2% 0-0.2% 0-0.2% H <0.002% <0.002% <0.002% Hf 0-2.5% 0-2.5% 0-2.5% O <0.06% <0.06% <0.06% Os <1% <1% <1% La2O3 0-2% 0-2% 0-2% N <20 ppm <20 ppm <20 ppm Nb <0.01% <0.01% <0.01% Pt <1% <1% <1% Re 1-40% 5-40% 10-40% S <0.008% <0.008% <0.008% Sn <0.002% <0.002% <0.002% Ta 0-50% 0.5-50% 0-50% Tc <1% <1% <1% Ti <1% <1% <1% V <1% <1% <1% w 0-50% 0-50% 0-50% Y2O3 0-1% 0-1% 0-1% ZrO2 0.1-3% 0-3% 0-3% CNT 0-10% 0-10% 0-10%
Ex, 105 Ex, 106 Ex, 107 Ex, 108 98-99.15% 98-99.7% 50-99.66% 40-80% 0.05-0.15% 0-0.15% 0-0.15% 0-0.15% 0-0.2% 0-0.2% 0.04-0.1% 0-0.2% 0.8-1.4% 0-2% 0-2.5% 0-2.5% 0-2% 0.3-0.7% 0-2% 0-2% 0-2% 0-2% 0-40% 0-40% 0-2% 0-2% 0-50% 0-50% 0-2% 0-2% 0-50% 20-50% 0-1% 0-1% 0.3-0.5% 0-1%
Figure imgf000032_0001
0-3% 0-3% 0-3% 0-3%
Metal/Wt. % Ex, 109 Ex, 110 Ex, 111
Mo 97-98.8% 50-90% 60-99.5%
C 0-0.15% 0-0.15% 0-0.15%
Cs2O 0-0.2% 0-0.2% 0-0.2%
Hf 0-2.5% 0-2.5% 0-2.5%
La2O3 0-2% 0-2% 0-2%
Re 0-3% 0-40% 0.5-40%
Ta 0-3% 10-50% 0-40%
W 0-3% 0-50% 0-40%
Y2O3 0-1% 0-1% 0-1%
ZrO2 1.2-1.8% 0-3% 0-3%
Metal/Wt. % Ex, 112 Ex, 113 Ex, 114
W 20-99% 60-99% 20-80%
Re 1-47.5% 1-40% 1-47.5%
Mo 0-47.5% <0.5% 1-47.5%
Cu <0.5% <0.5% <0.5%
C <0.15% <0.15% <0.15%
Co <0.002% <0.002% <0.002% Cs2O <0.2% <0.2% <0.2% Fe <0.02% <0.02% <0.02% H <0.002% <0.002% <0.002% Hf <0.5% <0.5% <0.5% La2O3 <0.5% <0.5% <0.5% O <0.06% <0.06% <0.06% Os <0.5% <0.5% <0.5% N <20 ppm <20 ppm <20 ppm Nb <0.01% <0.01% <0.01% Pt <0.5% <0.5% <0.5% S <0.008% <0.008% <0.008% Sn <0.002% <0.002% <0.002% Ta <0.5% <0.5% <0.5% Tc <0.5% <0.5% <0.5% Ti <0.5% <0.5% <0.5% V <0.5% <0.5% <0.5% Y2O3 <0.5% <0.5% <0.5%
Zr <0.5% <0.5% <0.5% ZrO2 <0.5% <0.5% <0.5% CNT 0-10% 0-10% <0.5%.
Figure imgf000033_0001
ZrO2 0-3% 0-3% 0-3% 0-3%
CNT 0-10% 0-10% 0-10% 0-10%
Ex, 119 Ex, 120 Ex, 121 20-98% 25-98% 30-95% 2-80% 2-75% 5-70% 0-0.3% 0-0.3% 0-0.3% <0.002% <0.002% <0.002% 0-0.2% 0-0.2% 0-0.2% <0.002% <0.002% <0.002% 0-2.5% 0-2.5% 0-2.5% <0.06% <0.06% <0.06% <1% <1% <1% 0-2% 0-2% 0-2% 0-3% 0-2% 0-1% <20 ppm <20 ppm <20 ppm <0.01% <0.01% <0.01% <1% <1% <1% 0-40% 0-40% 0.5-40% <0.008% <0.008% <0.008% <0.002% <0.002% <0.002% 0-50% 0.5-50% 0-50% <1% <1% <1% <1% <1% <1% <1% <1% <1% 0-1% 0-1% 0-1% 0.1-3% 0-3% 0-3%
Figure imgf000034_0001
0-10% 0-10% 0-10%
Metal/Wt. % Ex, 122 Ex, 123 Ex, 124 Ex, 125
W 25-95% 35-95% 40-95% 50-95%
Cu 5-75% 5-65% 5-60% 5-50%
C 0.05-0.15% 0-0.15% 0-0.15% 0-0.15%
Cs2O 0-0.2% 0-0.2% 0.04-0.1% 0-0.2%
Hf 0.8-1.4% 0-2.5% 0-2.5% 0-2.5%
La2O3 0-2% 0.3-0.7% 0-2% 0-2%
Re 0-40% 0-40% 0-40% 0-40%
Ta 0-50% 0-50% 0-50% 0-50%
Y2O3 0-1% 0-1% 0.3-0.5% 0-1%
ZrO2 0-3% 0-3% 0-3% 0-3%
Metal/Wt. % Ex, 126 Ex, 127 Ex, 128
W 55-99% 60-99% 70-99%
Cu 1-45% 1-40% 1-30%
C 0-0.15% 0-0.15% 0-0.15%
Cs2O 0-0.2% 0-0.2% 0-0.2% Hf 0-2.5% 0-2.5% 0-2.5%
La2C>3 0-2% 0-2% 0-2%
Re 0-40% 0-40% 5-40%
Ta 0-50% 10-50% 0-50%
W 0-50% 0-50% 0-50%
Y2O3 0-1% 0-1% 0-1%
ZrO2 1.2-1.8% 0-3% 0-3%
Metal/Wt. % Ex, 129 Ex, 130 Ex, 131
Ti 55-80% 65-80% 70-80%
Mo 20-30% 20-30% 20-25%
Re <0.5% <0.5% <0.5%
Yt <0.5% <0.5% <0.5%
Nb <0.5% <0.5% <0.5%
Co <0.5% <0.5% <0.5%
Cr <0.5% <0.5% <0.5%
Zr <0.5% <0.5% <0.5%
C <0.15% <0.15% <0.15%
O <0.06% <0.06% <0.06%
N <20 ppm <20 ppm <20 ppm
Metal/Wt. % Ex, 132 Ex, 133 Ex, 134
W 20-99% 60-99% 20-80%
Re 1-47.5% 1-40% 1-47.5%
Mo 0-47.5% <0.5% 1-47.5%
Metal/Wt. % Ex, 135 Ex, 136 Ex, 137
W 50.1-99% 65-99% 70-99%
Re 1-40% 1-35% 1-30%
Mo 0-40% <0.5% 1-30%
Metal/Wt. % Ex, 138 Ex, 139 Ex, 140
W 20-49% 20-49% 20-49%
Re 1-40% 1-40% 1-39%
Mo 20-60% 30-60% 40-60%
Metal/Wt. % Ex, 141 Ex, 142 Ex, 143
W 20-40% 20-35% 20-30%
Re 1-40% 10-40% 25-40%
Mo 0-40% 10-40% 25-40%
Metal/Wt. % Ex, 144 Ex, 145 Ex, 146
W 20-99% 60-99% 20-80%
Re 1-47.5% 1-40% 1-47.5%
Mo 0-47.5% <0.5% 1-47.5%
Cu <0.5% <0.5% <0.5% C <0.15% <0.15% <0.15% Co <0.002% <0.002% <0.002% Cs2O <0.2% <0.2% <0.2% Fe <0.02% <0.02% <0.02% H <0.002% <0.002% <0.002% Hf <0.5% <0.5% <0.5% La2O3 <0.5% <0.5% <0.5% O <0.06% <0.06% <0.06% Os <0.5% <0.5% <0.5% N <20 ppm <20 ppm <20 ppm Nb <0.01% <0.01% <0.01% Pt <0.5% <0.5% <0.5% S <0.008% <0.008% <0.008% Sn <0.002% <0.002% <0.002% Ta <0.5% <0.5% <0.5% Tc <0.5% <0.5% <0.5% Ti <0.5% <0.5% <0.5% V <0.5% <0.5% <0.5% Y2O3 <0.5% <0.5% <0.5% Zr <0.5% <0.5% <0.5% ZrO2 <0.5% <0.5% <0.5% CNT 0-10% 0-10% <0.5%.
[0038] In Examples 1-146, it will be appreciated that all of the above ranges include any value between the range and any other range that is between the ranges set forth above. Any of the above values that include the < symbol includes the range from 0 to the stated value and all values and ranges therebetween.
[0039] In the above refractory metal alloys, the average grain size of the refractory metal alloy can be about 4-20 ASTM, the tensile elongation of the refractory metal alloy can be about 25-50%, the average density of the refractory metal alloy can be at least about 5 gm/cc, the average yield strength of the refractory metal alloy can be about 70-250 (ksi), the average ultimate tensile strength of the refractory metal alloy can be about 80-550 UTS (ksi), and an average Vickers hardness can be 234 DPH to 700 DPH or a Rockwell C hardness of 19-60 at 77°F; however, this is not required.
[0040] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is optionally at least partially formed by a swaging process; however, this is not required. In one non-limiting embodiment, swaging is performed on the refractory metal alloy to at least partially or fully achieve final dimensions of one or more portions of the medical device. The swaging dies can be shaped to fit the final dimension of the medical device; however, this is not required. Where there are undercuts of hollow structures in the medical device (which is not required), a separate piece of metal can be placed in the undercut to at least partially fill the gap. The separate piece of metal (when used) can be designed to be later removed from the undercut; however, this is not required. The swaging operation can be performed on the medical device in the areas to be hardened. For a round or curved portion of a medical device, the swaging can be rotary. For non-round portion of the medical device, the swaging of the non-round portion of the medical device can be performed by non-rotating swaging dies. The dies can optionally be made to oscillate in radial and/or longitudinal directions instead of or in addition to rotating. The medical device can optionally be swaged in multiple directions in a single operation or in multiple operations to achieve a hardness in desired location and/or direction of the medical device. The swaging temperature for a particular refractory metal alloy can vary. For a refractory metal alloy (e.g., MoRe alloy, ReW alloy, ReCr alloy, etc.), the swaging temperature can be from room temperature (RT) (e.g., 10-27°C and all values and ranges therebetween) to about 400°C (e.g., 10-400°C and all values and ranges therebetween) if the swaging is conducted in air or an oxidizing environment. The swaging temperature can be increased to up to about 1500°C (e.g., 10-1500°C and all values and ranges therebetween) if the swaging process is performed in a controlled neutral or non-reducing environment (e.g., inert environment). The swaging process can be conducted by repeatedly hammering the medical device at the location to be hardened at the desired swaging temperature. In one non-limiting embodiment, during the swaging process ions of boron and/or nitrogen are allowed to impinge upon rhenium atoms in the refractory metal alloys that include rhenium to form ReEF, ReN2 and/or ReNy however, this is not required. It has been found that ReEF, ReN2 and/or ReNs are ultra-hard compounds. As can be appreciated, other refractory metal alloys that include Re and that are subjected to a swaging process can also form ReB2, ReN2 and/or ReN In one non -limiting process, the refractory metal alloy for the medical device can be machined and shaped to at least partially form the medical device when the refractory metal alloy is in a less hardened state; however, this is not required. As such, the raw starting material can be first annealed to soften and then machined into a desired shape. After the refractory metal alloy is shaped, the refractory metal alloy can be re-hardened. The hardening of the refractory metal alloy of the medical device can improve the wear resistance and/or shape retention of the medical device. The refractory metal alloy of the medical generally cannot be re- hardened by annealing, thus a special rehardening processes is required. Such rehardening can be achieved by the swaging process of the present disclosure.
[0041] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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. After the refractory metal alloy is nitrided, the refractory metal alloy is typically cleaned; however, this is not required. During the nitride process, 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. In gas nitriding, the nitrogen diffuses onto the surface of the refractory metal alloy, thereby creating a nitride layer. The thickness and phase constitution of the resulting nitrided layers can be selected and the process optimized for the particular properties required. During gas nitriding, the refractory metal alloy is generally nitrided in the presence of nitrogen gas or a nitrogen gas mixture (e.g., 90-99% vol.% nitrogen and 1-10 vol.% hydrogen, etc.) for at least 10 seconds a temperature of at least about 400°C (e.g., 400-1000°C and all values and ranges therebetween). In one non-limiting nitriding process, the refractory metal alloy is heated in the presence of nitrogen or a nitrogen-hydrogen mixture to a temperature of at least 400°C, and generally about 400-800°C (and all values and ranges therebetween) for at least 10 seconds (e.g., 10 seconds to 60 minutes and all values and ranges therebetween), and generally about 1-30 minutes. In salt bath nitriding, a nitrogen-containing salt such as cyanide salt is used. During the salt bath nitriding, the refractory metal alloy is generally exposed to temperatures of about 520- 590°C. In plasma nitriding, the gas used for plasma nitriding is usually pure nitrogen. Plasma nitriding is often coupled with physical vapor deposition (PVD) process; however, this is not required. Plasma nitriding of the refractory metal alloy generally occurs at a temperature of 220- 630°C (and all values and ranges therebetween). The refractory metal alloy can optionally be exposed to argon and/or hydrogen gas prior to the nitriding process to clean and/or preheat the refractory metal alloy. These gases can be optionally used to clean oxide layers and/or solvents from the surface of the refractory metal alloy. During the nitriding process, the refractory metal alloy can optionally be exposed to hydrogen gas to inhibit or prevent the formation of oxides on the surface of the refractory metal alloy. The thickness of the nitrided surface layer is less than about 1 mm. In one non-limiting embodiment, the thickness of the nitrided surface layer is at least about 50 nanometer and less than about 1 mm (and all values and ranges therebetween). In another non-limiting embodiment, the thickness of the nitrided surface layer is at least about 50 nanometer and less than about 0.1 mm. Generally, the weight percent of nitrogen in the nitrided surface layer is 0.0001-5 wt.% nitrogen (and all values and ranges therebetween). In one non-limiting embodiment, the weight percent of nitrogen in the nitrided surface layer is generally less than one of the primary components of the refractory metal alloy, and typically less than each of the two primary components of the refractory metal alloy. For example, when a refractory metal alloy in the form of a MoRe alloy is nitrided, the weight percent of the nitrogen in the nitrided surface layer is less than a weight percent of the molybdenum in the nitrided surface layer. Also, the weight percent of nitrogen in the nitrided surface layer is less than a weight percent of the rhenium in the nitrided surface layer. In one non-limiting composition of 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). In another non-limiting composition of the nitrided surface layer, the nitride surface layer comprises 40-99 wt.% molybdenum, 1-40 wt.% rhenium, and 0.001-1 wt.% nitrogen. As can be appreciated, other refractory metal alloys can be nitrided. For such other refractory metal alloys, the nitride surface layer typically includes 0.001-5 wt.% nitrogen (and all values and ranges therebetween), and the primary constituents of the refractory metal alloy (e.g., metals that constitute at least 5 wt.% of the refractory metal alloy) are present in the nitride surface layer in a greater weight percent than the nitrogen content in the refractory metal alloy. The nitriding process for the refractory metal alloy can be used to increase surface hardness and/or wear resistance of the medical device, and/or to inhibit or prevent discoloration of the refractory metal alloy (e.g., discoloration by oxidation, etc.). For example, the nitriding process can be used to increase the wear resistance of articulation surfaces or surfaces wear on the refractory metal alloy used in the medical device to extend the life of the medical device, and/or to increase the wear life of mating surfaces on the medical device (e.g., polyethylene liners of joint implants like knees, hips, shoulders, etc.), to reduce particulate generation from use of the medical device, and/or to maintain the outer surface appearance of the refractory metal alloy on the medical device.
[0042] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the surface of the refractory metal alloy is optionally nitrided prior to at least one drawing step for the refractory metal alloy.
[0043] In accordance with another and/or alternative non-limiting aspect of the present disclosure, after the refractory metal alloy has been annealed, the refractory metal alloy is optionally nitrided prior to being drawn.
[0044] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy the refractory metal alloy is optionally cleaned to remove nitride compounds on the surface of the refractory metal alloy prior to annealing the refractory metal alloy. The nitride compounds can be removed by a variety of steps such as, but not limited to, grit blasting, polishing, etc. After the refractory metal alloy has been annealed, the refractory metal alloy can be again nitrided prior to one or more drawing steps; however, this is not required. As can be appreciated, the complete outer surface of the refractory metal alloy can be nitrided or a portion of the outer surface of the refractory metal alloy can be nitrided.
[0045] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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.
[0046] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the final formed refractory metal alloy can optionally include a nitride outer surface.
[0047] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy, just prior to or after being partially or fully formed into the desired medical device, can optionally be cleaned, polished, sterilized, nitrided, etc., for final processing of the refractory metal alloy. In one non-limiting embodiment of the disclosure, the refractory metal alloy is optionally electropolished. In one non-limiting aspect of this embodiment, the refractory metal alloy is cleaned prior to being exposed to the polishing solution; however, this is not required. The cleaning process (when used) can be accomplished by a variety of techniques such as, but not limited to, 1) using a solvent (e.g., acetone, methyl alcohol, etc.) and wiping the refractory metal alloy with a Kimwipe or other appropriate towel, and/or 2) at least partially dipping or immersing the refractory metal alloy in a solvent and then ultrasonically cleaning the refractory metal alloy. As can be appreciated, the refractory metal alloy can be cleaned in other or additional ways. In accordance with another and/or alternative non-limiting aspect of this embodiment, the polishing solution can include one or more acids. One non-limiting formulation of the polishing solution includes about 10-80 percent by volume sulfuric acid (and all values and ranges therebetween). As can be appreciated, other polishing solution compositions can be used. In still another and/or alternative non-limiting aspect of this embodiment, about 5-12 volts (and all values and ranges therebetween) are directed to the refractory metal alloy during the electropolishing process; however, other voltage levels can be used. In yet another and/or alternative non-limiting aspect of this embodiment, the refractory metal alloy is rinsed with water and/or a solvent and allowed to dry to remove polishing solution on the refractory metal alloy.
[0048] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the use of the refractory metal alloy to partially or fully form the medical device can be used to increase the strength, hardness, and/or durability of the medical device compared with stainless steel, chromium-cobalt alloys, or titanium alloys; thus, a lesser quantity of refractory metal alloy can be used in the medical device to achieve similar strengths compared to medical devices formed of different metals. As such, the resulting medical device can be made smaller and less bulky by use of the refractory metal alloy without sacrificing the strength and durability of the medical device. Such a medical device can have a smaller profile, thus can be inserted in smaller areas, openings, and/or passageways. The refractory metal alloy also can increase the radial strength of the medical device. For example, the thickness of the walls of the medical device and/or the wires used to at least partially form the medical device can be made thinner and achieve a similar or improved radial strength as compared with thicker walled medical devices formed of stainless steel, titanium alloys, or cobalt and chromium alloys. The refractory metal alloy also can improve stress-strain properties, bendability, and flexibility of the medical device, thus increasing the life of the medical device. For example, the medical device can be used in regions that subject the medical device to bending. Due to the improved physical properties of the medical device from the refractory metal alloy, the medical device has improved resistance to fracturing in such frequent bending environments. In addition or alternatively, the improved bendability and flexibility of the medical device due to the use of the refractory metal alloy enables the medical device to be more easily inserted into various regions of a body. The refractory metal alloy can also reduce the degree of recoil during the crimping and/or expansion of the medical device. For example, the medical device better maintains its crimped form and/or better maintains its expanded form after expansion due to the use of the refractory metal alloy. As such, 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 into various regions of a body. Also, the medical device better maintains its expanded profile after expansion to facilitate in the success of the medical device in the treatment area. In addition to the improved physical properties of the medical device by use of the refractory metal alloy, the refractory metal alloy has improved radiopaque properties as 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. For instance, the refractory metal alloy is believed to at least about 10-20% more radiopaque than stainless steel or cobalt-chromium alloy.
[0049] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device can include, contain and/or be coated with one or more agents that facilitate in the success of the medical device and/or treated area. The term “agent” includes, but is not limited to a substance, pharmaceutical, biologic, veterinary product, drug, and analogs or derivatives otherwise formulated and/or designed to prevent, inhibit and/or treat one or more clinical and/or biological events, and/or to promote healing. Non-limiting examples of clinical events that can be addressed by one or more agents include, but are not limited to, viral, fungus and/or bacterial infection; vascular diseases and/or disorders; digestive diseases and/or disorders; reproductive diseases and/or disorders; lymphatic diseases and/or disorders; cancer; implant rejection; pain; nausea; swelling; arthritis; bone diseases and/or disorders; organ failure; immunity diseases and/or disorders; cholesterol problems; blood diseases and/or disorders; lung diseases and/or disorders; heart diseases and/or disorders; brain diseases and/or disorders; neuralgia diseases and/or disorders; kidney diseases and/or disorders; ulcers; liver diseases and/or disorders; intestinal diseases and/or disorders; gallbladder diseases and/or disorders; pancreatic diseases and/or disorders; psychological disorders; respiratory diseases and/or disorders; gland diseases and/or disorders; skin diseases and/or disorders; hearing diseases and/or disorders; oral diseases and/or disorders; nasal diseases and/or disorders; eye diseases and/or disorders; fatigue; genetic diseases and/or disorders; bums; scarring and/or scars; trauma; weight diseases and/or disorders; addiction diseases and/or disorders; hair loss; cramps; muscle spasms; tissue repair; nerve repair; neural regeneration and/or the like. Non-limiting examples of agents that can be used include, but are not limited to, 5 -fluorouracil and/or derivatives thereof; 5-phenylmethimazole and/or derivatives thereof; ACE inhibitors and/or derivatives thereof; acenocoumarol and/or derivatives thereof; acyclovir and/or derivatives thereof; actilyse and/or derivatives thereof; adrenocorticotropic hormone and/or derivatives thereof; adriamycin and/or derivatives thereof; agents that modulate intracellular Ca2+ transport such as L-type (e.g., diltiazem, nifedipine, verapamil, etc.) or T-type Ca2+ channel blockers (e.g., amiloride, etc.); alpha-adrenergic blocking agents and/or derivatives thereof; alteplase and/or derivatives thereof; amino glycosides and/or derivatives thereof (e.g., gentamycin, tobramycin, etc.); angiopeptin and/or derivatives thereof; angiostatic steroid and/or derivatives thereof; angiotensin II receptor antagonists and/or derivatives thereof; anistreplase and/or derivatives thereof; antagonists of vascular epithelial growth factor and/or derivatives thereof; antibiotics; anti -coagulant compounds and/or derivatives thereof; antifibrosis compounds and/or derivatives thereof; antifungal compounds and/or derivatives thereof; anti-inflammatory compounds and/or derivatives thereof; anti-invasive factor and/or derivatives thereof; anti-metabolite compounds and/or derivatives thereof (e.g., staurosporin, trichothecenes, and modified diphtheria and ricin toxins, pseudomonas exotoxin, etc.); anti-matrix compounds and/or derivatives thereof (e.g., colchicine, tamoxifen, etc.); anti-microbial agents and/or derivatives thereof; anti-migratory agents and/or derivatives thereof (e.g., caffeic acid derivatives, nilvadipine, etc.); anti-mitotic compounds and/or derivatives thereof; anti -neoplastic compounds and/or derivatives thereof; anti-oxidants and/or derivatives thereof; anti-platelet compounds and/or derivatives thereof; anti-proliferative and/or derivatives thereof; anti-thrombogenic agents and/or derivatives thereof; argatroban and/or derivatives thereof; ap-1 inhibitors and/or derivatives thereof (e.g., for tyrosine kinase, protein kinase C, myosin light chain kinase, Ca2+/calmodulin kinase II, casein kinase II, etc.); aspirin and/or derivatives thereof; azathioprine and/or derivatives thereof; P-estradiol and/or derivatives thereof; P-1 -anticollagenase and/or derivatives thereof; calcium channel blockers and/or derivatives thereof; calmodulin antagonists and/or derivatives thereof (e.g., H7, etc.); CAPTOPRIL and/or derivatives thereof; cartilage-derived inhibitor and/or derivatives thereof; ChIMP-3 and/or derivatives thereof; cephalosporin and/or derivatives thereof (e.g., cefadroxil, cefazolin, cefaclor, etc.); chloroquine and/or derivatives thereof; chemotherapeutic compounds and/or derivatives thereof (e.g., 5 -fluorouracil, vincristine, vinblastine, cisplatin, doxyrubicin, adriamycin, tamocifen, etc.); chymostatin and/or derivatives thereof; CILAZAPRIL and/or derivatives thereof; clopidigrel and/or derivatives thereof; clotrimazole and/or derivatives thereof; colchicine and/or derivatives thereof; cortisone and/or derivatives thereof; coumadin and/or derivatives thereof; curacin-A and/or derivatives thereof; cyclosporine and/or derivatives thereof; cytochalasin and/or derivatives thereof (e.g., cytochalasin A, cytochalasin B, cytochalasin C, cytochalasin D, cytochalasin E, cytochalasin F, cytochalasin G, cytochalasin H, cytochalasin J, cytochalasin K, cytochalasin L, cytochalasin M, cytochalasin N, cytochalasin O, cytochalasin P, cytochalasin Q, cytochalasin R, cytochalasin S, chaetoglobosin A, chaetoglobosin B, chaetoglobosin C, chaetoglobosin D, chaetoglobosin E, chaetoglobosin F, chaetoglobosin G, chaetoglobosin J, chaetoglobosin K, deoxaphomin, proxiphomin, protophomin, zygosporin D, zygosporin E, zygosporin F, zygosporin G, aspochalasin B, aspochalasin C, aspochalasin D, etc.); cytokines and/or derivatives thereof; desirudin and/or derivatives thereof; dexamethazone and/or derivatives thereof; dipyridamole and/or derivatives thereof; eminase and/or derivatives thereof; endothelin and/or derivatives thereof endothelial growth factor and/or derivatives thereof; epidermal growth factor and/or derivatives thereof; epothilone and/or derivatives thereof; estramustine and/or derivatives thereof; estrogen and/or derivatives thereof; fenoprofen and/or derivatives thereof; fluorouracil and/or derivatives thereof; flucytosine and/or derivatives thereof; forskolin and/or derivatives thereof; ganciclovir and/or derivatives thereof; glucocorticoids and/or derivatives thereof (e.g., dexamethasone, betamethasone, etc.); glycoprotein Ilb/IIIa platelet membrane receptor antibody and/or derivatives thereof; GM-CSF and/or derivatives thereof; griseofulvin and/or derivatives thereof; growth factors and/or derivatives thereof (e.g., VEGF; TGF; IGF; PDGF; FGF, etc.); growth hormone and/or derivatives thereof; heparin and/or derivatives thereof; hirudin and/or derivatives thereof; hyaluronate and/or derivatives thereof; hydrocortisone and/or derivatives thereof; ibuprofen and/or derivatives thereof; immunosuppressive agents and/or derivatives thereof (e.g., adrenocorticosteroids, cyclosporine, etc.); indomethacin and/or derivatives thereof; inhibitors of the sodium/calcium antiporter and/or derivatives thereof (e.g., amiloride, etc.); inhibitors of the IP3 receptor and/or derivatives thereof; inhibitors of the sodium/hydrogen antiporter and/or derivatives thereof (e.g., amiloride and derivatives thereof, etc.); insulin and/or derivatives thereof; interferon a-2- macroglobulin and/or derivatives thereof; ketoconazole and/or derivatives thereof; lepirudin and/or derivatives thereof; LISINOPRIL and/or derivatives thereof; LOVASTATIN and/or derivatives thereof; marevan and/or derivatives thereof; mefloquine and/or derivatives thereof; metalloproteinase inhibitors and/or derivatives thereof; methotrexate and/or derivatives thereof; metronidazole and/or derivatives thereof; miconazole and/or derivatives thereof; monoclonal antibodies and/or derivatives thereof; mutamycin and/or derivatives thereof; naproxen and/or derivatives thereof; nitric oxide and/or derivatives thereof; nitroprusside and/or derivatives thereof; nucleic acid analogues and/or derivatives thereof (e.g., peptide nucleic acids, etc.); nystatin and/or derivatives thereof; oligonucleotides and/or derivatives thereof; paclitaxel and/or derivatives thereof; penicillin and/or derivatives thereof; pentamidine isethionate and/or derivatives thereof; phenindione and/or derivatives thereof; phenylbutazone and/or derivatives thereof; phosphodiesterase inhibitors and/or derivatives thereof; plasminogen activator inhibitor- 1 and/or derivatives thereof; plasminogen activator inhibitor-2 and/or derivatives thereof; platelet factor 4 and/or derivatives thereof; platelet derived growth factor and/or derivatives thereof; plavix and/or derivatives thereof; POSTMI 75 and/or derivatives thereof; prednisone and/or derivatives thereof; prednisolone and/or derivatives thereof; probucol and/or derivatives thereof; progesterone and/or derivatives thereof; prostacyclin and/or derivatives thereof; prostaglandin inhibitors and/or derivatives thereof; protamine and/or derivatives thereof; protease and/or derivatives thereof; protein kinase inhibitors and/or derivatives thereof (e.g., staurosporin, etc.); quinine and/or derivatives thereof; radioactive agents and/or derivatives thereof (e.g., Cu-64, Ca-67, Cs-131, Ga- 68, Zr-89, Ku-97, Tc-99m, Rh-105, Pd-103, Pd-109, In-111, 1-123, 1-125, 1-131, Re-186, Re-188, Au-198, Au-199, Pb-203, At-211, Pb-212, Bi-212, H3P32O4, etc.); rapamycin and/or derivatives thereof; receptor antagonists for histamine and/or derivatives thereof; refludan and/or derivatives thereof; retinoic acids and/or derivatives thereof; revasc and/or derivatives thereof; rifamycin and/or derivatives thereof; sense or anti-sense oligonucleotides and/or derivatives thereof (e.g., DNA, RNA, plasmid DNA, plasmid RNA, etc.); seramin and/or derivatives thereof; steroids; seramin and/or derivatives thereof; serotonin and/or derivatives thereof; serotonin blockers and/or derivatives thereof; streptokinase and/or derivatives thereof; sulfasalazine and/or derivatives thereof; sulfonamides and/or derivatives thereof (e.g., sulfamethoxazole, etc.); sulphated chitin derivatives; Sulphated Polysaccharide Peptidoglycan Complex and/or derivatives thereof; TH1 and/or derivatives thereof (e.g., Interleukins-2, -12, and -15, gamma interferon, etc.); thioprotese inhibitors and/or derivatives thereof; taxol and/or derivatives thereof (e.g., taxotere, baccatin, 10- deacetyltaxol, 7-xylosyl-10-deacetyltaxol, cephalomannine, 10-deacetyl-7-epitaxol, 7 epitaxol, 10-deacetylbaccatin III, 10-deacetylcephaolmannine, etc.); ticlid and/or derivatives thereof; ticlopidine and/or derivatives thereof; tick anti -coagulant peptide and/or derivatives thereof; thioprotese inhibitors and/or derivatives thereof; thyroid hormone and/or derivatives thereof; tissue inhibitor of metalloproteinase- 1 and/or derivatives thereof; tissue inhibitor of metalloproteinase-2 and/or derivatives thereof; tissue plasma activators; TNF and/or derivatives thereof, tocopherol and/or derivatives thereof; toxins and/or derivatives thereof; tranilast and/or derivatives thereof; transforming growth factors alpha and beta and/or derivatives thereof; trapidil and/or derivatives thereof; triazolopyrimidine and/or derivatives thereof; vapiprost and/or derivatives thereof; vinblastine and/or derivatives thereof; vincristine and/or derivatives thereof; zidovudine and/or derivatives thereof. As can be appreciated, the agent can include one or more derivatives of the above listed compounds and/or other compounds. In one non-limiting embodiment, the agent includes, but is not limited to, trapidil, trapidil derivatives, taxol, taxol derivatives (e.g., taxotere, baccatin, 10-deacetyltaxol, 7-xylosyl-10-deacetyltaxol, cephalomannine, 10-deacetyl-7-epitaxol, 7 epitaxol, 10-deacetylbaccatin III, 10-deacetylcephaolmannine, etc.), cytochalasin, cytochalasin derivatives (e.g., cytochalasin A, cytochalasin B, cytochalasin C, cytochalasin D, cytochalasin E, cytochalasin F, cytochalasin G, cytochalasin H, cytochalasin J, cytochalasin K, cytochalasin L, cytochalasin M, cytochalasin N, cytochalasin O, cytochalasin P, cytochalasin Q, cytochalasin R, cytochalasin S, chaetoglobosin A, chaetoglobosin B, chaetoglobosin C, chaetoglobosin D, chaetoglobosin E, chaetoglobosin F, chaetoglobosin G, chaetoglobosin J, chaetoglobosin K, deoxaphomin, proxiphomin, protophomin, zygosporin D, zygosporin E, zygosporin F, zygosporin G, aspochalasin B, aspochalasin C, aspochalasin D, etc.), paclitaxel, paclitaxel derivatives, rapamycin, rapamycin derivatives, 5-phenylmethimazole, 5-phenylmethimazole derivatives, GM- CSF (granulo-cytemacrophage colony-stimulating-factor), GM-CSF derivatives, statins or HMG- CoA reductase inhibitors forming a class of hypolipidemic agents, combinations, or analogs thereof, or combinations thereof. The type and/or amount of agent included in medical device and/or coated on medical device can vary. When two or more agents are included in and/or coated on medical device, the amount of two or more agents can be the same or different. The type and/or amount of agent included on, in and/or in conjunction with medical device are generally selected to address one or more clinical events.
[0050] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the amount of agent included on, in and/or used in conjunction with medical device, when the agent is used, is about O.Ol-lOOug per mm2 (and all values and ranges wherein between) and/or at least about 0.00001 wt.% of device; however, other amounts can be used. The amount of two of more agents on, in and/or used in conjunction with medical device can be the same or different. 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. The amount of two of more agents on, in and/or used in conjunction with medical device, when two one more agents are used, can be the same or different.
[0051] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the one or more agents on and/or in the medical device, when used on the medical device, can be released in a controlled manner so the area in question to be treated is provided with the desired dosage of agent over a sustained period of time. As can be appreciated, controlled release of one or more agents on the medical device is not always required and/or desirable. As such, one or more of the agents on and/or in the medical device can be uncontrollably released from the medical device during and/or after insertion of the medical device in the treatment area. It can also be appreciated that one or more agents on and/or in the medical device can be controllably released from the medical device and one or more agents on and/or in the medical device can be uncontrollably released from the medical device. It can also be appreciated that one or more agents on and/or in one region of the medical device can be controllably released from the medical device and one or more agents on and/or in the medical device can be uncontrollably released from another region on the medical device. As such, the medical device can be designed such that 1) all the agent on and/or in the medical device is controllably released, 2) some of the agent on and/or in the medical device is controllably released and some of the agent on the medical device is non-controllably released, or 3) none of the agent on and/or in the medical device is controllably released. The medical device can also be designed such that the rate of release of the one or more agents from the medical device is the same or different. The medical device can also be designed such that the rate of release of the one or more agents from one or more regions on the medical device is the same or different. Non-limiting arrangements that can be used to control the release of one or more agents from the medical device include 1) at least partially coat one or more agents with one or more polymers, 2) at least partially incorporate and/or at least partially encapsulate one or more agents into and/or with one or more polymers, and/or 3) insert one or more agents in pores, passageway, cavities, etc. in the medical device and at least partially coat or cover such pores, passageway, cavities, etc. with one or more polymers. As can be appreciated, other or additional arrangements can be used to control the release of one or more agents from the medical device.
[0052] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the one or more polymers used to at least partially control the release of one or more agents from the medical device can be porous or non-porous. The one or more agents can be inserted into and/or applied to one or more surface structures and/or micro-structures on the medical device, and/or be used to at least partially form one or more surface structures and/or micro-structures on the medical device. As such, the one or more agents on the medical device can be 1) coated on one or more surface regions of the medical device, 2) inserted and/or impregnated in one or more surface structures and/or micro-structures, etc. of the medical device, and/or 3) form at least a portion or be included in at least a portion of the structure of the medical device. When the one or more agents are coated on the medical device, the one or more agents can 1) be directly coated on one or more surfaces of the medical device, 2) be mixed with one or more coating polymers or other coating materials and then at least partially coated on one or more surfaces of the medical device, 3) be at least partially coated on the surface of another coating material that has been at least partially coated on the medical device, and/or 4) be at least partially encapsulated between a) a surface or region of the medical device and one or more other coating materials and/or b) two or more other coating materials. As can be appreciated, many other coating arrangements can be additionally or alternatively used. When the one or more agents are inserted and/or impregnated in one or more internal structures, surface structures and/or micro-structures of the medical device, 1) one or more other coating materials can be applied at least partially over the one or more internal structures, surface structures and/or micro-structures of the medical device, and/or 2) one or more polymers can be combined with one or more agents. As such, the one or more agents can be 1) embedded in the structure of the medical device; 2) positioned in one or more internal structures of the medical device; 3) encapsulated between two polymer coatings; 4) encapsulated between the base structure and a polymer coating; and/or 5) mixed in the base structure of the medical device that includes at least one polymer coating. In addition or alternatively, the one or more coating of the one or more polymers on the medical device can include 1) one or more coatings of non-porous polymers; 2) one or more coatings of a combination of one or more porous polymers and one or more non-porous polymers; and/or 3) one or more coating of porous polymer.
[0053] In accordance with another and/or alternative non-limiting aspect of the present disclosure, different agents can optionally be located in and/or between different polymer coating layers and/or on and/or the structure of the medical device. As can also be appreciated, many other and/or additional coating combinations and/or configurations can be used. The concentration of one or more agents, the type of polymer, the type and/or shape of internal structures in the medical device and/or the coating thickness of one or more agents can be used to control the release time, the release rate and/or the dosage amount of one or more agents; however, other or additional combinations can be used. As such, the agent and polymer system combination and location on the medical device can be numerous. As can also be appreciated, one or more agents can be deposited on the top surface of the medical device to provide an initial uncontrolled burst effect of the one or more agents prior to 1) the controlled release of the one or more agents through one or more layers of a polymer system that include one or more non-porous polymers and/or 2) the uncontrolled release of the one or more agents through one or more layers of a polymer system. The one or more agents and/or polymers can be coated on the medical device by a variety of mechanisms such as, but not limited to, spraying (e.g., atomizing spray techniques, etc.), dip coating, roll coating, sonication, brushing, plasma deposition, and/or depositing by vapor deposition.
[0054] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the thickness of each polymer layer and/or layer of agent is generally at least about 0.01 pm and is generally less than about 150 pm (e.g., 0.01-149.9999 pm and all values and ranges therebetween). In one non-limiting embodiment, the thickness of a polymer layer and/or layer of agent is about 0.02-75pm, more particularly about 0.05-50 pm, and even more particularly about 1-30 pm. As can be appreciated, other thicknesses can be used.
[0055] In accordance with another and/or alternative non-limiting aspect of the present disclosure, a variety of polymers can be coated on the medical device and/or be used to form at least a portion of the medical device. When one or more layers of polymer are coated onto at least a portion of the medical device, the one or more coatings can be applied by a variety of techniques such as, but not limited to, vapor deposition and/or plasma deposition, spraying, dip-coating, roll coating, sonication, atomization, brushing and/or the like; however, other or additional coating techniques can be used. The one or more polymers that can be coated on the medical device and/or used to at least partially form the medical device can be polymers that are considered to be biodegradable, bioresorbable, or bioerodable; polymers that are considered to be biostable; and/or polymers that can be made to be biodegradable and/or bioresorbable with modification. Nonlimiting examples of polymers that are considered to be biodegradable, bioresorbable, or bioerodable include, but are not limited to, aliphatic polyesters; poly(glycolic acid) and/or copolymers thereof (e.g., poly(glycolide trimethylene carbonate); poly(caprolactone glycolide)); poly(lactic acid) and/or isomers thereof (e.g., poly-L(lactic acid) and/or poly-D Lactic acid) and/or copolymers thereof (e.g. DL-PLA), with and without additives (e.g. calcium phosphate glass), and/or other copolymers (e.g. poly(caprolactone lactide), poly(lactide glycolide), poly(lactic acid ethylene glycol)); polyethylene glycol); poly(ethylene glycol) diacrylate; poly(lactide); polyalkylene succinate; polybutylene diglycolate; polyhydroxybutyrate (PHB); polyhydroxyvalerate (PHV); polyhydroxybutyrate/polyhydroxyvalerate copolymer (PHB/PHV); poly(hydroxybutyrate-co-valerate); polyhydroxyalkaoates (PHA); polycaprolactone; poly(caprolactone-polyethylene glycol) copolymer; poly(valerolactone); polyanhydrides; poly(orthoesters) and/or blends with polyanhydrides; poly(anhydride-co-imide); polycarbonates (aliphatic); poly(hydroxyl-esters); polydioxanone; polyanhydrides; polyanhydride esters; polycyanoacrylates; poly(alkyl 2-cyanoacrylates); poly(amino acids); poly(phosphazenes); polypropylene fumarate); polypropylene fumarate-co-ethylene glycol); poly(fumarate anhydrides); fibrinogen; fibrin; gelatin; cellulose and/or cellulose derivatives and/or cellulosic polymers (e.g., cellulose acetate, cellulose acetate butyrate, cellulose butyrate, cellulose ethers, cellulose nitrate, cellulose propionate, cellophane); chitosan and/or chitosan derivatives (e.g., chitosan NOCC, chitosan NOOC-G); alginate; polysaccharides; starch; amylase; collagen; polycarboxylic acids; poly(ethyl ester-co-carboxylate carbonate) (and/or other tyrosine derived polycarbonates); poly(iminocarbonate); poly(BPA-iminocarbonate); poly(trimethylene carbonate); poly(iminocarbonate-amide) copolymers and/or other pseudo-poly(amino acids); poly(ethylene glycol); poly(ethylene oxide); poly(ethylene oxide)/poly(butylene terephthalate) copolymer; poly(epsilon-caprolactone-dimethyltrimethylene carbonate); poly(ester amide); poly(amino acids) and conventional synthetic polymers thereof; poly(alkylene oxalates); poly(alkylcarbonate); poly(adipic anhydride); nylon copolyamides; NO-carboxymethyl chitosan NOCC); carboxymethyl cellulose; copoly(ether-esters) (e.g., PEO/PLA dextrans); polyketals; biodegradable polyethers; biodegradable polyesters; polydihydropyrans; polydepsipeptides; polyarylates (L-tyrosine-derived) and/or free acid polyarylates; polyamides (e.g., nylon 6-6, polycaprolactam); polypropylene fumarate-co-ethylene glycol) (e.g., fumarate anhydrides); hyaluronates; poly-p-dioxanone; polypeptides and proteins; polyphosphoester; polyphosphoester urethane; polysaccharides; pseudo-poly(amino acids); starch; terpolymer; (copolymers of glycolide, lactide, or dimethyltrimethylene carbonate); rayon; rayon triacetate; latex; and/pr copolymers, blends, and/or composites of above. Non-limiting examples of polymers that considered to be biostable include, but are not limited to, parylene; parylene c; parylene f; parylene n; parylene derivatives; maleic anyhydride polymers; phosphoryl choline; poly n-butyl methacrylate (PBMA); polyethyl ene-co-vinyl acetate (PEVA); PBMA/PEVA blend or copolymer; polytetrafluoroethene (Teflon®) and derivatives; poly-paraphenylene terephthalamide (Kevlar®); poly(ether ketone) (PEEK); poly(styrene-b-isobutylene-b-styrene) (Translute™); tetramethyldisiloxane (side chain or copolymer); polyimides polysulfides; poly(ethylene terephthalate); poly(methyl methacrylate); poly(ethylene-co-m ethyl methacrylate); styrene- ethylene/butylene-styrene block copolymers; ABS; SAN; acrylic polymers and/or copolymers (e.g., n-butyl-acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, lauryl-acrylate, 2-hydroxy- propyl acrylate, polyhy dr oxy ethyl, methacrylate/methylmethacrylate copolymers); glycosaminoglycans; alkyd resins; elastin; polyether sulfones; epoxy resin; poly(oxymethylene); polyolefins; polymers of silicone; polymers of methane; polyisobutylene; ethylene-alphaolefin copolymers; polyethylene; polyacrylonitrile; fluorosilicones; polypropylene oxide); polyvinyl aromatics (e.g. polystyrene); poly(vinyl ethers) (e.g. polyvinyl methyl ether); poly(vinyl ketones); poly(vinylidene halides) (e.g. polyvinylidene fluoride, polyvinylidene chloride); poly(vinylpyrolidone); poly(vinylpyrolidone)/vinyl acetate copolymer; polyvinylpridine prolastin or silk-elastin polymers (SELP); silicone; silicone rubber; polyurethanes (polycarbonate polyurethanes, silicone urethane polymer) (e.g., chronoflex varieties, bionate varieties); vinyl halide polymers and/or copolymers (e.g. 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. Non-limiting examples of polymers that can be made to be biodegradable and/or bioresorbable with modification include, but are not limited to, hyaluronic acid (hyanluron); polycarbonates; polyorthocarbonates; copolymers of vinyl monomers; polyacetals; biodegradable polyurethanes; polyacrylamide; polyisocyanates; polyamide; and/or copolymers, blends, and/or composites of above. As can be appreciated, other and/or additional polymers and/or derivatives of one or more of the above listed polymers can be used. The one or more polymers can be coated on the medical device by a variety of mechanisms such as, but not limited to, spraying (e.g., atomizing spray techniques, etc.), dip coating, roll coating, sonication, brushing, plasma deposition, and/or depositing by vapor deposition. In one non-limiting embodiment, the medical device includes and/or is coated with parylene, PLGA, POE, PGA, PLLA, PAA, PEG, chitosan and/or derivatives of one or more of these polymers. In another and/or alternative non-limiting embodiment, the medical device includes and/or is coated with a non-porous polymer that includes, but is not limited to, polyamide, Parylene C, Parylene N and/or a parylene derivative. In still another and/or alternative non-limiting embodiment, the medical device includes and/or is coated with poly (ethylene oxide), poly(ethylene glycol), and polypropylene oxide), polymers of silicone, methane, tetrafluoroethylene (including TEFLON™ brand polymers), tetramethyldisiloxane, and the like.
[0056] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device, when including and/or is coated with one or more agents, can include and/or can be coated with one or more agents that are the same or different in different regions of the medical device and/or have differing amounts and/or concentrations in differing regions of the medical device. For instance, the medical device can be 1) coated with and/or include one or more biologicals on at least one portion of the medical device and at least another portion of the medical device is not coated with and/or includes agent, 2) coated with and/or include one or more biologicals on at least one portion of the medical device that is different from one or more biologicals on at least another portion of the medical device, and/or 3) coated with and/or include one or more biologicals at a concentration on at least one portion of the medical device that is different from the concentration of one or more biologicals on at least another portion of the medical device; etc.
[0057] In accordance with another and/or alternative non-limiting aspect of the present disclosure, one or more portions of the medical device can optionally 1) include the same or different agents, 2) include the same or different amount of one or more agents, 3) include the same or different polymer coatings, 4) include the same or different coating thicknesses of one or more polymer coatings, 5) have one or more portions of the medical device controllably release and/or uncontrollably release one or more agents, and/or 6) have one or more portions of the medical device controllably release one or more agents and one or more portions of the medical device uncontrollably release one or more agents. [0058] In accordance with another and/or alternative non-limiting aspect of the present disclosure, one or more surfaces of the medical device can optionally be treated to achieve the desired coating properties of the one or more agents and one or more polymers coated on the medical device. Such surface treatment techniques include, but are not limited to, cleaning, buffing, smoothing, nitriding, annealing, swaging, cold working, etching (chemical etching, plasma etching, etc.), etc. As can be appreciated, other or additional surface treatment processes can be used prior to the coating of one or more agents and/or polymers on the surface of the medical device. Once one or more surface regions of the medical device been treated, one or more coatings of polymer and/or agent can be applied to one or more regions of the medical device. The one or more layers of agent can be applied to the medical device by a variety of techniques (e.g., dipping, rolling, brushing, spraying, particle atomization, etc.). One non-limiting coating technique is by an ultrasonic mist coating process wherein ultrasonic waves are used to break up the droplet of agent and form a mist of very fine droplets. These fine droplets have an average droplet diameter of about 0.1-3 microns. The fine droplet mist facilitates in the formation of a uniform coating thickness and can increase the coverage area on the medical device.
[0059] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device can optionally include a marker material that facilitates enabling the medical device to be properly positioned in a body passageway (e.g., blood vessel, heart valve, etc.). The marker material is typically designed to be visible to electromagnetic waves (e.g., x- rays, microwaves, visible light, infrared waves, ultraviolet waves, etc.); sound waves (e.g., ultrasound waves, etc.); magnetic waves (e.g., MRI, etc.); and/or other types of electromagnetic waves (e.g., microwaves, visible light, infrared waves, ultraviolet waves, etc.). In one non-limiting embodiment, the marker material is visible to x-rays (i.e., radiopaque). The marker material can form all or a portion of the medical device and/or be coated on one or more portions (flaring portion and/or body portion, at ends of medical device, at or near transition of body portion and flaring section, etc.) of the medical device. The location of the marker material can be on one or multiple locations on the medical device. The size of the one or more regions including the marker material can be the same or different. The marker material can be spaced at defined distances from one another to form ruler-like markings on the medical device to facilitate in the positioning of the medical device in a body passageway. The marker material can be a rigid or flexible material. The marker material can be a biostable or biodegradable material. When the marker material is a rigid material, the marker material is typically formed of a metal material (e.g., metal band, metal plating, etc.); however, other or additional materials can be used. The metal, which at least partially forms the medical device, can function as a marker material; however, this is not required. When the marker material is a flexible material, the marker material typically is formed of one or more polymers that are marker materials in-of-themselves and/or include one or more metal powders and/or metal compounds. In one non-limiting embodiment, 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. In another and/or alternative non-limiting embodiment, the flexible marker material includes one or more metals and/or metal powders of aluminum, barium, bismuth, cobalt, copper, chromium, gold, iron, stainless steel, titanium, vanadium, nickel, zirconium, niobium, lead, molybdenum, platinum, yttrium, calcium, rare earth metals, rhenium, zinc, silver, depleted radioactive elements, tantalum and/or tungsten; and/or compounds thereof. The marker material can be coated with a polymer protective material; however, this is not required. When the marker material is coated with a polymer protective material, the polymer coating can be used to 1) at least partially insulate the marker material from body fluids, 2) facilitate in retaining the marker material on the medical device, 3) at least partially shield the marker material from damage during a medical procedure and/or 4) provide a desired surface profile on the medical device. As can be appreciated, the polymer coating can have other or additional uses. The polymer protective coating can be a biostable polymer or a biodegradable polymer (e.g., degrades and/or is absorbed). The coating thickness of the protective coating polymer material, when used, is typically less than about 300 microns (e.g., 0.001-299.999 microns and all values and ranges therebetween); however, other thickness can be used. In one non-limiting embodiment, the protective coating materials include parylene, PLGA, POE, PGA, PLLA, PAA, PEG, chitosan and/or derivatives of one or more of these polymers.
[0060] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device or one or more regions of the medical device can optionally be constructed by use of one or more microelectromechanical manufacturing (MEMS) techniques (e.g., micro-machining, laser micro-machining, laser micro-machining, micro-molding, 3D printing, etc.); however, other or additional manufacturing techniques can be used.
[0061] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device can optionally include one or more surface structures (e.g., pore, channel, pit, rib, slot, notch, bump, teeth, needle, well, hole, groove, etc.). These structures can be at least partially formed by MEMS (e.g., micro-machining, etc.) technology and/or other types of technology (e.g., 3D printing, etc.).
[0062] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device can optionally include one or more micro-structures (e.g., microneedle, micro-pore, micro-cylinder, micro-cone, micro-pyramid, micro-tube, micro- parallelopiped, micro-prism, micro-hemisphere, teeth, rib, ridge, ratchet, hinge, zipper, zip-tie-like structure, etc.) on the surface of the medical device. As defined herein, a “micro-structure” is a structure having at least one dimension (e.g., average width, average diameter, average height, average length, average depth, etc.) that is no more than about 2 mm, and typically no more than about 1 mm. As can be appreciated, when the medical device includes one or more surface structures, 1) all the surface structures can be micro-structures, 2) all the surface structures can be non-micro-structures, or 3) a portion of the surface structures can be micro-structures and a portion can be non-micro-structures. Non-limiting examples of structures that can be formed on the medical device are illustrated in United States Patent Publication Nos. 2004/0093076 and 2004/0093077, which are incorporated herein by reference. Typically, the micro-structures (when formed) extend from or into the outer surface no more than about 400 microns (0.01-400 microns and all values and ranges therebetween), and more typically less than about 300 microns, and more typically about 15-250 microns; however, other sizes can be used. The micro-structures can be clustered together or disbursed throughout the surface of the medical device. Similar shaped and/or sized micro-structures and/or surface structures can be used, or different shaped and/or sized micro-structures can be used. When one or more surface structures and/or micro-structures are designed to extend from the surface of the medical device, the one or more surface structures and/or micro-structures can be formed in the extended position and/or be designed to extend from the medical device during and/or after deployment of the medical device in a treatment area. The micro-structures and/or surface structures can be designed to contain and/or be fluidly connected to a passageway, cavity, etc.; however, this is not required. The one or more surface structures and/or micro-structures can be used to engage and/or penetrate surrounding tissue or organs once the medical device has been positioned on and/or in a patient; however, this is not required. The one or more surface structures and/or micro-structures can be used to facilitate in forming maintaining a shape of a medical device. In one non-limiting embodiment, the one or more surface structures and/or micro-structures can be at least partially formed of an agent and/or be formed of a polymer. One or more of the surface structures and/or micro-structures can include one or more internal passageways that can include one or more materials (e.g., agent, polymer, etc.); however, this is not required. The one or more surface structures and/or micro-structures can be formed by a variety of processes (e.g., machining, chemical modifications, chemical reactions, MEMS (e.g., micro-machining, etc.), etching, laser cutting, 3D printing, photo-etching, etc.). The one or more coatings and/or one or more surface structures and/or micro-structures of the medical device can be used for a variety of purposes such as, but not limited to, 1) increasing the bonding and/or adhesion of one or more agents, adhesives, marker materials and/or polymers to the medical device, 2) changing the appearance or surface characteristics of the medical device, and/or 3) controlling the release rate of one or more agents. The one or more micro-structures and/or surface structures can be biostable, biodegradable, etc. One or more regions of the medical device that are at least partially formed by MEMS techniques can be biostable, biodegradable, etc. The medical device or one or more regions of the medical device can be at least partially covered and/or filled with a protective material to at least partially protect one or more regions of the medical device, and/or one or more micro-structures and/or surface structures on the medical device from damage. One or more regions of the medical device, and/or one or more micro-structures and/or surface structures on the medical device can be damaged when the medical device is 1) packaged and/or stored, 2) unpackaged, 3) connected to and/or other secured and/or placed on another medical device, 4) inserted into a treatment area, and/or 5) handled by a user. As can be appreciated, the medical device can be damaged in other or additional ways. The protective material can be used to protect the medical device and/or one or more micro-structures and/or surface structures from such damage. The protective material can include one or more polymers previously identified above. The protective material can be 1) biostable and/or biodegradable and/or 2) porous and/or non-porous. In another and/or additional non-limiting design, 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. In still another and/or additional non-limiting design, 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.
[0063] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device can optionally be an expandable device that can be expanded by use of some other device (e.g., balloon, etc.).
[0064] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the medical device can optionally be fabricated from a material having no or substantially no shape-memory characteristics.
[0065] In accordance with another and/or alternative non-limiting aspect of the present disclosure, there is optionally provided a near net process for a frame and/or other metal component of the medical device. In one non-limiting embodiment of the disclosure, there is provided a method of powder pressing materials and optionally increasing the strength post-sintering by imparting additional cold work. In one non-limiting embodiment, the green part is pressed and then sintered. Thereafter, the sintered part is again pressed to increase its mechanical strength by imparting cold work into the pressed and sintered part. Generally, the temperature during the pressing process after the sintering process is 20-100°C (and all values and ranges therebetween), typically 20-80°C, and more typically 20-40°C. As defined 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. For a Mo47.5Re alloy, MoRe alloy, ReW alloy, ReCr alloy, other refractory metal alloys, 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.). There is also provided an optional process of increasing the mechanical strength of a pressed metal part by repressing the post-sintered part to add additional cold work into the material, thereby increasing its mechanical strength. There is also provided an optional process of powder pressing to a near net or final part using metal powder. In one nonlimiting embodiment, the metal powder used to form the near net or final part includes a minimum of 40 wt.% rhenium and at least 25 wt.% molybdenum, and remainder can optionally include one or more elements of tungsten, tantalum, chromium, niobium, zirconium, iridium, titanium, bismuth, and yttrium. In another non-limiting embodiment, the metal powder used to form the near net or final part includes 20-80 wt.% rhenium (and all values and ranges therebetween), 20- 80 wt.% molybdenum (and all values and ranges therebetween), and optionally one or more elements of tungsten, tantalum, chromium, niobium, zirconium, iridium, titanium, bismuth, and yttrium. In another non-limiting embodiment, the metal powder used to form the near net or final part includes tungsten (20-60 wt.% and all values and ranges therebetween), rhenium (20-80 wt.% and all values and ranges therebetween) and one or more other elements 0-5 wt.% (and all values and ranges therebetween). In another non-limiting embodiment, the metal powder used to form the near net or final part includes tungsten (20-80 wt.% and all values and ranges therebetween), rhenium (20-80 wt.% and all values and ranges therebetween), molybdenum (0.01-15 wt.% and all values and ranges therebetween), and one or more other elements 0-5 wt.% (and all values and ranges therebetween).
[0066] In another non-limiting embodiment, the metal powder used to form the near net or final part includes 35-65 wt.% rhenium (and all values and ranges therebetween), and two or more elements of tungsten, tantalum, molybdenum, chromium, niobium, zirconium, iridium, titanium, bismuth, and yttrium. In another non-limiting embodiment, the metal powder used to form the near net or final part includes 35-65 wt.% rhenium (and all values and ranges therebetween) molybdenum powder, and 11-41 wt.% (and all values and ranges therebetween) a combination of chromium powder and optionally a powder of one or more metals selected from the group consisting of bismuth, tungsten, tantalum, molybdenum, chromium, niobium, zirconium, iridium, niobium, tantalum, titanium, bismuth, and yttrium. In another non-limiting embodiment, the metal powder used to form the near net or final part includes 35-65 wt.% rhenium (and all values and ranges therebetween), and chromium, and 0.1-25 wt.% (and all values and ranges therebetween) and one or more elements of molybdenum, bismuth, niobium, tungsten, tantalum, titanium, vanadium, tungsten, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, iridium, and yttrium. In another non-limiting embodiment, the metal powder used to form the near net or final part includes 25-95 wt.% rhenium (and all values and ranges therebetween), and one or more of calcium, carbon, 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, zinc, zirconium, and/or alloys of one or more of such components. [0067] In accordance with another and/or alternative non-limiting aspect of the present disclosure, there is optionally provided a press of near net or finished part composite. The process of pressing metals into near net of finished parts is well established; however, pressing a composite structure formed of metal powder and polymer for purposes of making complex part geometries and foam like structures is new. Similarly, using a pressing process to impart particular biologic substances into the metal matrix is also new. In one non-limiting embodiment, there is provided a process of creating a metal part with pre-defined voids to create a trabecular or foam structure composed of mixing a metal and polymer powder, and then pressing the powder into a finished part or semi-finished green part, and then sintering the part under which conditions the polymer leaves the metal behind through a process of thermal degradation of the polymer. The resulting part has a porosity associated with the size of the polymer particles as well as the homogeneity of the mixture upon pressing prior to sintering. In another non-limiting embodiment, there is provided a process by which a residual of the polymer is left behind after thermal degradation (on the metal substrate) and the polymer residual has some desired biological affect (e.g., masking the metal from the body by encapsulation, promotion of cellular attachment and growth). The polymer and metal powders can be of varying sizes to create a multiplied of voids — some large, creating a pathway for cellular growth, and some small, creating a ruff surface to promote cellular attachment.
[0068] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the polymer can optionally be uniformly or non-uniformly dispersed with the metal powder. For example, if the final formed part is to have a uniform density and pore structure, the polymer material is uniformly dispersed with the metal powder prior to consolidating and pressing the polymer and metal powders together and then subsequently sintering together the metal powder to form the metal part or medical device. Alternatively, if 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. As such, the use of a polymer in combination with metal powder and subsequent pressing and sintering can be used to form novel and customized shapes for medical device or the near net form of the medical device. Generally, the polymer constitutes about 0.1-70 vol.% (and all values and ranges therebetween) of the consolidated and pressed material prior to the sintering step, typically the polymer constitutes about 1-60 vol.% of the consolidated and pressed material prior to the sintering step, more typically the polymer constitutes about 2-50 vol.% of the consolidated and pressed material prior to the sintering step, and even more typically the polymer constitutes about 2-45 vol.% of the consolidated and pressed material prior to the sintering step. As such, if the polymer constitutes about 5 vol.% of the consolidated and pressed material prior to the sintering step, if after the sintering step at least 95% (e.g., 95-100% and all values and ranges therebetween) of the polymer is degraded and removed from the part or medical device, then the part could include up to about 5 vol.% cavities and/or passageways in the medical device.
[0069] The type of polymer and the type of metal powder is non-limiting. The polymer and metal powders can be of varying sizes to create multiple voids/passageways/channels which can be used to create a pathway for cellular growth, create a ruff surface to promote cellular attachment, have a biological agent inserted into one or more of the voids/passageways/channels, have biological material inserted into one or more of the voids/passageways/channels, etc. In one nonlimiting embodiment, the average particle size of the polymer is greater than the average particle size of the metal powder prior to sintering.
[0070] In another non-limiting aspect of the present disclosure, after the sintering process, at least 95 vol.% (95%-100% and all values and ranges therebetween) of the polymer is thermally degraded and/or removed from the sintered material, typically at least 99 vol.% of the polymer is thermally degraded and/or removed from the sintered material, more typically at least 99.5 vol.% of the polymer is thermally degraded and/or removed from the sintered material, still even more typically at least 99.9 vol.% of the polymer is thermally degraded and/or removed from the sintered material, and even still more typically at least 99.95 vol.% of the polymer is thermally degraded and/or removed from the sintered material. The resulting part or medical device has a porosity associated with the size of the polymer particles as well as the homogeneity of the mixture upon pressing prior to sintering.
[0071] In another non-limiting aspect of the present disclosure, after the sintering process, some of the polymer may optionally remain in the sintered part or the medical device. The remaining polymer in the sintered part or the medical device can optionally have some desired biological affect (e.g., masking the metal from the body by encapsulation, promotion of cellular attachment and growth, etc.). Any remaining polymer can optionally include one or more biological agents that remain active after the sintering process. In one non-limiting embodiment, when polymer is designed to remain in the sintered part, after the sintering process, about 5-99.9 vol.% (and all values and ranges therebetween) of the polymer is thermally degraded and/or removed from the sintered material, typically about 10-95 vol.% of the polymer is thermally degraded and removed from the sintered material, and more typically about 10-80 vol.% of the polymer is thermally degraded and removed from the sintered material.
[0072] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy used to at least partially form the medical device is initially formed into a near net part, blank, a rod, a tube, etc., and then finished into final form by one or more finishing processes (e.g., centerless grinding, turning, electropolishing, drawing process, grinding, laser cutting, shaving, polishing, EDM cutting, micro-machining, laser micro-machining, micro-molding, machining, drilling (e.g., gun drilling, etc.), 3D printing, cold wording, swaging, cleaning, buffing, smoothing, nitriding, annealing, plug drawing, etching (chemical etching, plasma etching, etc.), chemical modifications, chemical reactions, photo-etching, chemical coatings, etc.).
[0073] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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 near net part, blank, rod, tube, etc. When the refractory metal alloy is formed into a blank, the shape and size of the blank is non-limiting. When the refractory metal alloy is formed into a rod or tube, the rod or tube generally has a length of about 48 inches or less (e.g., 0.1-48 inches and all values and ranges therebetween); however, longer lengths can be formed. In one non-limiting arrangement, the length of the rod or tube is about 8-20 inches. The average outer diameter of the rod or tube is generally less than about 2 inches (i.e., less than about 3.14 sq. in. cross-sectional area), more typically less than about 1 inch outer diameter, and even more typically no more than about 0.5 inch outer diameter; however, larger rod or tube diameter sizes can be formed. In one non-limiting configuration for a tube, the tube has an inner diameter of about 0.31 inch plus or minus about 0.002 inch and an outer diameter of about 0.5 inch plus or minus about 0.002 inch. The wall thickness of the tube is about 0.095 inch plus or minus about 0.002 inch. As can be appreciated, this is just one example of many different sized tubes that can be formed. In one non-limiting process, the near net frame of the medical device, blank, rod, tube, etc. In one non-limiting process, the near net medical device, blank, rod, tube, etc., can be formed from one or more ingots of metal or refractory metal alloy. In one non-limiting process, an arc melting process (e.g., vacuum arc melting process, etc.) can be used to form the near net medical device, blank, rod, tube, etc. In another non-limiting process, rhenium powder and tungsten powder and optionally molybdenum powder can be placed in a crucible (e.g., silica crucible, etc.) and heated under a controlled atmosphere (e.g., vacuum environment, carbon monoxide environment, hydrogen and argon environment, helium, argon, etc.) by an induction melting furnace to form the near net medical device, blank, rod, tube, etc. As can be appreciated, other metal particles can be used to form other refractory metal alloys (e.g., refractory metal alloys, MoRe alloys, MoReCr alloys, WRe alloys, ReCr alloys, MoReTa alloy, MoReTi alloy, ReCr alloy, etc.) by various processes such as melting, sintering, particle compression plus heat, etc. It can be appreciated that other or additional processes can be used to form the refractory metal alloy. When a tube of refractory metal alloy is to be formed, a close-fitting rod can be used during the extrusion process to form the tube; however, this is not required. In another and/or additional non-limiting process, 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 welding of the edges of the sheet or strip can be accomplished in several ways such as, but not limited to, a) holding the edges together and then e-beam welding the edges together in a vacuum, b) positioning a thin strip of refractory metal alloy above and/or below the edges of the rolled strip or sheet to be welded, then welding the one or more strips along the rolled strip or sheet edges, and then grinding off the outer strip, or c) laser welding the edges of the rolled sheet or strip in a vacuum, oxygen reducing atmosphere, or inert atmosphere. In still another and/or additional nonlimiting process, the near net frame of the medical device, blank, rod, tube, etc. of the refractory metal alloy is formed by consolidating metal powder. In this process, fine particles of metal (e.g., Re, W, Mo, Ti, Cu, Ni, Cr, etc.) along with any additives are mixed to form a homogenous blend of particles. Typically, the average particle size of the metal powders is less than about 200 mesh (e.g., less than 74 microns; 2-74 microns and all values and ranges therebetween). A larger average particle size can interfere with the proper mixing of the metal powders and/or adversely affect one or more physical properties of the near net frame of the medical device, blank, rod, tube, etc. formed from the metal powders. In one non-limiting embodiment, the average particle size of the metal powders is less than about 230 mesh (e.g., less than 63 microns). In another and/or alternative non-limiting embodiment, 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 blend of metal powder is then pressed together to form a solid solution of the refractory metal alloy into a near net medical device, blank, rod, tube, etc. Typically, the pressing process is by an isostatic process (i.e., uniform pressure applied from all sides on the metal powder); however other processes can be used. When the metal powders are pressed together isostatically, cold isostatic pressing (CIP) is typically used to consolidate the metal powders; however, this is not required. The pressing process can be performed in an inert atmosphere, an oxygen-reducing atmosphere (e.g., hydrogen, argon and hydrogen mixture, etc.) and/or under a vacuum; however, this is not required. The average density of the near net medical device, blank, rod, tube, etc., achieved by pressing together the metal powders is about 80-95% (and all values and ranges therebetween) of the final average density of the near net medical device, blank, rod, tube, etc., or about 70-99% (and all values and ranges therebetween) the minimum theoretical density of the refractory metal alloy. Pressing pressures of at least about 300 MPa (e.g., 300-800MPa and all values and ranges therebetween) are generally used. Generally, the pressing pressure is about 400-700MPa; however, other pressures can be used. After the metal powders are pressed together, the pressed metal powders are sintered at a temperature of at least 1600°C (e.g., 1600-3500°C and all values and ranges therebetween) to partially or fully fuse the metal powders together to form the near net medical device, blank, rod, tube, etc. The sintering of the consolidated metal powder can be performed in an oxygen-reducing atmosphere (e.g., helium, argon, hydrogen, argon, and hydrogen mixture, etc.) and/or under a vacuum; however, this is not required. At the high sintering temperatures, a high hydrogen atmosphere will reduce both the amount of carbon and oxygen in the formed near net medical device, blank, rod, tube, etc. The sintered metal powder generally has an as-sintered average density of about 90-99.9% (and all values and ranges therebetween) the minimum theoretical density of the refractory metal alloy. Typically, the sintered refractory metal alloy has a final average density of at least about 5 gm/cc (e.g., 5-20 gm/cc and all values and ranges therebetween), and typically at least about 8.3 gm/cc, and can be up to or greater than about 16 gm/cc; however, this is not required. The density of the formed near net medical device, blank, rod, tube, etc., will generally depend on the type of refractory metal alloy used.
[0074] In accordance with another and/or alternative non-limiting aspect of the present disclosure, when a solid rod of the refractory metal alloy is formed, the rod is then formed into a tube prior to reducing the outer cross-sectional area or diameter of the rod. The rod can be formed into a tube by a variety of processes such as, but not limited to, cutting or drilling (e.g., gun drilling, etc.) or by cutting (e.g., EDM, EDM sinker, wire EDM, etc.) or by 3D printing. The cavity or passageway formed in the rod typically is formed fully through the rod; however, this is not required.
[0075] In yet a further and/or alternative non-limiting aspect of the present disclosure, the near net medical device, blank, rod, tube, etc., can optionally be cleaned and/or polished after the near net medical device, blank, rod, tube, etc., has been form; however, this is not required. Typically, the near net medical device, blank, rod, tube, etc., is cleaned and/or polished prior to being further processed; however, this is not required. When a rod of the refractory metal alloy is formed into a tube, the formed tube is typically cleaned and/or polished prior to being further processed; however, this is not required. When the near net medical device, blank, rod, tube, etc. is resized and/or annealed, the near net medical device, blank, rod, tube, etc., is typically cleaned and/or polished prior to and/or after each or after a series of resizing and/or annealing processes; however, this is not required. The cleaning and/or polishing of the near net medical device, blank, rod, tube, etc., is used to remove impurities and/or contaminants from the surfaces of the near net medical device, blank, rod, tube, etc. Impurities and contaminants can become incorporated into the refractory metal alloy during the processing of the near net medical device, blank, rod, tube, etc. The inadvertent incorporation of impurities and contaminants in the near net medical device, blank, rod, tube, etc., can result in an undesired amount of carbon, nitrogen, and/or oxygen, and/or other impurities in the refractory metal alloy. The inclusion of impurities and contaminants in the refractory metal alloy can result in premature micro-cracking of the refractory metal alloy and/or an adverse effect on one or more physical properties of the refractory metal alloy (e.g., decrease in tensile elongation, increased ductility, increased brittleness, etc.). The cleaning of the refractory metal alloy can be accomplished by a variety of techniques such as, but not limited to, 1) using a solvent (e.g., acetone, methyl alcohol, etc.) and wiping the refractory metal alloy with a Kimwipe or other appropriate towel, 2) by at least partially dipping or immersing the refractory metal alloy in a solvent and then ultrasonically cleaning the refractory metal alloy, and/or 3) by at least partially dipping or immersing the refractory metal alloy in a pickling solution. As can be appreciated, the refractory metal alloy can be cleaned in other or additional ways. If the refractory metal alloy is to be polished, the refractory metal alloy is generally polished by use of a polishing solution that typically includes an acid solution; however, this is not required. In one non-limiting example, the polishing solution includes sulfuric acid; however, other or additional acids can be used. In one non-limiting polishing solution, the polishing solution can include by volume 60- 95% sulfuric acid and 5-40% de-ionized water (DI water). Typically, the polishing solution that includes an acid will increase in temperature during the making of the solution and/or during the polishing procedure. As such, the polishing solution is typically stirred and/or cooled during making of the solution and/or during the polishing procedure. The temperature of the polishing solution is typically about 20-100°C (and all values and ranges therebetween), and typically greater than about 25°C. One non-limiting polishing technique that can be used is an electropolishing technique. When an electropolishing technique is used, a voltage of about 2-30 V (and all values and ranges therebetween), and typically about 5-12 V is applied to the near net frame of the medical device, blank, rod, tube, etc. during the polishing process; however, it will be appreciated that other voltages can be used. The time used to polish the refractory metal alloy is dependent on both the size of the near net frame of the medical device, blank, rod, tube, etc. and the amount of material that needs to be removed from the near net frame of the medical device, blank, rod, tube, etc. The near net frame of the medical device, blank, rod, tube, etc. can be processed by use of a two-step polishing process wherein the refractory metal alloy piece is at least partially immersed in the polishing solution for a given period (e.g., 0.1-15 minutes, etc.), rinsed (e.g., DI water, etc.) for a short period of time (e.g., 0.02-1 minute, etc.), and then flipped over and at least partially immersed in the solution again for the same or similar duration as the first time; however, this is not required. The refractory metal alloy can be rinsed (e.g., DI water, etc.) for a period of time (e.g., 0.01-5 minutes, etc.) before rinsing with a solvent (e.g., acetone, methyl alcohol, etc.); however, this is not required. The refractory metal alloy can be dried (e.g., exposure to the atmosphere, maintained in an inert gas environment, etc.) on a clean surface. These polishing procedures can be repeated until the desired amount of polishing of the near net frame of the medical device, blank, rod, tube, etc. is achieved. The near net frame of the medical device, blank, rod, tube, etc. can be uniformly electropolished or selectively electropolished. When the near net frame of the medical device, blank, rod, tube, etc. is selectively electropolished, the selective electropolishing can be used to obtain different surface characteristics of the near net frame of the medical device, blank, rod, tube, etc. and/or selectively expose one or more regions of the near net frame of the medical device, blank, rod, tube, etc.; however, this is not required.
[0076] In still yet a further and/or alternative non-limiting aspect of the present disclosure, the near net medical device, blank, rod, tube, etc., can be resized to the desired dimension of the medical device. In one non-limiting embodiment, the cross-sectional area or diameter of the near net medical device, blank, rod, tube, etc., is reduced to a final near net medical device, blank, rod, tube, etc., dimension in a single step or by a series of steps. The reduction of the outer cross- sectional area or diameter of the near net medical device, blank, rod, tube, etc. may be obtained by centerless grinding, turning, electropolishing, drawing process, grinding, laser cutting, shaving, polishing, EDM cutting, etc. The outer cross-sectional area or diameter size of the near net medical device, blank, rod, tube, etc., can be reduced by the use of one or more drawing processes; however, this is not required. During the drawing process, care should be taken to not form microcracks in the near net medical device, blank, rod, tube, etc., during the reduction of the near net medical device, blank, rod, tube, etc., outer cross-sectional area or diameter.
[0077] In another and/or alternative non-limiting aspect of the present disclosure, the near net medical device, blank, rod, tube, etc. general if not reduced in cross-sectional area by more about 25% (e.g., 0.1-25% and all values and ranges therebetween) each time the near net medical device, blank, rod, tube, etc. is drawn down in size. When the near net medical device, blank, rod, tube, etc. optionally includes a nitride layer, the nitrided layer can optionally function as a lubricating surface during the drawing process to facilitate in the drawing of the near net medical device, blank, rod, tube, etc. Generally, the near net medical device, blank, rod, tube, etc. is reduced in cross-sectional area by about 0.1-20% each time the near net medical device, blank, rod, tube, etc. is drawn through a reducing mechanism. In another and/or alternative non-limiting process step, the near net medical device, blank, rod, tube, etc. is reduced in cross-sectional area by about 1- 15% each time the near net medical device, blank, rod, tube, etc. is drawn through a reducing mechanism. In still another and/or alternative non-limiting process step, the near net medical device, blank, rod, tube, etc. is reduced in cross-sectional area by about 2-15% each time the near net medical device, blank, rod, tube, etc. is drawn through reducing mechanism. In yet another one non-limiting process step, the near net medical device, blank, rod, tube, etc. is reduced in cross-sectional area by about 5-10% each time the near net medical device, blank, rod, tube, etc. is drawn through reducing mechanism. In another and/or alternative non-limiting embodiment of the disclosure, the near net medical device, blank, rod, tube, etc. of refractory metal alloy is drawn through a die to reduce the cross-sectional area of the near net medical device, blank, rod, tube, etc. Generally, before drawing the near net medical device, blank, rod, tube, etc. through a die, one end of the near net medical device, blank, rod, tube, etc. is narrowed down (nosed) so as to allow it to be fed through the die; however, this is not required. The tube drawing process is typically a cold drawing process or a plug drawing process through a die. When a cold drawing or mandrel drawing process is used, a lubricant (e.g., molybdenum paste, grease, etc.) is typically coated on the outer surface of the near net medical device, blank, rod, tube, etc. and the near net medical device, blank, rod, tube, etc. is then drawn though the die. Typically, little or no heat is used during the cold drawing process. After the near net medical device, blank, rod, tube, etc. has been drawn through the die, the outer surface of the near net medical device, blank, rod, tube, etc. is typically cleaned with a solvent to remove the lubricant so as to limit the amount of impurities that are incorporated in the refractory metal alloy; however, this is not required. This cold drawing process can be repeated several times until the desired outer cross-sectional area or diameter, inner cross-sectional area or diameter and/or wall thickness of the near net medical device, blank, rod, tube, etc. is achieved. A plug drawing process can also or alternatively be used to size the near net medical device, blank, rod, tube, etc. The plug drawing process typically does not use a lubricant during the drawing process. The plug drawing process typically includes a heating step to heat the near net medical device, blank, rod, tube, etc. prior and/or during the drawing of the near net medical device, blank, rod, tube, etc. through the die. The elimination of the use of a lubricant can reduce the incidence of impurities being introduced into the refractory metal alloy during the drawing process. During the plug drawing process, 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. One non-limiting protective environment includes argon, hydrogen or argon and hydrogen; however, other or additional inert gasses can be used. As indicated above, 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. Typically, the near net medical device, blank, rod, tube, etc. should be shielded from oxygen and nitrogen when the temperature of the near net medical device, blank, rod, tube, etc. is increased to above 500°C, and typically above 450°C, and more typically above 400°C; however, this is not required. When the near net medical device, blank, rod, tube, etc. is heated to temperatures above about 400-500°C, the near net medical device, blank, rod, tube, etc. tends to begin forming nitrides and/or in the presence of nitrogen and oxygen. In these higher temperature environments, a hydrogen environment, an argon and hydrogen environment, etc. is generally used. When the near net medical device, blank, rod, tube, etc. is drawn at temperatures below 400-500°C, the near net medical device, blank, rod, tube, etc. can be exposed to air with little or no adverse effects; however, an inert or slightly reducing environment is generally more desirable.
[0078] In another and/or alternative non-limiting aspect of the present disclosure, the near net medical device, blank, rod, tube, etc. is cooled after being annealed; however, this is not required. Generally, 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. Generally, the near net medical device, blank, rod, tube, etc. is cooled at 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.
[0079] In another and/or alternative non-limiting aspect of the present disclosure, 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. In other words, 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). A too-large reduction in the cross-sectional area of the refractory metal alloy blank, rod, tube, etc. during the drawing process prior to the near net medical device, blank, rod, tube, etc. being annealed can result in micro-cracking of the near net medical device, blank, rod, tube, etc. In one non-limiting processing step, the refractory metal alloy blank, rod, tube, etc. is annealed prior to about a 50% cross-sectional area size reduction of the refractory metal alloy blank, rod, tube, etc. In another and/or alternative non-limiting processing step, the refractory metal alloy blank, rod, tube, etc. is annealed prior to about a 45% cross-sectional area size reduction of the refractory metal alloy blank, rod, tube, etc. In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy blank, rod, tube, etc. is annealed prior to about a 1-45% cross-sectional area size reduction of the refractory metal alloy blank, rod, tube, etc. In yet another and/or alternative non-limiting processing step, the refractory metal alloy blank, rod, tube, etc. is annealed prior to about a 5-30% cross-sectional area size reduction of the refractory metal alloy blank, rod, tube, etc. In still yet another and/or alternative non-limiting processing step, 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.
[0080] In accordance with another and/or alternative non-limiting aspect of the present disclosure, when the near net medical device, blank, rod, tube, etc. is annealed, the near net medical device, blank, rod, tube, etc. is typically heated to a temperature of about 500-1700°C (and all values and ranges therebetween) for a period of about 1-200 minutes (and all values and ranges therebetween); however, other temperatures and/or times can be used. In one non-limiting processing step, the near net medical device, blank, rod, tube, etc. is annealed at a temperature of about 1000-1600°C for about 2-100 minutes. In another non-limiting processing step, the near net medical device, blank, rod, tube, etc. is annealed at a temperature of about 1100-1500°C for about 5-30 minutes. The annealing process typically occurs in an inert environment or an oxygenreducing environment so as to limit the amount of impurities that may embed themselves in the refractory metal alloy during the annealing process. One non-limiting oxygen-reducing environment that can be used during the annealing process is a hydrogen environment; however, it can be appreciated that a vacuum environment can be used or one or more other or additional gasses can be used to create the oxygen-reducing environment. At the annealing temperatures, a hydrogen-containing atmosphere can further reduce the amount of oxygen in the near net medical device, blank, rod, tube, etc. The chamber in which the near net medical device, blank, rod, tube, etc. is annealed should be substantially free (e.g., 0-50 ppm and all value and ranges therebetween) of impurities (e.g., carbon, oxygen, nitrogen, etc.) so as to limit the amount of impurities that can embed themselves in the near net medical device, blank, rod, tube, etc. during the annealing process. 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. A non-limiting material that can be used to form the annealing chamber includes, but is not limited to, molybdenum, rhenium, tungsten, molybdenum TZM alloy, cobalt, chromium, ceramic, etc. When the near net medical device, blank, rod, tube, etc. is restrained in the annealing chamber, the restraining apparatuses that are used to contact the near net medical device, blank, rod, tube, etc. are typically formed of materials that will not introduce impurities to the refractory metal alloy during the processing of the near net medical device, blank, rod, tube, etc. Non-limiting examples of materials that can be used to at least partially form the restraining apparatuses include, but are not limited to, molybdenum, titanium, yttrium, zirconium, rhenium, cobalt, chromium, tantalum, and/or tungsten. In one non-limiting embodiment, when the refractory metal alloy is exposed to temperatures above 150°C for any process step including annealing, the materials that contact the refractory metal alloy during the processing of the refractory metal alloy are typically made from chromium, cobalt, molybdenum, rhenium, tantalum and/or tungsten. When the refractory metal alloy is processed at lower temperatures (i.e., 150°C or less), materials made from Teflon™ parts can also or alternatively be used. [0081] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the parameters for annealing can be changed as the near net medical device, blank, rod, tube, etc. as the cross-sectional area or diameter; and/or wall thickness of the near net medical device, blank, rod, tube, etc. are changed. It has been found that good grain size characteristics of the near net medical device, blank, rod, tube, etc. can be achieved when the annealing parameters are varied as the parameters of the near net medical device, blank, rod, tube, etc. change. For example, as the wall thickness is reduced, the annealing temperature is correspondingly reduced; however, the times for annealing can be increased. As can be appreciated, the annealing temperatures of the near net medical device, blank, rod, tube, etc. can be decreased as the wall thickness decreases, but the annealing times can remain the same or also be reduced as the wall thickness reduces. After each annealing process, the grain size of the metal in the near net medical device, blank, rod, tube, etc. should be no greater than 4 ASTM. Generally, the grain size range is about 4-20 ASTM (and all values and ranges therebetween). It is believed that as the annealing temperature is reduced as the wall thickness reduces, small grain sizes can be obtained. The grain size of the metal in the near net medical device, blank, rod, tube, etc. should be as uniform as possible. In addition, the sigma phase of the metal in the near net medical device, blank, rod, tube, etc. should be as reduced as much as possible. The sigma phase is a spherical, elliptical or tetragonal crystalline shape in the refractory metal alloy. After the final drawing of the near net medical device, blank, rod, tube, etc., a final annealing of the near net medical device, blank, rod, tube, etc. can be done for final strengthening of the near net medical device, blank, rod, tube, etc.; however, this is not required. This final annealing process, when used, generally occurs at a temperature of about 500-1600°C (and all values and ranges therebetween) for at least about 1 minute; however, other temperatures and/or time periods can be used.
[0082] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the near net medical device, blank, rod, tube, etc. can be cleaned prior to and/or after being annealed. The cleaning process is designed to remove impurities, lubricants (e.g., nitride compounds, molybdenum paste, grease, oxides, carbides, etc.) and/or other materials from the surfaces of the near net medical device, blank, rod, tube, etc. Impurities that are on one or more surfaces of the near net medical device, blank, rod, tube, etc. can become permanently embedded into the near net medical device, blank, rod, tube, etc. during the annealing processes. These imbedded impurities can adversely affect the physical properties of the refractory metal alloy as the near net medical device, blank, rod, tube, etc. is formed into a medical device, and/or can adversely affect the operation and/or life of the medical device. In one non-limiting embodiment of the disclosure, the cleaning process includes a delubrication or degreasing process which is typically followed by pickling process; however, this is not required. The delubrication or degreasing process followed by pickling process is typically used when a lubricant has been used on the near net medical device, blank, rod, tube, etc. during a drawing process. 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 delubrication or degreasing process can be accomplished by a variety of techniques such as, but not limited to, 1) using a solvent (e.g., acetone, methyl alcohol, etc.) and wiping the refractory metal alloy with a Kimwipe or other appropriate towel, 2) by at least partially dipping or immersing the refractory metal alloy in a solvent and then ultrasonically cleaning the refractory metal alloy, 3) sand blasting the refractory metal alloy, and/or 4) chemical etching the refractory metal alloy. As can be appreciated, the refractory metal alloy can be delubricated or degreased in other or additional ways. After the near net medical device, blank, rod, tube, etc. has been delubricated or degreased, the near net medical device, blank, rod, tube, etc. can be further cleaned by use of a pickling process; however, this is not required. The pickling process (when used) includes the use of one or more acids to remove impurities from the surface of the near net medical device, blank, rod, tube, etc. Non-limiting examples of acids that can be used as the pickling solution include, but are not limited to, nitric acid, acetic acid, sulfuric acid, hydrochloric acid, and/or hydrofluoric acid. These acids are typically analytical reagent (ACS) grade acids. The acid solution and acid concentration are selected to remove oxides and other impurities on the near net medical device, blank, rod, tube, etc. surface without damaging or over-etching the surface of the near net medical device, blank, rod, tube, etc. A near net medical device, blank, rod, tube, etc. surface that includes a large amount of oxides and/or nitrides typically requires a stronger pickling solution and/or long pickling process times. Non-limiting examples of pickling solutions include 1) 25-60% DI water (and all values and ranges therebetween), 30-60% nitric acid (and all values and ranges therebetween), and 2-20% sulfuric acid (and all values and ranges therebetween); 2) 40-75% acetic acid (and all values and ranges therebetween), 10-35% nitric acid (and all values and ranges therebetween), and 1-12% hydrofluoric acid (and all values and ranges therebetween); and 3) 50-100% hydrochloric acid (and all values and ranges therebetween). As can be appreciated, one or more different pickling solutions can be used during the pickling process. During the pickling process, the near net medical device, blank, rod, tube, etc. is fully or partially immersed in the pickling solution for a sufficient amount of time to remove the impurities from the surface of the near net medical device, blank, rod, tube, etc. Typically, the time period for pickling is about 2-120 seconds (and all values and ranges therebetween); however, other time periods can be used. After the near net medical device, blank, rod, tube, etc. has been pickled, the near net medical device, blank, rod, tube, etc. is typically rinsed with a water (e.g., DI water, etc.) and/or a solvent (e.g., acetone, methyl alcohol, etc.) to remove any pickling solution from the near net medical device, blank, rod, tube, etc. and then the near net medical device, blank, rod, tube, etc. is allowed to dry. The near net medical device, blank, rod, tube, etc. may be keep in a protective environment during the rinse and/or drying process to inhibit or prevent oxides from reforming on the surface of the near net medical device, blank, rod, tube, etc. prior to the near net medical device, blank, rod, tube, etc. being drawn and/or annealed; however, this is not required. [0083] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the near net medical device, blank, rod, tube, etc., after a) being formed to the desired green shape, b) after being formed to have the desired outer cross-sectional area or diameter, and/or c) after being formed to have the desired inner cross-sectional area or diameter and/or wall thickness, can then be cut and/or etched to at least partially form the desired configuration of the medical device (e.g., stent, TAV valve, etc.). The near net medical device, blank, rod, tube, etc. can be cut or otherwise formed by one or more processes (e.g., centerless grinding, turning, electropolishing, drawing process, grinding, laser cutting, shaving, polishing, EDM cutting, etching, micro-machining, laser micro-machining, micro-molding, machining, etc.). As can be appreciated, a portion or all of the medical device can be formed by 3D printing. In one non limiting embodiment of the disclosure, the refractory metal alloy used to partially or fully form the near net medical device, blank, rod, tube, etc. is at least partially cut by a laser. The laser is typically desired to have a beam strength which can heat the refractory metal alloy near net medical device, blank, rod, tube, etc. to a temperature up to at least about 2200-2300°C. In one non-limiting aspect of this embodiment, a pulsed Nd:YAG neodymium-doped yttrium aluminum garnet (Nd: Y3AI5O12 or CO2 laser is used to at least partially cut a pattern of a medical device out of the refractory metal alloy blank, rod, tube, etc. In accordance with another and/or alternative non- limiting aspect of this embodiment, the cutting of the refractory metal alloy that is used to partially or fully form the near net medical device, blank, rod, tube, etc. by the laser can occur in a vacuum environment, an oxygen -reducing environment, or an inert environment; however, this is not required. It has been found that laser cutting of the near net medical device, blank, rod, tube, etc. in a non-protected environment can result in impurities being introduced into the cut near net medical device, blank, rod, tube, etc., which introduced impurities can induce micro-cracking of the near net medical device, blank, rod, tube, etc. during the cutting of the near net medical device, blank, rod, tube, etc. One non-limiting oxygen-reducing environment includes a combination of argon and hydrogen; however, a vacuum environment, an inert environment, or other or additional gasses can be used to form the oxygen reducing environment. In still another and/or alternative non-limiting aspect of this embodiment, the refractory metal alloy that used to partially or fully form the near net medical device, blank, rod, tube, etc. is stabilized so as to limit or prevent vibration of the near net medical device, blank, rod, tube, etc. during the cutting process. The apparatus used to stabilize the near net medical device, blank, rod, tube, etc. can be formed of molybdenum, rhenium, tungsten, tantalum, cobalt, chromium, molybdenum TZM alloy, ceramic, etc. so as to not introduce contaminants to the near net medical device, blank, rod, tube, etc. during the cutting process; however, this is not required. Vibrations in the near net medical device, blank, rod, tube, etc. during the cutting of the near net medical device, blank, rod, tube, etc. can result in the formation of micro-cracks in the near net medical device, blank, rod, tube, etc. as the near net medical device, blank, rod, tube, etc. is cut. The average amplitude of vibration during the cutting of the near net medical device, blank, rod, tube, etc. is generally no more than about 150% (0- 150% and all values and ranges therebetween) of the wall thickness of the near net medical device, blank, rod, tube, etc.; however, this is not required. In one non-limiting aspect of this embodiment, the average amplitude of vibration is no more than about 100% of the wall thickness of the near net medical device, blank, rod, tube, etc. In another non-limiting aspect of this embodiment, the average amplitude of vibration is no more than about 75% of the wall thickness of the near net medical device, blank, rod, tube, etc. In still another non-limiting aspect of this embodiment, the average amplitude of vibration is no more than about 50% of the wall thickness of the near net medical device, blank, rod, tube, etc. In yet another non-limiting aspect of this embodiment, the average amplitude of vibration is no more than about 25% of the wall thickness of the near net medical device, blank, rod, tube, etc. In still yet another non-limiting aspect of this embodiment, the average amplitude of vibration is no more than about 15% of the wall thickness of the near net medical device, blank, rod, tube, etc.
[0084] In accordance with another and/or alternative non-limiting aspect of the present disclosure, 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. In one non-limiting embodiment of the disclosure, the medical device is electropolished. In one non-limiting aspect of this embodiment, the medical device is cleaned prior to being exposed to the polishing solution; however, this is not required. The cleaning process (when used) can be accomplished by a variety of techniques such as, but not limited to, 1) using a solvent and wiping the medical device with a Kimwipe or other appropriate towel, and/or 2) by at least partially dipping or immersing the medical device in a solvent and then ultrasonically cleaning the medical device. As can be appreciated, the medical device can be cleaned in other or additional ways. In accordance with another and/or alternative non-limiting aspect of this embodiment, the polishing solution can include one or more acids. In yet another and/or alternative non-limiting aspect of this embodiment, the medical device is rinsed with water and/or a solvent and allowed to dry to remove polishing solution on the medical device. In another and/or alternative non-limiting embodiment of the disclosure, the formed medical device is optionally nitrided. After the medical device is nitrided, the medical device is typically cleaned; however, this is not required. During the nitride process, the surface of the medical device is modified by the present of nitrogen. The nitriding process for the medical device can be used to increase surface hardness and/or wear resistance of the medical device and/or limit or present discoloration of the surface of the frame of the medical device. For example, the nitriding process can be used to increase the wear resistance of articulation surfaces or surface wear on the medical device to extend the life of the medical device, and/or to increase the wear life of mating surfaces on the medical device, and/or to reduce particulate generation from use of the medical device.
[0085] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy can be coated with an enhancement coating 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.). 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. In one non-limiting embodiment, 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. Such vacuum coating process includes a physical vapor deposition (PVD) process (e.g., sputter deposition, cathodic arc deposition or electron beam heating, etc.), chemical vapor deposition (CVD) process, atomic layer deposition (ALD) process, or a plasma-enhanced chemical vapor deposition (PE-CVD) process. In one non-limiting embodiment, the coating process is one or more of a PVD, CVD, ALD and PE-CVD, and wherein the coating process occurs at a temperature of 200-400°C (and all values and ranges therebetween) for at least 10 minutes (e.g., 10-400 minutes and all values and ranges therebetween). In another non-limiting embodiment, the coating process is one or more of a PVD, CVD, ALD and PE-CVD, and wherein the coating process occurs at a temperature of 220-300°C for 60-120 minutes. The materials of the one or more enhancement coatings can be combine with one or more metals in the refractory metal alloy, and/or combined with nitrogen, oxygen, carbon, or other elements that are in the refractory metal alloy and/or present in the atmosphere about the refractory metal alloy to a form an enhancement coating on the outer surface of the refractory metal alloy that can have enhanced properties (e.g., enhancement coating is harder than case-hardened steel, enhancement coating is more scratch-resistant than hardened chrome, enhancement coating having high corrosion resistance, etc.). In another non-limiting embodiment, 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.). In another nonlimiting embodiment, 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. In another non-limiting embodiment, the hardness of the enhancement coating is at 5 GPa (ASTM C1327-15 or ASTM C1624-05), typically 5-50 GPa (and all values and ranges therebetween), more typically 10-25 GPa, and still more typically 14- 24 GPa. In another non-limiting embodiment, the coefficient of friction (COF) of the enhancement coating is 0.04-0.2 (and all values and ranges therebetween), and typically 0.6-0.15. In another non-limiting embodiment, the wear rate of the enhancement coating is 0.5 x 10'7 mm3/N-m to 3 x 10'7 mm3/N-m (an all values and ranges therebetween), and typically 1.2 x 10'7 mm3/N-m to 2 x 10'7 mm3/N-m. In another non-limiting embodiment, silicon-based precursors (e.g., trimethysilane, tetramethylsilane, hexachlorodisilane, silane, dichlorosilane, trichlorosilane, silicon tetrachloride, tris(dimethylamino) silane, bis(tert-butylamino)silane, trisilylamine, allyltrimethoxysilane, (3-aminopropyl)triethoxysilane, butyltrichlorosilane, n-sec- butyl(trimethylsilyl)amine, chloropentamethyldisilane, 1,2-dichlorotetramethyldisilane, [3- (diethylamino)propyl]trimethoxysilane, l,3-diethyl-l,l,3,3-tetramethyldisilazane, dimethoxydimethyl silane, dodecamethyl cyclohexasilane, hexamethyldi silane, isobutyl(trimethoxy)silane, methyltrichlorosilane, 2, 4, 6, 8, 10-pentam ethyl cyclopentasiloxane, pentamethyldisilane, n-propyltriethoxysilane, silicon tetrabromide, silicon tetrabromide, etc.) can be used to facilitate in the application of the enhancement coating to one or more portions or all of the outer surface of the refractory metal alloy.
[0086] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy wherein the enhancement coating composition includes a chromium nitride (CrN) coating. A portion or all of the outer surface of the refractory metal alloy can include the chromium nitride (CrN) coating. The enhancement coating can be used to improve hardness, improve toughness, reduced friction, resistant impact wear, improve resistance to corrosion and oxidation, and/or form a reduced stick surface when in contact with many different materials. In accordance with one non-limiting embodiment, the refractory metal alloy is coated with an enhancement coating that generally includes 40-85 wt.% Cr (and all values and ranges therebetween), 15-60 wt.% N (and all values and ranges therebetween), 0-10 wt.% Re (and all values and ranges therebetween), 0-10 wt.% Si (and all values and ranges therebetween), 0-2 wt.% O (and all values and ranges therebetween), and 0-2 wt.% C (and all values and ranges therebetween). In one non-limiting coating process, all or a portion of the outer surface of the refractory metal alloy is initially coated with Cr metal. 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. Thereafter, 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. In another non-limiting embodiment, 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. [0087] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy wherein the enhancement coating composition generally includes a diamond-Like Carbon (DLC) coating. A portion or all of the outer surface of the refractory metal alloy can include the diamond-Like Carbon (DLC) coating. The enhancement coating can be used to improve hardness, improve toughness, reduced friction, resistant impact wear, improve resistance to corrosion and oxidation, improve biocompatibility, and/or form a reduced stick surface when in contact with many different materials. In one nonlimiting embodiment, all or a portion of the outer surface of the refractory metal alloy is coated with the enhancement coating composition that generally includes 60-99.99 wt.% C (and all values and ranges therebetween), 0-2 wt.% N (and all values and ranges therebetween), 0-10 wt.% Re (and all values and ranges therebetween), 0-20 wt.% Si (and all values and ranges therebetween), and 0-2 wt.% O (and all values and ranges therebetween). The carbon coating can be applied by PVD, CVD, ALD and PE-CVD in an inert environment. The carbon layer can be applied by use of methane and/or acetylene gas; however, other or additional carbon sources can be used. The coating thickness of the carbon is 0.5-15 microns. In another non-limiting embodiment, all or a portion of the outer surface of the refractory metal alloy is coated with the enhancement coating composition that generally includes 90-99.99 wt.% C, 0-1 wt.% N, 0-8 wt.% Re, 0-1 wt.% Si, and 0-1 wt.% O.
[0088] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy wherein the enhancement coating composition generally includes a titanium nitride (TiN) coating. A portion or all of the outer surface of the refractory metal alloy can include the titanium nitride (TiN) 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. In one non-limiting embodiment, all or a portion of the outer surface of the refractory metal alloy is initially coated with Ti metal. The Ti metal coating can be applied by PVD, CVD, ALD and PE-CVD in an inert environment. The coating thickness of Ti metal is 0.5- 15 microns. Thereafter, the Ti metal coating is exposed to nitrogen gas and/or a nitrogen containing gas compound to cause the nitrogen to react with the Ti metal coating to form a layer of TiN on the outer surface of the Ti metal coating and/or the outer surface of the refractory metal alloy. In another non-limiting embodiment, the enhancement coating composition generally includes 20-85 wt.% Ti (and all values and ranges therebetween), 5-30 wt.% N (and all values and ranges therebetween), 0-10 wt.% Re (and all values and ranges therebetween), 0-20 wt.% Si (and all values and ranges therebetween), 0-2 wt.% O (and all values and ranges therebetween), and 0- 2 wt.% C (and all values and ranges therebetween). In another non-limiting embodiment, the enhancement coating composition generally includes 70-80 wt.% Ti, 20-25 wt.% N, 0-8 wt.% Re, 0-1 wt.% Si, 0-1 wt.% O, and 0-1 wt.% C.
[0089] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy wherein the enhancement coating composition generally includes a zirconium nitride (ZrN) coating. A portion or all of the outer surface of the refractory metal alloy can include the zirconium nitride (ZrN) 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. In one non-limiting embodiment 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. Thereafter, the Zr metal coating is exposed to nitrogen gas and/or a nitrogen containing gas compound to cause the nitrogen to react with the Zn metal coating to form a layer of ZrN on the outer surface of the Zr metal coating and/or the outer surface of the refractory metal alloy. The ZrN coating has been found to produce a gold colored enhancement coating color. In another non-limiting embodiment, the enhancement coating composition generally includes 35-90 wt.% Zr (and all values and ranges therebetween), 5-25 wt.% N (and all values and ranges therebetween), 0-10 wt.% Re (and all values and ranges therebetween), 0-20 wt.% Si (and all values and ranges therebetween), 0-2 wt.% O (and all values and ranges therebetween), and 0-2 wt.% C (and all values and ranges therebetween). In another non-limiting embodiment, 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.
[0090] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy wherein the enhancement coating composition generally includes a zirconium oxide (ZrCh) coating. A portion or all of the outer surface of the refractory metal alloy can include the zirconium oxide (ZrCh) 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. In one non-limiting embodiment 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. Thereafter, the Zr metal coating is exposed to oxygen gas and/or oxygen containing gas compound to cause the oxygen to react with the Zn metal coating to form a layer of zirconium oxide (ZrCh) on the outer surface of the Zr metal coating and/or the outer surface of the refractory metal alloy. The zirconium oxide (ZrCh) coating has been found to produce a blue colored enhancement coating color. In another non-limiting embodiment, the enhancement coating composition generally includes 35-90 wt.% Zr (and all values and ranges therebetween), 10-35 wt.% O (and all values and ranges therebetween), 0-2 wt.% N (and all values and ranges therebetween), 0-10 wt.% Re (and all values and ranges therebetween), 0-20 wt.% Si (and all values and ranges therebetween), and 0-2 wt.% C (and all values and ranges therebetween). In another non-limiting embodiment, the enhancement coating composition generally includes 70-80 wt.% Zr, 20-30 wt.%, 0-1 wt.% N, 0-8 wt.% Re, 0-1 wt.% Si, and 0-1 wt.% C.
[0091] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy wherein the enhancement coating composition generally includes both a zirconium oxide (ZrCb) coating and a zirconium nitride coating (ZrN). A portion or all of the outer surface of the refractory metal alloy can include the zirconium oxide (ZrO2) coating and the zirconium nitride coating (ZrN). 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. In one non-limiting embodiment 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. Thereafter, 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.
[0092] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy wherein the enhancement coating composition generally includes a zirconium oxycarbide (ZrOC) coating. 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. In one non-limiting embodiment 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. Thereafter, the Zr metal coating is exposed to a) both to oxygen gas and/or an oxygen containing gas compound and to carbon and/or a carbon containing gas compound (e.g., methane and/or acetylene gas), b) carbon and/or a carbon containing gas compound and then to oxygen gas and/or an oxygen containing gas compound, or c) oxygen gas and/or oxygen containing gas compound and then to carbon and/or carbon containing gas compound. In another non-limiting embodiment, the enhancement coating composition generally includes 40-95 wt.% Zr (and all values and ranges therebetween), 5-25 wt.% O (and all values and ranges therebetween), and 10- 40 wt.% C (and all values and ranges therebetween), 0-2 wt.% N (and all values and ranges therebetween), 0-10 wt.% Re (and all values and ranges therebetween), and 0-20 wt.% Si (and all values and ranges therebetween). In another non-limiting embodiment, the enhancement coating composition generally includes 40-65 wt.% Zr, 5-25 wt.% O, and 25-40 wt.% C, 0-1 wt.% N, 0-8 wt.% Re, and 0-1 wt.% Si.
[0093] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the refractory metal alloy is coated with an enhancement coating to improve one or more properties of the refractory metal alloy wherein the enhancement coating composition generally includes a zirconium-nitrogen-carbon (ZrNC) coating. A portion or all of the outer surface of the refractory metal alloy can include the zirconium-nitrogen-carbon (ZrNC) 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. In one non-limiting embodiment 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. Thereafter, the Zr metal coating is exposed to nitrogen gas and/or a nitrogen containing gas compound and then to carbon and/or a carbon containing gas compound (e.g., methane and/or acetylene gas). The color of the ZrNC will vary depending on the amount of C and N in the coating. In one non-limiting embodiment, the enhancement coating composition generally includes 40-95 wt.% Zr (and all values and ranges therebetween), 5-40 wt.% N (and all values and ranges therebetween), and 5-40 wt.% C (and all values and ranges therebetween), 0-2 wt.% O (and all values and ranges therebetween), 0-10 wt.% Re (and all values and ranges therebetween), and 0-20 wt.% Si (and all values and ranges therebetween). In another non-limiting embodiment, 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.
[0094] In accordance with another and/or alternative non-limiting aspect of the present disclosure, the use of the refractory metal alloy to form all or a portion of the medical device can result in several advantages over medical devices formed from other materials. These advantages include, but are not limited to:
[0095] • The refractory metal alloy has increased strength and/or hardness as compared with stainless steel, chromium-cobalt alloys, or titanium alloys, thus a less quantity of refractory metal alloy can be used in the medical device to achieve similar strengths as compared to medical devices formed of different metals. As such, the resulting medical device can be made smaller and less bulky by use of the refractory metal alloy without sacrificing the strength and durability of the medical device. The medical device can also have a smaller profile, thus can be inserted into smaller areas, openings, and/or passageways. The thinner struts of refractory metal alloy to form the frame or other portions of the medical device can be used to form a frame or other portion of the medical device having a strength that would require thicker struts or other structures of the medical device when formed by stainless steel, chromium-cobalt alloys, or titanium alloys.
[0096] • The increased strength of the refractory metal alloy also results in the increased radial strength of the medical device. For instance, the thickness of the walls of the medical device can be made thinner and achieve a similar or improved radial strength as compared with thicker walled medical devices formed of stainless steel, cobalt and chromium alloy, or titanium alloy.
[0097] • The refractory metal alloy has improved stress-strain properties, bendability properties, elongation properties, and/or flexibility properties of the medical device compared with stainless steel and chromium-cobalt alloys, thus resulting in an increase life for the medical device. For example, the medical device can be used in regions that subject the medical device to repeated bending. Due to the improved physical properties of the medical device from the refractory metal alloy, the medical device has improved resistance to fracturing in such frequent bending environments. These improved physical properties at least in part result from the composition of the refractory metal alloy, the grain size of the refractory metal alloy, the carbon, oxygen, and nitrogen content of the refractory metal alloy, and/or the carbon/oxygen ratio of the refractory metal alloy.
[0098] • 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. As such, 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.
[0099] • The use of the refractory metal alloy in the medical device results in the medical device better conforming to an irregularly shaped body passageway when expanded in the body passageway compared to a medical device formed by stainless steel, chromium-cobalt alloys, or titanium alloys.
[00100] • 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. For example, the refractory metal alloy is at least about 10-20% more radiopaque than stainless steel or cobalt-chromium alloy.
[00101] • The refractory metal alloy has improved fatigue ductility when subjected to coldworking compared to the cold-working of stainless steel, chromium-cobalt alloys, or titanium alloys.
[00102] • The refractory metal alloy has improved durability compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
[00103] • The refractory metal alloy has improved hydrophilicity compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
[00104] • The refractory metal alloy has reduced ion release in the body passageway compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
[00105] • The refractory metal alloy is less of an irritant to the body than stainless steel, cobalt-chromium alloy, or titanium alloys, thus can result in reduced inflammation, faster healing, increased success rates of the medical device. When the medical device is expanded in a body passageway, some minor damage to the interior of the passageway can occur. When the body begins to heal such minor damage, the body has less adverse reaction to the presence of the refractory metal alloy compared to other metals such as stainless steel, cobalt-chromium alloy, or titanium alloy.
[00106] • The refractory metal alloy has a magnetic susceptibility that is lower that CoCr alloy, TiAIV alloys, and/or stainless steel, thus resulting in less incidence of potential defects to the medical device or complications to the patent after implantation of the medical device when the patient is subjected to an MRI or other medical device that generates a strong magnetic field. [00107] One non-limiting object of the present disclosure is the provision of the refractory metal alloy in accordance with the present disclosure that can be used to partially or fully form a medical device.
[00108] Another and/or alternative non-limiting object of the present disclosure is the provision of a medical device that is partially or fully formed of the refractory metal alloy of the present disclosure and which medical device has improved procedural success rates.
[00109] 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.
[00110] Another and/or alternative non-limiting object of the present disclosure is the provision of a medical device that is partially or fully formed of the refractory metal alloy in accordance with the present disclosure and wherein the medical device has improved physical properties.
[00111] Another and/or alternative non-limiting object of the present disclosure is the provision of a medical device that is at least partially formed of the refractory metal alloy in accordance with the present disclosure that has increased strength and/or hardness.
[00112] Another and/or alternative non-limiting object of the present disclosure is the provision of a medical device that at least partially includes the refractory metal alloy in accordance with the present disclosure and which refractory metal alloy enables the medical device to be formed with less material without sacrificing the strength of the medical device compared to prior medical devices.
[00113] 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.
[00114] 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 crack propagation and/or fatigue failure of the refractory metal alloy.
[00115] Another and/or alternative non-limiting object of the present disclosure is the provision of a medical device that includes a refractory metal alloy having a nitriding process to form a nitrided layer on the outer surface of the refractory metal alloy.
[00116] 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 refractory metal alloy has been subjected to a swaging process.
[00117] 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 refractory metal alloy has been subjected to a cold-working process.
[00118] Another and/or alternative non-limiting object of the present disclosure is the provision of a medical device that includes a refractory metal alloy that has increased strength and/or hardness as compared with stainless steel, chromium-cobalt alloys, or titanium alloys.
[00119] Another and/or alternative non-limiting object of the present disclosure is the provision of a medical device that includes a refractory metal alloy thereby requiring a less quantity of refractory metal alloy to achieve similar strengths compared to medical devices formed of different metals.
[00120] 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.
[00121] 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 thinner walls and/or struts than in frames of a same shape that are formed of stainless steel, cobalt and chromium alloy or titanium alloy, and such frame formed of refractory metal alloy has the same or increase radial strength when the frame is expanded form a crimped configuration to an expanded configuration as compared to such frames formed of stainless steel or cobalt and chromium alloy, or titanium alloy.
[00122] 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 improved stress-strain properties, bendability properties, elongation properties, and/or flexibility properties as compared to medical devices formed of stainless steel, titanium alloy, or chromium-cobalt alloys.
[00123] 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 an increase life as compared to medical devices formed of stainless steel, titanium alloy, or chromium-cobalt alloys.
[00124] 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 reduced degree of recoil during the crimping and/or expansion of the medical device compared with frames of a similar size, shape and configuration that are formed of stainless steel, chromium-cobalt alloys, or titanium alloys.
[00125] 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 better conforms to an irregularly shaped body passageway when expanded in the body passageway as compared with frames of a similar size, shape and configuration that are formed of stainless steel, chromium-cobalt alloys, or titanium alloys.
[00126] 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 improved fatigue ductility when subjected to cold-working as compared to the cold-working of frames of a similar size, shape and configuration that are formed of stainless steel, chromium-cobalt alloys, or titanium alloys.
[00127] 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 improved durability as compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
[00128] 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 improved hydrophilicity as compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
[00129] 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 reduced ion release in the body passageway as compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
[00130] 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 is less of an irritant to the body than stainless steel, cobalt-chromium alloy, or titanium alloys, thus can result in reduced inflammation, faster healing, and increased success rates of the medical device.
[00131] Another and/or alternative non-limiting object of the present disclosure is the provision of 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.).
[00132] These and other advantages will become apparent to those skilled in the art upon the reading and following of this description.
[00133] Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.
[00134] The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.
[00135] As used in the specification and in the claims, 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. However, such description should be construed as also describing compositions or processes as “consisting of’ and “consisting essentially of’ the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any unavoidable impurities that might result therefrom, and excludes other ingredients/steps.
[00136] Numerical values in the specification and claims of this application should be understood to include numerical values which are the same when reduced to the same number of significant figures and numerical values which differ from the stated value by less than the experimental error of conventional measurement technique of the type described in the present application to determine the value.
[00137] All ranges disclosed herein are inclusive of the recited endpoint and independently combinable (for example, the range of “from 2 grams to 10 grams” is inclusive of the endpoints, 2 grams and 10 grams, and all the intermediate values).
[00138] The terms “about” and “approximately” can be used to include any numerical value that can vary without changing the basic function of that value. When used with a range, “about” and “approximately” also disclose the range defined by the absolute values of the two endpoints, e.g., “about 2 to about 4” also discloses the range “from 2 to 4.” Generally, the terms “about” and “approximately” may refer to plus or minus 10% of the indicated number.
[00139] Percentages of elements should be assumed to be percent by weight of the stated element, unless expressly stated otherwise.
[00140] 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 of the prosthetic heart valve comparted to prior art prosthetic heart valves formed of CoCr alloys, TiAIV alloys, and stainless steel, thereby reducing the incidence of stroke and/or by increasing the incidence of success of the implanted medical device; 4) improving the radial strength of the expanded struts, posts, and/or strut joints in the expandable frame and the strength of the expandable frame itself after expansion the medical device; 5) reducing the amount of recoil of the expandable frame during the crimping and/or expansion of the expandable frame of the medical device; 6) enabling the medical device to be used in a heart that has a permanent pacemaker; 7) reducing the incidence of minor stroke during the insertion and operation of the medical device at the treatment area; 8) reducing the incidence of coronary ostium compromise; 9) improving foreshortening; 10) reducing further aortic valve calcification and/or calcification in a blood vessel after implantation of the medical device; 11) reducing the need for multiple crimping cycles when inserting the medical device on a catheter or other type of delivery system; 12) reducing the incidence of frame/stent fracture during the crimping and/or expansion of the medical device; 13) reducing the incidence of biofilm- endocarditis after implantation of the medical device; 14) reducing allergic reactions to the medical device after implantation of the medical device; 15) improving the hydrophilicity of the medical device to improve tissue growth on and/or about the implanted medical device, 16) reduce the magnetic susceptibility of the medical device, 17) reduce the toxicity of the medical device, 18) reduce the amount of metal ion release from the medical device, and/or 19) increasing the longevity of leaflets and/or stent/frame and/or other components of the medical device after insertion of the medical device.
[00141] In another non-limiting object of the present disclosure, there is provided a refractory metal alloy comprising rhenium and one or more alloying metals, and wherein the refractory metal alloy is used to at least partially form a medical device.
[00142] In another non-limiting object of the present disclosure, there is provided a refractory metal alloy comprising rhenium and one or more alloying metals, and wherein the refractory metal alloy is used to at least partially form a medical device; and wherein at least one region of the medical device includes at least one biological agent.
[00143] In another non-limiting object of the present disclosure, there is provided a refractory metal alloy comprising rhenium and one or more alloying metals, and wherein the refractory metal alloy is used to at least partially form a medical device; and wherein at least one region of the medical device includes at least one polymer.
[00144] In another non-limiting object of the present disclosure, there is provided a refractory metal alloy comprising rhenium and one or more alloying metals, and wherein the refractory metal alloy is used to at least partially form a medical device; and wherein at least one region of the medical device includes at least one polymer, the at least one polymer at least partially coats, encapsulates, or combinations thereof at least one biological agent.
[00145] In another non-limiting object of the present disclosure, there is provided a refractory metal alloy comprising rhenium and one or more alloying metals, and wherein the refractory metal alloy is used to at least partially form a medical device; and wherein at least one micro- structure is located on an outer surface of the medical device; and wherein the at least one microstructure optionally is at least partially formed of, includes, or combinations thereof, a material consisting of a polymer, an agent, or combinations thereof.
[00146] In another non-limiting object of the present disclosure, there is provided a refractory metal alloy comprising rhenium and one or more alloying metals, and wherein the refractory metal alloy is used to at least partially form a medical device; and wherein the medical device includes an expandable frame formed of the refractory metal alloy; the expandable frame including a plurality of struts; the expandable frame is optionally configured to be crimped to a crimped state such that a maximum outer diameter of the expandable frame when in the crimped state is less than a maximum outer diameter of the expandable frame when fully expanded to an expanded state; and wherein the expandable frame optionally has a recoil of less than 5% (e.g., 0.1-4.99 and all values and ranges therebetween) after being subjected to a first crimping process; and wherein the expandable frame optionally has a recoil of less than 5% (e.g., 0.1-4.99 and all values and ranges therebetween) after being expanded from the crimped state to the expanded state; and wherein the refractory metal alloy optionally has a hydrophilicity wherein a contact angle of a water droplet on a surface of said refractory metal alloy of 25-45° (e.g., 0.1-4.99 and all values and ranges therebetween); and wherein the refractory metal alloy optionally has a maximum ion release of a primary component of said refractory metal alloy when inserted or implanted on or in the body of the patient of no more than 0.5 pg/cm2 per day (e.g., 0.001-0.5 pg/cm2 per day and all values and ranges therebetween); and wherein the primary component constitutes at least 2 wt.% of the refractory metal alloy; and wherein the refractory metal alloy optionally has an absolute increase in ion release per dose of refractory metal alloy in tissue about said medical device of no more than 50 days after inserted or implanted on or in the body of a patient.
[00147] In another non-limiting object of the present disclosure, there is provided a refractory metal alloy comprising rhenium and one or more alloying metals, and wherein the refractory metal alloy is used to at least partially form a medical device; and wherein the medical device is an expandable stent or an expandable prosthetic heart valve.
[00148] In another non-limiting object of the present disclosure, there is provided a refractory metal alloy comprising rhenium and one or more alloying metals, and wherein the refractory metal alloy is optionally used to at least partially form a medical device; and wherein the one or more alloying metals are selected from the group consisting 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; and wherein 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.%; and wherein the refractory metal alloy optionally has a maximum ion release of a primary component of the refractory metal alloy when inserted or implanted on or in a body of a patient of no more than 0.5 pg/cm2 per day (e.g., 0.001- 0.5 pg/cm2 per day and all values and ranges therebetween); and wherein the primary component constitutes at least 2 wt.% of the refractory metal alloy.
[00149] It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained, and since certain changes may be made in the constructions set forth without departing from the spirit and scope of the disclosure, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. The disclosure has been described with reference to preferred and alternate embodiments. Modifications and alterations will become apparent to those skilled in the art upon reading and understanding the detailed discussion of the disclosure provided herein. This disclosure is intended to include all such modifications and alterations insofar as they come within the scope of the present disclosure. It is also to be understood that the following claims are intended to cover all of the generic and specific features of the disclosure herein described and all statements of the scope of the disclosure, which, as a matter of language, might be said to fall therebetween.

Claims

What is claimed:
1. A refractory metal alloy comprising rhenium and one or more alloying agents selected from the group consisting 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; a combined weight percentage of rhenium and one or more alloy agents in said refractory metal alloy is at least 98 wt.%; and wherein at least a portion of an outer surface of said refractory metal alloy includes an enhancement coating material.
2. The refractory metal alloy defined in claim 1, wherein said enhancement coating material can be of a single layer or multi layers consisting of the same or different coating layer compositions.
3. The refractory metal alloy as defined in claim 1, wherein said enhancement coating material includes that includes two or more elements selected form the group consisting of chromium, carbon, nitrogen, titanium, zirconium, oxygen, aluminum, chromium, and boron.
4. The refractory metal alloy as defined in claim 2, wherein said enhancement coating material includes that includes two or more elements selected form the group consisting of chromium, carbon, nitrogen, titanium, zirconium, oxygen, aluminum, chromium, and boron.
5. The refractory metal as defined in claim 1, wherein said enhancement coating material includes nitrides and/or oxides of one or more elements selected from the group consisting of Cr, Ti, Zr, and Al.
6. The refractory metal as defined in any one of claims 2-4, wherein said enhancement coating material includes nitrides and/or oxides of one or more elements selected from the group consisting of Cr, Ti, Zr, and Al.
- 92 -
7. The refractory metal as defined in claim 1, wherein said enhancement coating material includes two or more of a) 40-85 wt.% Cr, b) 5-60 wt.% N, c) 60-99.99 wt.% C, d) 20-85 wt.% Ti, e) 35-95 wt.% Zr, f) 0-10 wt.% Re, g) 0-20 wt.% Si, h) 0-35 wt.% O, and i) 0-40 wt.% C.
8. The refractory metal as defined in any one of claims 2-6, wherein said enhancement coating material includes two or more of a) 40-85 wt.% Cr, b) 5-60 wt.% N, c) 60-99.99 wt.% C, d) 20-85 wt.% Ti, e) 35-95 wt.% Zr, f) 0-10 wt.% Re, g) 0-20 wt.% Si, h) 0-35 wt.% O, and i) 0- 40 wt.% C.
9. The refractory metal as defined in claim 1, wherein said enhancement coating material includes two or more of a) 5-60 wt.% N, b) 35-95 wt.% Zr, f) 0-8 wt.% Re, g) 0-1 wt.% Si, h) 0-35 wt.% O, and i) 0-1 wt.% C.
10. The refractory metal as defined in any one of claims 2-8, wherein said enhancement coating material includes two or more of a) 5-60 wt.% N, b) 35-95 wt.% Zr, f) 0-8 wt.% Re, g) 0- 1 wt.% Si, h) 0-35 wt.% O, and i) 0-1 wt.% C.
11. The refractory metal as defined in claim 1, wherein said enhancement coating material includes first and second coating layers, said first layer 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, and a second coating layer that is applied to a top surface of said first layer, and wherein said second layer includes 70-80 wt.% Zr, 20-30 wt.%, 0-1 wt.% N, 0-8 wt.% Re, 0-1 wt.% Si, and 0-1 wt.% C.
12. The refractory metal as defined in any one of claims 2-10, wherein said enhancement coating material includes first and second coating layers, said first layer 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, and a second coating layer that is applied to a top surface of said first layer, and wherein said second layer includes 70-80 wt.% Zr, 20-30 wt.%, 0-1 wt.% N, 0-8 wt.% Re, 0-1 wt.% Si, and 0-1 wt.% C.
- 93 -
13. The refractory metal as defined in claim 1, wherein said enhancement coating material includes one or more of chromium nitride (CrN), diamond-like carbon (DLC), titanium nitride (TiN), zirconium nitride (ZrN), zirconium oxide (ZrO2), zirconium-nitrogen-carbon (ZrNC), zirconium OxyCarbide (ZrOC), and combinations of such coatings.
14. The refractory metal as defined in any one of claims 2-12, wherein said enhancement coating material includes one or more of chromium nitride (CrN), diamond-like carbon (DLC), titanium nitride (TiN), zirconium nitride (ZrN), zirconium oxide (ZrO2), zirconium-nitrogen-carbon (ZrNC), zirconium OxyCarbide (ZrOC), and combinations of such coatings.
15. The refractory metal alloy as defined in claim 1, wherein said enhancement coating material is applied by a physical vapor deposition (PVD) process, a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, a plasma-enhanced chemical vapor deposition (PE-CVD) process, ion implantation, direct energy deposition (DED), and/or thermal spray techniques like plasma arc spraying, flame spraying, high velocity oxy fuel spraying (HVOF).
16. The refractory metal alloy as defined in any one of claims 2-14, wherein said enhancement coating material is applied by a physical vapor deposition (PVD) process, a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, a plasma-enhanced chemical vapor deposition (PE-CVD) process, ion implantation, direct energy deposition (DED), and/or thermal spray techniques like plasma arc spraying, flame spraying, high velocity oxy fuel spraying (HVOF).
17. The refractory metal alloy as defined in claim 1, wherein said enhancement coating material is used to improve one or more properties of the refractory metal alloy selected from the group consisting of 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, and reduce toxicity of metal
- 94 - alloy having the coated surface.
18. The refractory metal alloy as defined in any one of claims 2-16, wherein said enhancement coating material is used to improve one or more properties of the refractory metal alloy selected from the group consisting of 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, and reduce toxicity of metal alloy having the coated surface.
19. The refractory metal alloy as defined in claim 1, wherein said enhancement coating material has a coating thickness of 2 nanometers to 100 microns.
20. The refractory metal alloy as defined in any one of claims 2-18, wherein said enhancement coating material has a coating thickness of 2 nanometers to 100 microns.
21. The refractory metal alloy as defined in claim 1, wherein said enhancement coating material has a hardness of 5-50 GPa.
22. The refractory metal alloy as defined in any one of claims 2-20, wherein said enhancement coating material has a hardness of 5-50 GPa.
23. The refractory metal alloy as defined in claim 1, wherein said enhancement coating material has a coefficient of friction (COF) of 0.04-0.2.
24. The refractory metal alloy as defined in any one of claims 2-22, wherein said enhancement coating material has a coefficient of friction (COF) of 0.04-0.2.
25. The refractory metal alloy as defined in claim 1, wherein said enhancement coating material has a wear rate of 0.5 x 10'7 mm3/N-m to 3 x 10'7 mm3/N-m.
- 95 -
26. The refractory metal alloy as defined in any one of claims 2-24, wherein said enhancement coating material has a wear rate of 0.5 x 10'7 mm3/N-m to 3 x 10'7 mm3/N-m.
27. The refractory metal alloy as defined in claim 1, wherein said refractory metal alloy includes less than 0.1 wt.% metals and impurities.
28. The refractory metal alloy as defined in any one of claims 2-26, wherein said refractory metal alloy includes less than 0.1 wt.% metals and impurities.
29. The refractory metal alloy as defined in claim 1, wherein said refractory metal alloy includes has a controlled amount of nitrogen, oxygen, and carbon to reduce micro-cracking in said refractory metal alloy, a nitrogen content in said refractory metal alloy is less than a combined content of oxygen and carbon in said refractory metal alloy, said refractory metal alloy has an oxygen to nitrogen atomic ratio of at least about 1.2: 1, said refractory metal alloy has a carbon to nitrogen atomic ratio of at least about 2: 1.
30. The refractory metal alloy as defined in any one of claims 2-28, wherein said refractory metal alloy includes has a controlled amount of nitrogen, oxygen, and carbon to reduce micro-cracking in said refractory metal alloy, a nitrogen content in said refractory metal alloy is less than a combined content of oxygen and carbon in said refractory metal alloy, said refractory metal alloy has an oxygen to nitrogen atomic ratio of at least about 1.2: 1, said refractory metal alloy has a carbon to nitrogen atomic ratio of at least about 2: 1.
31. A medical device that is at least partially formed of said refractory metal alloy as defined in claim 1.
32. A medical device that is at least partially formed of said refractory metal alloy as defined in any one of claims 2-30.
33. The medical device as defined in claim 31, wherein at least one region of said medical device includes at least one biological agent.
- 96 -
34. The medical device as defined in claim 32, wherein at least one region of said medical device includes at least one biological agent.
35. The medical device as defined in claim 31, wherein at least one region of said medical device includes at least one polymer, said at least one polymer optionally at least partially coats, encapsulates, or combinations thereof at least one biological agent.
36. The medical device as defined in any one of claims 32-34, wherein at least one region of said medical device includes at least one polymer, said at least one polymer optionally at least partially coats, encapsulates, or combinations thereof said at least one biological agent.
37. The medical device as defined in claim 31, further comprising at least one microstructure on an outer surface of said medical device, said at least one microstructure is at least partially formed of, includes, or combinations thereof, a material consisting of a polymer, an agent, or combinations thereof.
38. The medical device as defined in any one of claims 32-36, further comprising at least one micro-structure on an outer surface of said medical device, said at least one microstructure is at least partially formed of, includes, or combinations thereof, a material consisting of a polymer, an agent, or combinations thereof.
39. The medical device as defined in claim 31, wherein said medical device includes an expandable frame formed of a refractory metal alloy; said expandable frame including a plurality of struts; said expandable frame is configured to be crimped to a crimped state such that a maximum outer diameter of said expandable frame when in said crimped state is less than a maximum outer diameter of said expandable frame when fully expanded to an expanded state; said expandable frame has a recoil of less than 5% after being subjected to a first crimping process; said expandable frame has a recoil of less than 5% after being expanded from said crimped state to said expanded state; said refractory metal alloy has a hydrophilicity wherein a contact angle of a water droplet on a surface of said refractory metal alloy of 25-45°; said refractory metal alloy has a maximum ion release of a primary component of said refractory metal alloy when inserted or
- 97 - implanted on or in the body of the patient of no more than 0.5 pg/cm2 per day, wherein said primary component constitutes at least 2 wt.% of said refractory metal alloy; said refractory metal alloy has an absolute increase in ion release per dose of refractory metal alloy in tissue about said medical device of no more than 50 days after inserted or implanted on or in the body of a patient.
40. The medical device as defined in any one of claims 32-38, wherein said medical device includes an expandable frame formed of a refractory metal alloy; said expandable frame including a plurality of struts; said expandable frame is configured to be crimped to a crimped state such that a maximum outer diameter of said expandable frame when in said crimped state is less than a maximum outer diameter of said expandable frame when fully expanded to an expanded state; said expandable frame has a recoil of less than 5% after being subjected to a first crimping process; said expandable frame has a recoil of less than 5% after being expanded from said crimped state to said expanded state; said refractory metal alloy has a hydrophilicity wherein a contact angle of a water droplet on a surface of said refractory metal alloy of 25-45°; said refractory metal alloy has a maximum ion release of a primary component of said refractory metal alloy when inserted or implanted on or in the body of the patient of no more than 0.5 pg/cm2 per day, wherein said primary component constitutes at least 2 wt.% of said refractory metal alloy; said refractory metal alloy has an absolute increase in ion release per dose of refractory metal alloy in tissue about said medical device of no more than 50 days after inserted or implanted on or in the body of a patient.
41. A method for forming a refractory metal alloy as defined in claim 1 comprising: providing powered metal; said powdered metal includes rhenium metal powder and one or or more alloying agent powders is selected from the group consisting 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; compressing said powdered metal; sintering said compressed powdered metal to form a metal alloy wherein a combined weight percentage of rhenium and one or more alloy agents in said metal alloy is at least 98 wt.%;
- 98 - coating an outer surface of said metal alloy with said enhancement coating material; said enhancement coating material includes that includes two or more elements selected form the group consisting of chromium, carbon, nitrogen, titanium, zirconium, oxygen, aluminum, chromium, and boron; said step of coating by a physical vapor deposition (PVD) process, a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, a plasma-enhanced chemical vapor deposition (PE-CVD) process, ion implantation, direct energy deposition (DED), and/or thermal spray techniques like plasma arc spraying, flame spraying, high velocity oxy fuel spraying (HVOF).
42. A method for forming a refractory metal alloy as defined in any one of claims 2-30 comprising: providing powered metal; said powdered metal includes rhenium metal powder and one or or more alloying agent powders is selected from the group consisting 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; compressing said powdered metal; sintering said compressed powdered metal to form a metal alloy wherein a combined weight percentage of rhenium and one or more alloy agents in said metal alloy is at least 98 wt.%; coating an outer surface of said metal alloy with said enhancement coating material; said enhancement coating material includes that includes two or more elements selected form the group consisting of chromium, carbon, nitrogen, titanium, zirconium, oxygen, aluminum, chromium, and boron; said step of coating by a physical vapor deposition (PVD) process, a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, a plasma-enhanced chemical vapor deposition (PE-CVD) process, ion implantation, direct energy deposition (DED), and/or thermal spray techniques like plasma arc spraying, flame spraying, high velocity oxy fuel spraying (HVOF).
- 99 -
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US17/586,270 2022-01-27
US202263316077P 2022-03-03 2022-03-03
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