WO2023009739A1 - Dispositif médical comprenant un alliage métallique réfractaire - Google Patents

Dispositif médical comprenant un alliage métallique réfractaire Download PDF

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Publication number
WO2023009739A1
WO2023009739A1 PCT/US2022/038698 US2022038698W WO2023009739A1 WO 2023009739 A1 WO2023009739 A1 WO 2023009739A1 US 2022038698 W US2022038698 W US 2022038698W WO 2023009739 A1 WO2023009739 A1 WO 2023009739A1
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WIPO (PCT)
Prior art keywords
alloy
medical device
expandable
refractory metal
frame
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PCT/US2022/038698
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English (en)
Inventor
Jay Yadav
Noah Roth
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 US17/512,174 external-priority patent/US11504451B2/en
Priority claimed from US17/586,270 external-priority patent/US20230040416A1/en
Application filed by Mirus Llc filed Critical Mirus Llc
Publication of WO2023009739A1 publication Critical patent/WO2023009739A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon

Definitions

  • the disclosure relates generally to medical devices and medical device applications, and more particularly to a medical device that is at least partially formed of a biocompatible metal alloy.
  • the medical device can optionally be in the form into an implant for the treatment of structural heart disease and cardiovascular implants for example a prosthetic heart valve and a transcatheter heart valve that is at least partially formed of the biomedical material such as a biocompatible metal alloy.
  • Stainless steel, cobalt-chromium alloys, TiNi alloys, and TiAlV 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.
  • Many cardiovascular devices such as stents, expandable heart valves and the like are inserted into a patient via the vascular system of a patient and then expanded at the treatment site. These devices are typically crimped onto catheter prior to insertion into a patient. The minimum diameter to which the cardiovascular device can be crimped onto the catheter will set a limit to the size of the cardiovascular passageway (e.g., blood vessel) to which the cardiovascular device can be inserted.
  • the cardiovascular passageway e.g., blood vessel
  • Smaller crimp diameters can result in reduced damage to a blood vessel and/or organ (e.g., heart, etc.) when inserting to and/or placing the cardiovascular device at the treatment site. Smaller crimp diameters can also allow the cardiovascular device to be placed in smaller diameter blood vessels (e.g., blood vessels located in the brain, etc.).
  • a blood vessel and/or organ e.g., heart, etc.
  • Smaller crimp diameters can also allow the cardiovascular device to be placed in smaller diameter blood vessels (e.g., blood vessels located in the brain, etc.).
  • the crimp diameter of the expandable cardiovascular device can be reduced by reducing the thickness and/or size of the frame, struts, strut joints, etc. of the cardiovascular device.
  • reduction in size also affects the strength of the cardiovascular device after being expanded. After the cardiovascular device is expanded, it must retain its expanded shape at the treatment area, otherwise the cardiovascular device could become dislodged from the treatment area, could damage the treatment area, and/or fail to properly function at the treatment area.
  • cardiovascular devices formed of tradition materials such as stainless steel (e.g., 316L: 17- 19 wt.% chromium, 13-15 wt.% nickel, 2-4 wt.% molybdenum, 2 wt.% max manganese, 0.75 wt.% max silicon, 0.03 wt.% max carbon, balance iron) and cob alt- chromium alloys (e.g., MP35N: 19-21 wt.% chromium, 34-36 wt.% nickel, 9-11 wt.% molybdenum, 1 wt.% max iron, 1 wt.% max titanium, 0.15 wt.% max manganese, 0.15 wt.% max silicon, 0.025 wt.% max carbon, balance cobalt) are required to maintain a frame and/or strut size/thickness and/or strut joint size/thickness that limits how small of crimping diameter can be obtained by the crimped cardiovascular device.
  • CoCr alloys that have been used are Phynox and Elgiloy alloy (38-42 wt.% cobalt, 18-22 wt.% chromium, 14-18 wt.% iron, 13-17 wt.% nickel, 6-8 wt.% molybdenum), and L605 alloy (18-22 wt.% chromium, 14-16 wt.% W, 9-11 wt.% nickel, balance cobalt).
  • tradition materials such as stainless steel (316L) and cobalt-chromium alloys (e.g., MP35N, etc.) have a degree of recoil after being crimped and expanded that can interfere with obtaining a minimum crimping diameter and/or can adversely affect the placement of the expandable cardiovascular device at a treatment area.
  • a crimping device is typically used to crimp the cardiovascular device onto a catheter.
  • tradition materials such as stainless steel and cobalt-chromium alloys coil to a larger diameter by 9+% of the minimum crimped diameter.
  • the cardiovascular device must be crimped multiple times onto a catheter to attempt to obtain a smaller crimped diameter on the catheter.
  • subjecting the cardiovascular device can result is damage to the cardiovascular device (e.g., damage to the frame and/or struts and/or strut joints of the cardiovascular device, damage to leaflets on an expandable heart valve, etc.).
  • the traditional materials of the cardiovascular device will recoil 9+% of the maximum expanded diameter.
  • the inflatable balloon on the catheter must be pressurized multiple times to repeatedly expand the cardiovascular device at the treatment area to ensure proper expansion of the cardiovascular device.
  • cardiovascular device subjecting the cardiovascular device to multiple balloon expansions can result in damage to the cardiovascular device (e.g., damage or breakage of a frame and/or strut and/or strut joints, etc.) and/or damage to the treatment area (e.g., rupture of blood vessel, tear and/or puncture of tissue of an organ, etc.).
  • damage to the cardiovascular device e.g., damage or breakage of a frame and/or strut and/or strut joints, etc.
  • the treatment area e.g., rupture of blood vessel, tear and/or puncture of tissue of an organ, etc.
  • TAVs Transcatheter aortic valves
  • SAVR open heart surgical aortic valve replacement
  • Non-limiting TAVs are disclosed in US 5,411,522; US 6,730,118; US 10,729,543; US 10,820,993; US 10,856,970; US 10,869,761; US 10,952,852; US 10,980,632; US 10,980,633; and US 2020/0405482, all of which are incorporated fully herein by reference.
  • the frame material used to form the TAV is typically CoCr alloy or Nitinol.
  • the vast majority of cardiovascular implants include valves that are made at least impart by using a CoCr alloy or Nitinol materials for construction of the structural frame of the valve.
  • a TAV is designed to be compressed into a small diameter catheter, remotely placed within a patient’s diseased aortic valve so as to take over the function of the native valve.
  • Some TAVs are balloon-expandable, while others are self-expandable. In both cases, the TAVs are deployed within a calcified native valve that is forced permanently open and becomes the surface against which the stent is held in place by friction.
  • TAVs can also be used to replace failing bioprosthetic or transcatheter valves, commonly known as a valve in valve procedure.
  • Major TAVR advantages to the traditional surgical approaches include refraining cardiopulmonary bypass, aortic cross-clamping and sternotomy that significantly reduces patients’ morbidity.
  • TAV devices include mispositioning, crimp-induced leaflet damage, paravalvular leak, thrombosis, conduction abnormalities and prosthesis-patient mismatch.
  • complications are potentially associated with the calcification landscape of the native valve, geometric and mechanical properties of the aortic root, blood biochemistry and coagulability associated with the patient, and concomitant conditions such as hypertension, coronary artery disease, heart failure, etc.
  • TAVs Some limitations of current TAVs that prevent its use in lower risks patients are a) vascular complications from large delivery systems, which necessitates smaller profiles, b) paravalvular leak, c) device mispositioning, and d) device failure.
  • TAVR involves delivery, deployment, and implantation of a crimped, stented valve within a diseased aortic valve or degenerated bioprosthesis, some limitation of these procedures is the diameter to which the stent can be crimped without damaging the leaflet tissues within, vascular complications such as dissection due to the size of the delivery system, and/or recoil associated with the valve frame as defined as the frame being opened to a certain positional diameter and then relaxing or settling to a smaller diameter post implantation which can lead to valve embolization and/or paravalvular leak. Damage to the leaflet tissue can result in increased calcification and early failure of the TAV.
  • the present disclosure is direct to a medical device that is at least partially made of a biomedical material that includes a refractory metal alloy, and more particularly to a prosthetic heart valve that is at least partially formed of a biomedical medical that includes a refractory metal alloy.
  • a refractory metal alloy is a metal alloy that includes at least 20 wt.% of one or more of molybdenum, rhenium, niobium, tantalum or tungsten.
  • Non-limiting refractory metal alloys include MoRe alloy, ReW alloy, MoReCr alloy, MoReTa alloy, MoReTi alloy, WCu alloy, ReCr, molybdenum alloy, rhenium alloy, tungsten alloy, tantalum alloy, niobium alloy, etc.
  • 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 in the non-limiting form of a prosthetic heart valve (e.g., TAV valve, mitral valve replacement, tricuspid valve replacement, pulmonary valve replacement).
  • the prosthetic heart valve includes a radially collapsible and expandable frame and a leaflet structure comprising a plurality of leaflets.
  • the prosthetic heart valve can optionally include an annular skirt or cover member disposed on and covering the cells of at least a portion of the frame.
  • the frame can comprise a plurality of interconnected struts and strut joints defining a plurality of open cells in the frame.
  • the frame is partially (e.g., 40-99.99% and all values and ranges therebetween) or fully made of a refractory metal alloy.
  • a prosthetic heart valve that includes a frame or stent, a leaflet structure supported by the frame, and an optional inner skirt secured to the surface of the frame and/or leaflet structure.
  • the prosthetic heart valve can be implanted in the annulus of the native aortic valve; however, the prosthetic heart valve also can be configured to be implanted in other valves of the heart (e.g., tricuspid valve, pulmonary valve, mitral valve).
  • the prosthetic heart valve has a “lower” end and an “upper” end, wherein the lower end of the prosthetic heart valve is the inflow end and the upper end of the prosthetic heart valve is the outflow end.
  • a medical device partially or fully formed of a refractory metal alloy.
  • 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.
  • 50-100% (and all values and ranges therebetween) of the medical device is formed of the refractory metal alloy.
  • 50-100% (and all values and ranges therebetween) of the medical device is formed of a MoRe alloy.
  • 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, rhenium, niobium, tantalum or tungsten.
  • the medical device is a prosthetic heart valve and the frame of the prosthetic heart valve is partially or fully formed of a refractory metal alloy.
  • 50-100% (and all values and ranges therebetween) of the frame of the prosthetic heart valve is formed of a refractory metal alloy.
  • 50-100% (and all values and ranges therebetween) of the frame of the prosthetic heart valve is formed of a MoRe alloy.
  • the refractory metal alloy that is used to form at least a portion of the medical device is configured to be radially collapsible to a collapsed or crimped state for introduction into the body (e.g., on a delivery catheter, etc.) and radially expandable to an expanded state for implanting the medical device at a desired location in the body (e.g., the aortic valve, tricuspid valve, pulmonary valve, mitral valve, blood vessel, ureter, bile duct, pancreatic duct, esophagus, lung, eyes, sinus, oral stent, etc.).
  • the frame of the medical device can be formed of a plastically-expandable material that permits crimping of the frame to a smaller profile for delivery and expansion of the frame.
  • the expansion of the crimped frame of the medical device can be by an expansion device such as, but not limited to, a balloon of on a balloon catheter.
  • a medical device that includes a frame at least partially formed of a plurality of angularly spaced, vertically extending posts, or struts.
  • the posts or struts can optionally be interconnected via a lower row of circumferentially extending struts and an upper row of circumferentially extending struts via strut j oints.
  • the struts can be arrangement in a variety of patterns (e.g., zig-zag pattern, saw-tooth pattern, triangular pattern, polygonal pattern, oval pattern, etc.).
  • One or more of the posts and/or struts can have the same or different thicknesses and/or cross-sectional shape and/or cross-sectional area.
  • a medical device that includes a frame that can be optionally coated with a polymer material (e.g., silicone, PTFE, ePTFE, polyurethane, polyolefins, hydrogels, biological materials (e.g., pericardium or biological polymers such as collagen, gelatin, or hyaluronic acid derivatives), etc.).
  • a polymer material e.g., silicone, PTFE, ePTFE, polyurethane, polyolefins, hydrogels, biological materials (e.g., pericardium or biological polymers such as collagen, gelatin, or hyaluronic acid derivatives), etc.
  • the coating can be used to partially or fully encapsulate the struts on the frame and/or to fill-in the openings between the struts on the frame.
  • a medical device in the form of a prosthetic heart valve.
  • the prosthetic heart valve can be configured such that it can be crimped so the prosthetic heart valve has a crimped diameter of less than 24 FR (less than 8 mm). Most prior art prosthetic heart values can only be crimped to a diameter of about 24-27 FR (8-9 mm) or larger.
  • a medical device in the form of a prosthetic heart valve that includes an inner skirt that can be formed of a variety of flexible materials (e.g., polymer [e.g., polyethylene terephthalate (PET), polyester, nylon, Kevlar,®, silicon, etc.], composite material, metal, fabric material, etc.).
  • the material used to partially or fully form the inner skirt can optionally be substantially non-elastic (i.e., substantially non-stretchable and non- compressible).
  • the material used to partially or fully form the inner skirt can optionally be a stretchable and/or compressible material (e.g., silicone, PTFE, ePTFE, polyurethane, polyolefins, hydrogels, biological materials [e.g., pericardium or biological polymers such as collagen, gelatin, or hyaluronic acid derivatives], etc.).
  • the inner skirt can optionally be formed from a combination of a cloth or fabric material that is coated with a flexible material or with a stretchable and/or compressible material so as to provide additional structural integrity to the inner skirt.
  • the size, configuration, and thickness of the inner skirt is non-limiting (e.g., thickness of 0.1-20 mils and all values and ranges therebetween).
  • the inner skirt can be secured to the inside and/or outside of the frame using various means (e.g., sutures, clamp arrangement, etc.).
  • a medical device in the formed of a prosthetic heart valve that optionally includes an inner skirt that can be used to 1) at least partially seal and/or prevent perivalvular leakage, 2) at least partially secure the leaflet structure to the frame, 3) at least partially protect the leaflets from damage during the crimping and/or expansion process, and/or 4) at least partially protect the leaflets from damage during the operation of the prosthetic heart valve in the heart.
  • a medical device in the form of a prosthetic heart valve that optionally includes an outer or sleeve that is positioned at least partially about the exterior region of the frame.
  • the outer skirt or sleeve generally is positioned completely around a portion of the outside of the frame.
  • the outer skirt is positioned about the lower portion of the frame, but does not fully cover the upper half of the frame; however, this is not required.
  • the outer skirt can be connected to the frame by a variety of arrangements (e.g., sutures, adhesive, melted connection, clamping arrangement, etc.). At least a portion of the outer skirt can optionally be located on the interior surface of the frame.
  • the outer skirt is formed of a more flexible and/or compressible material than the inner skirt; however, this is not required.
  • the outer skirt can be formed of a variety of a stretchable and/or compressible material (e.g., silicone, PTFE, ePTFE, polyurethane, polyolefins, hydrogels, biological materials [e.g., pericardium or biological polymers such as collagen, gelatin, or hyaluronic acid derivatives], etc.).
  • the outer skirt can optionally be formed from a combination of a cloth or fabric material that is coated with the stretchable and/or compressible material to provide additional structural integrity to the outer skirt.
  • the size, configuration, and thickness of the outer skirt is non-limiting. The thickness of the outer skirt is generally 0.1-20 mils (and all values and ranges therebetween).
  • a medical device in the form of a prosthetic heart valve that includes a leaflet structure that can be can be attached to the frame and/or skirt.
  • the connection arrangement used to secure the leaflet structures to the frame and/or skirt is non-limiting (e.g., sutures, melted bold, adhesive, clamp arrangement, etc.).
  • the material used to form the leaflet structures include bovine pericardial tissue, biocompatible synthetic materials, or various other suitable natural or synthetic materials.
  • a medical device in the form of a prosthetic heart valve that includes a leaflet structure comprised of two or more leaflets (e.g., 2, 3, 4, 5, 6, etc.).
  • the leaflet structure includes three leaflets arranged to collapse in a tricuspid arrangement.
  • the configuration of the leaflet structures is non-limiting.
  • a medical device in the form of a prosthetic heart valve that includes a leaflet structure wherein the leaflets of the leaflet structure can optionally be secured to one another at their adjacent sides to form commissures of the leaflet structure (the edges where the leaflets come together).
  • the leaflet structure can be secured together by a variety of connection arrangement (e.g., sutures, adhesive, melted bond, clamping arrangement, etc.).
  • a medical device in the form of a prosthetic heart valve that includes a leaflet structure wherein one or more of the leaflets can optionally include reinforcing structures or strips to 1) facilitate in securing the leaflets together, 2) facilitate in securing the leaflets to the skirt and/or frame, and/or 3) inhibit or prevent tearing or other types of damage to the leaflets.
  • a method for crimping a medical device having a frame there is provided.
  • the method includes placing the medical device in the crimping aperture of a crimping device such that the frame of the medical device is disposed adjacent to the crimping jaws of the crimping device. Pressure is applied against the frame with the crimping jaws to radially crimp the medical device to a smaller profile.
  • 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, less foreshortening, 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,
  • These one or more improved physical properties of the refractory metal alloy can be achieved in the medical device or portion of the medical device (e.g., frame of the medical device, etc.) without having to increase the bulk, volume, and/or weight of the medical device or portion of the medical device (e.g., frame of the medical device, etc.), and in some instances these improved physical properties can be obtained even when the volume, bulk, and/or weight of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) is reduced as compared to medical devices or the frame of the medical device 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 or portion of the medical device can thus 1) increase the radiopacity of the medical device or portion of the medical device (e.g., frame of the medical device, etc.), 2) increase the radial strength of the medical device or portion of the medical device (e.g., frame of the medical device, etc.), 3) increase the yield strength and/or ultimate tensile strength of the medical device or portion of the medical device (e.g., frame of the medical device, etc.), 4) improve the stress-strain properties of the medical device or portion of the medical device (e.g., frame of the medical device, etc.), 5) improve the crimping and/or expansion properties of the medical device or portion of the medical device (e.g., frame of the medical device, etc.), 6) improve the bendability and/or flexibility of the medical device or portion of the medical device or portion of the medical device.
  • the medical device or portion of 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.
  • the refractory metal alloy that is used to at least partially form the medical device or portion of 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 or portion of the medical device (e.g., frame of the medical device, etc.), and/or during the use and/or expansion of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) 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 or portion of the medical device (e.g., frame of the medical device, etc.), and/or during the use and/or expansion of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) in a body passageway.
  • a medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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. 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).
  • the refractory metal alloy will have a very low tendency to form micro-cracks during the formation of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) 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.
  • 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.
  • 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).
  • 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 or portion of 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).
  • the medical device or portion of the medical device includes at least about 50 wt.% of the refractory metal alloy.
  • the medical device or portion of the medical device includes at least about 95 wt.% of the refractory metal alloy.
  • 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.
  • 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 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.
  • the medical device or portion of 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 or portion of the medical device (e.g., frame of the medical device, etc.).
  • the medical device can be at least partially or fully formed from by 3D printing.
  • 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.
  • the average Vickers hardness of refractory metal alloy of the present disclosure used to at least partially form the medical device or portion of 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).
  • 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.
  • 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.
  • the average grain size of the refractory metal alloy of the present disclosure used to at least partially form the medical device or portion of 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 or portion of the medical device (e.g., frame of the medical device, etc.) to have the desired elongation and ductility properties that are useful in enabling the medical device or portion of the medical device (e.g., frame of the medical device, etc.) to be formed, crimped, and/or expanded.
  • the average tensile elongation of the refractory metal alloy of the present disclosure used to at least partially form the medical device or portion of 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 or portion of the medical device (e.g., frame of the medical device, etc.) being properly expanded when positioned in the treatment area of a body passageway.
  • a medical device or frame of a medical device that is partially or fully formed of a material that does not have an average tensile elongation of at least about 25% may be more prone to the formation of micro-cracks and/or break during the forming, crimping, and/or expansion of the medical device or portion of the medical device (e.g., frame of the medical device, etc.).
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), 5) a reduction or prevention of micro-crack formation and/or breaking of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) when the medical device or portion of the
  • 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.
  • at least 40 wt.% of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten.
  • at least 50 wt.% of the refractory metal alloy includes one or more of molybdenum, niobium, rhenium, tantalum, or tungsten.
  • 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.
  • 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
  • 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 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.
  • the refractory metal alloy includes 0-2 wt.% (and all values and ranges therebetween
  • 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.
  • the refractory metal alloy includes 0-0.1 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 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
  • 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.
  • wt.% e.g., 40-99.9 wt.% and all values and ranges therebetween
  • rhenium and 0.1-60 wt.% and all
  • 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
  • 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., 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.
  • wt.% e.g., 20-99.9 wt.% and all values and ranges therebetween
  • 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 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., 30-99.9 wt.% and all values and ranges therebetween
  • 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 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.
  • 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 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.
  • 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., 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 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., 50- 99.9 wt.% and all values and ranges therebetween
  • rhenium e.g., 50- 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 tungsten- rhenium 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 refractory metal alloy wherein at least 30 wt.% (e.g., 30-99 wt.% and all values and ranges therebetween) of the refractory metal alloy includes rhenium. In another non-limiting embodiment, at least 35 wt.% of the refractory metal alloy includes rhenium.
  • At least 35 wt.% (e.g., 35-99.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes rhenium, and 0.1-65 wt.% (and all values and ranges therebetween) of the refractory metal alloy includes one or more of molybdenum, niobium, tantalum, tantalum, titanium, vanadium, chromium, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and/or iridium.
  • 35-60 wt.% (and all values and ranges therebetween) of the refractory metal alloy includes rhenium, and 40-65 wt.% (and all values and ranges therebetween) of the refractory metal alloy includes one or more of molybdenum, niobium, tantalum, tungsten, titanium, vanadium, chromium, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and/or iridium.
  • 35-60 wt.% (e.g., and all values and ranges therebetween) of the refractory metal alloy includes rhenium, and 40-65 wt.% (and all values and ranges therebetween) of the refractory metal alloy includes two or more of molybdenum, niobium, tantalum, tantalum, titanium, vanadium, chromium, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and/or iridium.
  • 35-60 wt.% (e.g., and all values and ranges therebetween) of the refractory metal alloy includes rhenium, and 40-65 wt.% (and all values and ranges therebetween) of the refractory metal alloy includes three or more of molybdenum, niobium, tantalum, tantalum, titanium, vanadium, chromium, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and/or iridium.
  • the metals used to form the refractory metal alloy include at least 35 wt.% rhenium (e.g., 35-99.9 wt.% and all values and ranges therebetween) and one or more alloying agents such as, but are not limited to, molybdenum, niobium, tantalum, tantalum, titanium, vanadium, chromium, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and/or iridium, and/or alloys of one or more of such components.
  • rhenium e.g., 35-99.9 wt.% and all values and ranges therebetween
  • alloying agents such as, but are not limited to, molybdenum, niobium, tantalum, tantalum, titanium, vanadium, chromium, manganese, zirconium, technetium, ruthenium, rhodium
  • the refractory metal alloy includes 40-99.9 wt.% rhenium and one or more molybdenum, niobium, tantalum, tantalum, titanium, vanadium, chromium, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and/or iridium.
  • the refractory metal alloy includes rhenium and one or more molybdenum, niobium, tantalum, tantalum, titanium, vanadium, chromium, manganese, zirconium, technetium, ruthenium, rhodium, hafnium, osmium, copper, and/or iridium.
  • 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.
  • 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.
  • 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 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).
  • 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.
  • 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.
  • 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 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).
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • at least 25 wt.% (e.g., 25-49.9 wt.% and all values and ranges therebetween) of the refractory metal alloy includes chromium.
  • at least 30 wt.% of the refractory metal alloy includes chromium.
  • 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 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
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • the refractory metal alloy includes less than about 0.5 wt.% other metals and/or impurities.
  • 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.
  • V ⁇ 1% ⁇ 1% ⁇ 1% ⁇ 1% w 0-50% 0-50% 0-50% 0.5-50%
  • V V ⁇ 1% ⁇ 1% ⁇ 1% w 0-50% 0-50% 0-50%
  • V ⁇ 1% ⁇ 1% ⁇ 1% ⁇ 1% w 0-50% 0-50% 0-50% 0.5-50%
  • V V ⁇ 1% ⁇ 1% ⁇ 1% w 0-50% 0-50% 0-50%
  • 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.
  • the refractory metal alloy is optionally at least partially formed by a swaging process; however, this is not required.
  • swaging is performed on the refractory metal alloy to at least partially or fully achieve final dimensions of one or more portions of the prosthetic heart valve.
  • the swaging dies can be shaped to fit the final dimension of the prosthetic heart valve; however, this 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 prosthetic heart valve in the areas to be hardened.
  • the swaging can be rotary.
  • the swaging of the non-round portion of the prosthetic heart valve 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 prosthetic heart valve 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 prosthetic heart valve.
  • the swaging temperature for a particular refractory metal alloy can vary.
  • 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.
  • RT room temperature
  • 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 prosthetic heart valve at the location to be hardened at the desired swaging temperature.
  • ions of boron and/or nitrogen are allowed to impinge upon rhenium atoms in the refractory metal alloys that include rhenium to form ReB2, ReN2 and/or ReN 3 ; however, this is not required. It has been found that ReB2, ReN2 and/or ReN 3 are ultra-hard compounds.
  • other refractory metal alloys that include Re and that are subjected to a swaging process can also form ReB2, ReN2 and/or ReN 3 .
  • the refractory metal alloy for the prosthetic heart valve can be machined and shaped to at least partially form the prosthetic heart valve when the refractory metal alloy is in a less hardened state; however, this is not required.
  • 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 prosthetic heart valve can improve the wear resistance and/or shape retention of the prosthetic heart valve.
  • 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.
  • 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 frame of the prosthetic heart valve.
  • 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.
  • 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.
  • 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).
  • nitrogen gas or a nitrogen gas mixture e.g., 90-99% vol.% nitrogen and 1-10 vol.% hydrogen, etc.
  • 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.
  • a nitrogen-containing salt such as cyanide salt is used.
  • the refractory metal alloy is generally exposed to temperatures of about 520-590°C.
  • 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.
  • 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.
  • the weight percent of nitrogen in the nitrided surface layer is 0.0001-5 wt.% nitrogen (and all values and ranges therebetween).
  • 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.
  • 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.
  • the weight percent of nitrogen in the nitrided surface layer is less than a weight percent of the rhenium in the nitrided surface layer.
  • 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 nitride surface layer comprises 40-99 wt.% molybdenum, 1-40 wt.% rhenium, and 0.001-1 wt.% nitrogen.
  • other refractory metal alloys can be nitrided.
  • 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 prosthetic heart valve, and/or to inhibit or prevent discoloration of the refractory metal alloy (e.g., discoloration by oxidation, etc.).
  • 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 prosthetic heart valve to extend the life of the prosthetic heart valve, and/or to increase the wear life of mating surfaces on the prosthetic heart valve (e.g., polyethylene liners of joint implants like knees, hips, shoulders, etc.), to reduce particulate generation from use of the prosthetic heart valve, and/or to maintain the outer surface appearance of the refractory metal alloy on the prosthetic heart valve.
  • mating surfaces on the prosthetic heart valve e.g., polyethylene liners of joint implants like knees, hips, shoulders, etc.
  • the surface of the refractory metal alloy is optionally nitrided prior to at least one drawing step for the refractory metal alloy.
  • 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 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.
  • 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.
  • 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 final formed refractory metal alloy can optionally include a nitride outer surface.
  • the refractory metal alloy just prior to or after being partially or fully formed into the desired frame of the prosthetic heart valve, can optionally be cleaned, polished, sterilized, nitrided, etc., for final processing of the refractory metal alloy.
  • 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 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.
  • a solvent e.g., acetone, methyl alcohol, etc.
  • the refractory metal alloy can be cleaned in other or additional ways.
  • 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).
  • polishing solution compositions can be used.
  • 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.
  • 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.
  • the use of the refractory metal alloy to partially or fully form the frame of the prosthetic heart valve can be used to increase the strength, hardness, and/or durability of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) 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 or portion of the medical device (e.g., frame of the medical device, etc.) to achieve similar strengths compared to medical devices or frames of medical devices formed of different metals.
  • 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.
  • 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.
  • the thickness of the walls of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) and/or the wires used to at least partially form the medical device or portion of the medical device (e.g., frame of the medical device, etc.) 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.
  • the medical device can be used in regions that subject the medical device to bending.
  • the medical device 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.
  • 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.
  • 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 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.
  • the refractory metal alloy has improved radiopaque properties as compared to standard materials such as stainless steel, TiNi alloys, or cobalt-chromium alloy, thus reducing or eliminating the need for using marker materials on the medical device.
  • the refractory metal alloy is believed to at least about 10-20% more radiopaque than stainless steel, TiNi alloys, or cobalt-chromium alloy.
  • 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.
  • 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
  • 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;reteplase and/or derivatives thereof; amino glycosides and/or derivatives thereof (e.g., gentamycin, tobramycin, etc.); angiopeptin and
  • the agent can include one or more derivatives of the above listed compounds and/or other compounds.
  • the agent includes, but is not limited to, trapidil, trapidil derivatives, taxol, taxol derivatives (e.g., taxotere, baccatin, 10-deacetyltaxol, 7-xylosyl-lO-deacetyltaxol, cephalomannine, 10-deacetyl-7-epitaxol, 7 epitaxol, 10-deacetylbaccatin III, 10-deacetyl cephaolmannine, etc.), cytochalasin, cytochalasin derivatives (e.g., cytochalasin A, cytochalasin B, cytochalasin C, cytochalasin D, cytochalasin E, cytochalasin F, cytochalasin G, cytochalasin H, cytochalasin J
  • 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.
  • the amount of agent included on, in and/or used in conjunction with medical device, when the agent is used is about 0.01-100ug per mm 2 (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.
  • 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
  • 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.
  • controlled release of one or more agents on the medical device is not always required and/or desirable.
  • 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.
  • 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.
  • 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.
  • other or additional arrangements can be used to control the release of one or more agents from the medical device.
  • 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.
  • 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.
  • 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.
  • many other coating arrangements can be additionally or alternatively used.
  • the one or more agents 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the agent and polymer system combination and location on the medical device can be numerous.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • Non- limiting 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.
  • 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); polyethylene-co-vinyl acetate (PEVA); PBMA/PEVA blend or copolymer; polytetrafluoroethene (Teflon®) and derivatives; poly-paraphenylene ter ephthal amide (Kevlar®); poly(ether ketone) (PEEK); poly(styrene-b-isobutylene-b-styrene) (TransluteTM); tetramethyldisiloxane (side chain or copolymer); polyimides polysulfides; poly(ethylene terephthalate); poly(methyl methacrylate); poly(ethylene-co-m ethyl methacryl
  • 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.
  • hyaluronic acid hyanluron
  • polycarbonates polyorthocarbonates
  • copolymers of vinyl monomers polyacetals
  • biodegradable polyurethanes polyacrylamide
  • polyisocyanates polyamide
  • polyamide polyisocyanates
  • polyamide polyamide
  • copolymers blends, and/or composites of above.
  • 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.
  • 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.
  • 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.
  • the medical device includes and/or is coated with poly (ethylene oxide), poly(ethylene glycol), and polypropylene oxide), polymers of silicone, methane, tetrafluoroethylene (including TEFLONTM brand polymers), tetramethyldisiloxane, and the like.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.).
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • the protective coating materials include parylene, PLGA, POE, PGA, PLLA, PAA, PEG, chitosan and/or derivatives of one or more of these polymers.
  • 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.
  • MEMS microelectromechanical manufacturing
  • 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.).
  • surface structures e.g., pore, channel, pit, rib, slot, notch, bump, teeth, needle, well, hole, groove, etc.
  • MEMS micro-machining, etc.
  • other types of technology e.g., 3D printing, etc.
  • the medical device can optionally include one or more micro-structures (e.g., micro needle, 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.
  • 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.
  • the medical device 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.
  • 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.
  • 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.
  • 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.
  • 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 medical device can optionally be an expandable device that can be expanded by use of some other device (e.g., balloon, etc.).
  • the medical device can optionally be fabricated from a material having no or substantially no shape-memory characteristics.
  • a near net process for a frame and/or other metal component of the medical device there is optionally provided a near net process for a frame and/or other metal component of the medical device.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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).
  • 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).
  • the metal powder used to form the near net or final part includes tungsten (20-80 wt.% and all values and ranges therebetween), copper (1-30 wt.% and all values and ranges therebetween), and one or more other elements 0-5 wt.% (and all values and ranges therebetween).
  • 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.
  • 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.
  • 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.
  • 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.
  • a press of near net or finished part composite 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.
  • a process of creating a metal part with pre-defmed 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.
  • 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.
  • the polymer can optionally be uniformly or non-uniformly dispersed with the metal powder.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.).
  • the formed metal part or medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the formed metal part or medical device or portion of the 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 or portion of the medical device (e.g., frame of the medical device, etc.)
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.) 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 or portion of the medical device (e.g., frame of the medical device, etc.) thereby forming such one or more channels, passageways, and/or voids on the outer
  • 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 portion of the medical device (e.g., frame of the medical device, etc.) or the near net form of the medical device or portion of the medical device (e.g., frame of the medical device, etc.).
  • 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.
  • the polymer constitutes about 5 vol.% of the consolidated and pressed material prior to 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 or portion of the medical device (e.g., frame of the medical device, etc.)
  • the part could include up to about 5 vol.% cavities and/or passageways in the medical device or portion of the medical device (e.g., frame of the medical device, etc.).
  • 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.
  • the average particle size of the polymer is greater than the average particle size of the metal powder prior to sintering.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.) has a porosity associated with the size of the polymer particles as well as the homogeneity of the mixture upon pressing prior to sintering.
  • some of the polymer may optionally remain in the sintered metal part or medical device or portion of the medical device (e.g., frame of the medical device, etc.).
  • the remaining polymer in the sintered part or the medical device or portion of 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.
  • the polymer 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.
  • the refractory metal alloy used to at least partially form the medical device or portion of 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.).
  • 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
  • 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 shape and size of the blank is non-limiting.
  • the rod or tube 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.
  • 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.
  • this is just one example of many different sized tubes that can be formed.
  • the near net frame of the medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. can be formed from one or more ingots of metal or refractory metal alloy.
  • an arc melting process e.g., vacuum arc melting process, etc.
  • an arc melting process can be used to form the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • a controlled atmosphere e.g., vacuum environment, carbon monoxide environment, hydrogen and argon environment, helium, argon, etc.
  • metal particles can be used to form other refractory metal alloys (e.g., molybdenum alloys, rhenium alloys, MoRe alloys, MoReCr alloys, FeCrMoCB alloys, WCu alloys, WRe alloys, ReCr alloys, MoReTa alloy, MoReTi alloy, ReCr alloy, W alloy, Ta alloy, Nb 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.
  • refractory metal alloys e.g., molybdenum alloys, rhenium alloys, MoRe alloys, MoReCr alloys, FeCrMoCB alloys, WCu alloys, WRe alloys, ReCr alloys, MoReTa alloy, MoReTi alloy, ReCr alloy, W alloy, Ta alloy, Nb alloy, etc.
  • 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.
  • the near net frame of the medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the refractory metal alloy is formed by consolidating metal powder.
  • fine particles of metal e.g., Re, W, Mo, Ti, Cu, Ni, Cr, etc.
  • any additives are mixed to form a homogenous blend of particles.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. formed from the metal powders.
  • 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.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • 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.
  • CIP cold isostatic pressing
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), 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 are generally used. Generally, the pressing pressure is about 400-700MPa; however, other pressures can be used.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), 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.
  • an oxygen-reducing atmosphere e.g., helium, argon, hydrogen, argon, and hydrogen mixture, etc.
  • a high hydrogen atmosphere will reduce both the amount of carbon and oxygen in the formed near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc., will generally depend on the type of refractory metal alloy used.
  • the rod 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.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the near net medical device or portion of the medical device can optionally be cleaned and/or polished after the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc., has been form; however, this is not required.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is cleaned and/or polished prior to being further processed; however, this is not required.
  • the formed tube is typically cleaned and/or polished prior to being further processed; however, this is not required.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is resized and/or annealed
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device is used to remove impurities and/or contaminants from the surfaces of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • Impurities and contaminants can become incorporated into the refractory metal alloy during the processing of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the inadvertent incorporation of impurities and contaminants in the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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.
  • a solvent e.g., acetone, methyl alcohol, etc.
  • the refractory metal alloy can be cleaned in other or additional ways.
  • the refractory metal alloy is generally polished by use of a polishing solution that typically includes an acid solution; however, this is not required.
  • the polishing solution includes sulfuric acid; however, other or additional acids can be used.
  • the polishing solution can include by volume 60-95% sulfuric acid and 5-40% de-ionized water (DI water).
  • DI water de-ionized water
  • 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.
  • 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 medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. and the amount of material that needs to be removed from the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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.
  • a given period e.g., 0.1-15 minutes, etc.
  • rinsed e.g., DI water, etc.
  • a short period of time e.g., 0.02-1 minute, etc.
  • 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.
  • a solvent e.g., acetone, methyl alcohol, etc.
  • 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 medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is achieved.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. can be uniformly electropolished or selectively electropolished.
  • the selective electropolishing can be used to obtain different surface characteristics of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. and/or selectively expose one or more regions of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.; however, this is not required.
  • the near net medical device or portion of the medical device can be resized to the desired dimension of the medical device.
  • the cross-sectional area or diameter of the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is reduced to a final near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. can be reduced by the use of one or more drawing processes; however, this is not required.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is drawn down in size.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is reduced in cross-sectional area by about 0.1- 20% each time the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is drawn through a reducing mechanism.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is reduced in cross-sectional area by about 1-15% each time the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is drawn through a reducing mechanism.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is drawn through a reducing mechanism.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is drawn through reducing mechanism.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is reduced in cross-sectional area by about 5-10% each time the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is drawn through reducing mechanism.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. one end of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the tube drawing process is typically a cold drawing process or a plug drawing process through a die.
  • a lubricant e.g., molybdenum paste, grease, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is then drawn though the die.
  • little or no heat is used during the cold drawing process.
  • the outer surface of the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is achieved.
  • a plug drawing process can also or alternatively be used to size the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 vacuum environment e.g., 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 or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.; however, this is not required.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the temperature of the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is heated to temperatures above about 400-500°C
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. tends to begin forming nitrides and/or in the presence of nitrogen and oxygen.
  • a hydrogen environment, an argon and hydrogen environment, etc. is generally used.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is drawn at temperatures below 400-500°C
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device e.g., frame of the medical device, etc.
  • refractory metal alloy 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. being annealed can result in micro-cracking of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is annealed
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. is annealed at a temperature of about 1000-1600°C for about 2-100 minutes.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 oxygen-reducing 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.
  • a hydrogen-containing atmosphere can further reduce the amount of oxygen in the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the chamber in which the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the annealing chamber typically is formed of a material that will not impart impurities to the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • 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.
  • the restraining apparatuses that are used to contact the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), 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.
  • 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.
  • TeflonTM parts can also or alternatively be used.
  • the parameters for annealing can be changed as the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. as the cross- sectional area or diameter; and/or wall thickness of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. are changed. It has been found that good grain size characteristics of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the annealing parameters can be varied as the parameters of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. change.
  • the annealing temperature is correspondingly reduced; however, the times for annealing can be increased.
  • the annealing temperatures of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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.
  • the grain size of the metal in the near net medical device or portion of the medical device 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 or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. should be as uniform as possible.
  • the sigma phase of the metal in the near net medical device or portion of the medical device should be as reduced as much as possible.
  • the sigma phase is a spherical, elliptical or tetragonal crystalline shape in the refractory metal alloy.
  • 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.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • lubricants e.g., nitride compounds, molybdenum paste, grease, oxides, carbides, etc.
  • Impurities that are on one or more surfaces of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. can become permanently embedded into the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is formed into a medical device, and/or can adversely affect the operation and/or life of the medical device.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), 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.
  • a solvent e.g., acetone, methyl alcohol, etc.
  • Kimwipe or other appropriate towel e.g., acetone, methyl alcohol, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube, etc. can be further cleaned by use of a pickling process; however, this is not required.
  • the pickling process includes the use of one or more acids to remove impurities from the surface of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. surface without damaging or over-etching the surface of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • a near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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).
  • one or more different pickling solutions can be used during the pickling process.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the time period for pickling is about 2-120 seconds (and all values and ranges therebetween); however, other time periods can be used.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. and then the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is allowed to dry.
  • a water e.g., DI water, etc.
  • a solvent e.g., acetone, methyl alcohol, etc.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. prior to the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. being drawn and/or annealed; however, this is not required.
  • the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.) (e.g., stent, TAV valve, etc.).
  • the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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.).
  • a portion or all of the medical device or portion of the medical device can be formed by 3D printing.
  • the refractory metal alloy used to partially or fully form the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. to a temperature up to at least about 2200- 2300°C.
  • a pulsed Nd:YAG neodymium-doped yttrium aluminum garnet (NdiYsAEOo) or CO2 laser is used to at least partially cut a pattern of a medical device or portion of the medical device (e.g., frame of the medical device, etc.) out of the refractory metal alloy blank, rod, tube, etc.
  • laser cutting of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. in a non-protected environment can result in impurities being introduced into the cut near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc., which introduced impurities can induce micro-cracking of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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.
  • the refractory metal alloy that used to partially or fully form the near net medical device or portion of the medical device e.g., frame of the medical device, etc.
  • blank, rod, tube etc.
  • the apparatus used to stabilize the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. during the cutting process; however, this is not required.
  • Vibrations in the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. during the cutting of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. can result in the formation of micro-cracks in the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. as the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc. is cut.
  • the average amplitude of vibration during the cutting of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.; however, this is not required.
  • the average amplitude of vibration is no more than about 100% of the wall thickness of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), blank, rod, tube, etc.
  • the average amplitude of vibration is no more than about 75% of the wall thickness of the near net medical device or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), 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 or portion of the medical device (e.g., frame of the medical device, etc.), 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.
  • the refractory metal alloy that is used to partially or fully form the near net medical device or portion of the medical device can optionally be cleaned, polished, sterilized, nitrided, etc.
  • the medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the medical device or portion of the medical device is cleaned prior to being exposed to the polishing solution; however, this is not required.
  • the cleaning process can be accomplished by a variety of techniques such as, but not limited to, 1) using a solvent and wiping the medical device or portion of the medical device (e.g., frame of the medical device, etc.) with a Kimwipe or other appropriate towel, and/or 2) by at least partially dipping or immersing the medical device or portion of the medical device (e.g., frame of the medical device, etc.) in a solvent and then ultrasonically cleaning the metal part or medical device or portion of the medical device (e.g., frame of the medical device, etc.).
  • the medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the polishing solution can include one or more acids.
  • the medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the medical device or portion of the medical device is rinsed with water and/or a solvent and allowed to dry to remove polishing solution on the metal part or medical device or portion of the medical device (e.g., frame of the medical device, etc.).
  • the formed medical device or portion of the medical device is optionally nitrided.
  • the medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the medical device or portion of the medical device is typically cleaned; however, this is not required.
  • the surface of the medical device or portion of the medical device is modified by the present of nitrogen.
  • the nitriding process for the medical device or portion of the medical device can be used to increase surface hardness and/or wear resistance of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) and/or limit or present discoloration of the surface of the frame of the medical device or portion of the medical device (e.g., frame of the medical device, etc.).
  • the nitriding process can be used to increase the wear resistance of articulation surfaces or surface wear on the medical device or portion of the medical device (e.g., frame of the medical device, etc.) to extend the life of the medical device or portion of the medical device (e.g., frame of the medical device, etc.), and/or to increase the wear life of mating surfaces on the medical device or portion of the medical device (e.g., frame of the medical device, etc.), and/or to reduce particulate generation from use of the medical device.
  • the medical device or portion of the medical device e.g., frame of the medical device, etc.
  • the nitriding process can be used to increase the wear resistance of articulation surfaces or surface wear on the medical device or portion of the medical device (e.g., frame of the medical device, etc.) to extend the life of the medical device or portion of the medical device (e.g., frame of the medical device, etc.), and/or to increase the wear life of mating surfaces on the medical device or portion of the
  • a prosthetic heart valve that is configured to be inserted into a desired location in the body (e.g., the aortic valve, tricuspid valve, pulmonary valve, mitral valve).
  • the frame of the prosthetic heart valve can be at least partially formed of a plastically-expandable material that permits crimping of the frame to a smaller profile for delivery and expansion of the prosthetic heart valve to a larger profile.
  • the expansion of the crimped frame can be optionally be use of an expansion device such as, but not limited to, a balloon of on a balloon catheter.
  • the medical device can be a device other than a prosthetic heart valve (e.g., stent, etc.) that includes a frame that is at least partially formed of a plastically expandable material that permits crimping of the frame to a smaller profile for delivery and expansion of the medical device to a larger profile.
  • a prosthetic heart valve e.g., stent, etc.
  • the use of the refractory metal alloy to partially or fully form the medical device or portion of the medical device can be used to increase the strength and/or hardness and/or durability of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) as compared with stainless steel or chromium-cobalt alloys or titanium alloys; thus, less quantity of refractory metal alloy can be used in the medical device or portion of the medical device (e.g., frame of the medical device, etc.) to achieve similar strengths as compared to frames of medical devices formed of different metals.
  • 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.
  • 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 or portion of the medical device (e.g., frame of the medical device, etc.).
  • the thickness of the walls of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) and/or the wires used to at least partially form the medical device or portion of the medical device (e.g., frame of the medical device, etc.) can be made thinner and achieve a similar or improved radial strength as compared with thicker walled frames of 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 or portion of the medical device (e.g., frame of the medical device, etc.), thus increase the life of the medical device.
  • the medical device can be used in regions that subject the medical device to bending.
  • the medical device 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.
  • the improved bendability and flexibility of the medical device or portion of the medical device (e.g., frame of the medical device, etc.) due to the use of the refractory metal alloy can enable 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 or portion of the medical device (e.g., frame of the medical device, etc.).
  • 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.
  • 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 into various regions of a body. Also, the medical device better maintains its expanded profile after expansion so as to facilitate in the success of the medical device in the treatment area.
  • 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.
  • the refractory metal alloy is believed to at least about 10-20% more radiopaque than stainless steel or cobalt-chromium alloy.
  • 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:
  • 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.
  • ⁇ The increased strength of the refractory metal alloy also results in the increased radial strength of the medical device.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • the refractory metal alloy has improved fatigue ductility when subjected to cold working compared to the cold-working of stainless steel, chromium-cobalt alloys, or titanium alloys.
  • the refractory metal alloy has improved durability compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
  • the refractory metal alloy has improved hydrophilicity compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
  • the refractory metal alloy has reduced ion release in the body passageway compared to stainless steel, chromium-cobalt alloys, or titanium alloys.
  • 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.
  • the medical device is expanded in a body passageway, some minor damage to the interior of the passageway can occur.
  • 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.
  • the refractory metal alloy has a magnetic susceptibility that is lower that CoCr alloy, TiAlV 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.
  • One non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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 obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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 obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • Another and/or alternative non-limiting obj ect 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.
  • FIGS. 1A-1E are illustrations of a TAV, a portion of a catheter and a typical TAVR procedure for inserting the TAV into a valve of a heart.
  • FIG. 2A is an illustration of a TAV that includes an inner skirt and leaflet structure.
  • FIG. 2B is an illustration of a TAV frame.
  • FIGS. 3 and 4 are illustrations of a prior art TAV frame formed of CoCr alloy and a TAV frame in accordance with the present disclosure formed of refractory metal alloy of MoRe alloy and having a similar shape and configuration to the TAV frame formed of CoCr alloy, and which illustrates that the frame of the TAV formed of CoCr alloy requires multiple crimping cycles to fully crimp the TAV which can result increased incidence of leaflet damage, and the frame of the TAV formed of MoRe alloy only requires a single crimping cycle to fully crimp the TAV, thereby resulting in reduced incidence of leaflet damage during crimping, and also which results in a decrease crimped outer diameter as compared to a TAV formed of CoCr alloy, and which also illustrates that after each crimping procedure, the frame formed of CoCr alloy has a recoil of greater than 9% after each crimping cycle whereas the recoil of the frame of the refractory metal alloy has a recoil of less than
  • FIG. 5 is a graph that illustrates the amount of recoil of several different metal alloys.
  • FIG. 6 is an illustration of a prior art TAV frame formed of CoCr alloy and a TAV frame in accordance with the present disclosure formed of refractory metal alloy, and which illustrates that the recoil after balloon expansion of the TAV frame formed of CoCr is greater than the recoil of the TAV frame formed of refractory metal alloy after balloon expansion, thus the effective orifice area after expansion of the TAV frame formed of refractory metal alloy is greater than the effective orifice area after expansion of the TAV frame formed of CoCr alloy.
  • FIG. 7 is an illustration that compares the conformability of a metal strip or wire formed of refractory metal to the shape of a die surface as compared to the conformity of a metal strip or wire of CoCr alloy on the same die surface.
  • FIG. 8 is an illustration that compares the conformability of a TAV frame formed of refractory metal alloy that is expanded in a non-circular aortic valve that includes calcium deposits to a similar shaped and configured TAV frame formed of CoCr alloy that is expanded in the same non-circular aortic valve, and which illustrates that the paravalvular leak (PVL) about a TAV having a frame formed of CoCr alloy is greater than the PVL about a TAV having a frame formed of refractory metal alloy due the increase conformability of the frame formed of refractory metal alloy as compared to the conformability of the frame formed of CoCr alloy.
  • PVL paravalvular leak
  • FIGS. 9A-9C illustrate stress vs. reduction in percent area graphs of TiAlV alloy, CoCr alloy and MoRe alloy.
  • FIG. 10 is a graph that illustrates the differences of stiffness and yield strength of a MoRe alloy, CoCr alloy and TiAlV alloy.
  • FIGS. 11-13 are graphs that illustrate the strength and fatigue ductility of a TiAlV alloy, CoCr alloy and MoRe alloy.
  • FIG. 14 illustrates the durability of a MoRe alloy compared to CoCr alloy and a TiAlV alloy.
  • FIG. 15 illustrates the purity of a MoRe alloy to a CoCr alloy and a TiAlV alloy.
  • FIG. 16 illustrates the hydrophilicity of a MoRe alloy, a CoCr alloy, and a TiAlV alloy.
  • FIGS. 17-18 illustrate the ion release rates of a refractory metal alloy such as MoRe.
  • FIG. 19 illustrates the ion release rates in tissue from a MoRe alloy, a CoCr alloy, and a TiAlV alloy.
  • 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.
  • 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.
  • FIGS. 1 A-1E are illustrations of implantable prosthetic heart valve 100 (e.g., TAV) and a method for inserting the prosthetic heart valve 100 in a valve region A (e.g., aortic valve, etc.) of a heart H.
  • the prosthetic heart valve 100 can be implanted in the annulus of the native aortic valve A; however, the prosthetic heart valve 100 also can be configured to be implanted in other valves of the heart.
  • the medical device illustrated is a TAV, the present disclosure is not limited to TAVs or any other heart valve replacement.
  • the medical device in accordance with the present disclosure can be any medical device that can be inserted or otherwise applied to a patient.
  • Non-limiting medical devices in accordance with the present disclosure include orthopedic devices, PFO devices, stents, valves (e.g., heart valve, etc.), spinal implants, devices for treating aneurysms, occlusive devices for use in blood vessels and other body passageways, flow adjusting and/or diversion devices for blood vessels, devices for de- endothelializing a wall of an aneurysm, frame and other structures for use with a spinal implants, vascular implant, graft, dental implant, wire for used in medical procedures, bone implant; artificial disk, artificial spinal disk, prosthetic implant or device to repair, replace and/or support a bone and/or cartilage, bone plate, nail; rod, screw, post; cage, plate, pedicle screw, joint system, anchor, bone spacer, or disk 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.
  • the prosthetic heart valve 100 generally comprises a frame 110 or stent formed of a plurality of posts and/or struts 112, 114 strut joints 113, leaflet structure 200 supported by the frame 110, and an inner skirt 300 secured to the outer surface of the frame 110 and/or leaflet structure 200.
  • the prosthetic heart valve 100 has a “lower” end 120 and an “upper” end 130, wherein the lower end 120 of the prosthetic heart valve 100 is the inflow end and the upper end 130 of the prosthetic heart valve 100 is the outflow end.
  • the configuration of the frame 110 of the prosthetic heart valve 100 is non-limiting. Many different frame configurations can be used for the frame 110 of the prosthetic heart valve 100.
  • the frame 110 includes a plurality of spaced, vertically extending struts or posts 112, or non- vertically extending struts 114 that are connected together at strut joints 113.
  • the frame 110 can be fully formed of non-vertically extending struts 114 that are connected together at strut joints 113.
  • the frame 110 has a 12-post configuration wherein twelve vertically extending struts or post 112 are position about the upper portion of the frame 110.
  • the vertically extending struts or posts 112 are interconnected via a lower row of circumferentially non-vertically extending struts 114 at strut joints 113 and an upper row of circumferentially non- vertically extending struts 114.
  • the non-vertically extending struts 114 can be arrangement in a variety of patterns (e.g., zig-zag pattern, saw-tooth pattern, triangular pattern, polygonal pattern, oval pattern, S-shaped, Y-shaped, H-shaped, E-shaped, V-shaped, Z-shaped, L-shaped, J-sped, W- shaped, U-shaped, N-shaped, M-shaped, C-shaped, X-shaped, F-shaped, etc.).
  • One or more of the posts and/or struts 112, 114 can have the same or different a) thicknesses, b) cross-sectional shape, and/or c) cross-sectional area along a portion or all of the longitudinal length.
  • the upper portion of the frame 110 when expanded, forms twelve hexagonal shaped structures on the upper portion of the frame 110, and three rings of quadrangle shaped structures that form the lower portion of the frame 110.
  • the twelve hexagonal shaped structures are formed of a combination of vertically extending struts or post 112 and non- vertically extending struts 114, and the three rings of quadrangle shaped structures are formed only of non-vertically extending struts 114.
  • many of the frame configurations can be used to form frame 110 for the prosthetic heart valve 100.
  • the frame 110 is partially or fully formed of a refractory metal alloy in accordance with the present disclosure.
  • refractory metal alloys include a Re alloy (30-60 wt.% Re, 40-70 wt.% one or more metal additives [e.g., Mo, Bi, Nb, Ni, Ta, Ti, V, W, Mn, Zr, Ir, Tc, Ru, Rh, Hf, Os, Cu, Y); MoRe alloy, ReW alloy, MoReCr alloy, MoReTa alloy, MoReTi alloy, WCu alloy, ReCr alloy, Mo alloy, W alloy, Ta alloy, Nb alloy, etc.
  • a Re alloy (30-60 wt.% Re, 40-70 wt.% one or more metal additives
  • 90-100% of the frame 110 of the prosthetic heart valve 100 is formed of a refractory metal alloy.
  • 90-100% of the frame 110 of the prosthetic heart valve 100 is formed of MoRe alloy (e.g., 40-60 wt.% Mo, 40-60 wt.% Re and 0-10 wt.% of one or more other metal additives).
  • the frame 110 can be optionally be coated with a polymer material (e.g., silicone, PTFE, ePTFE, polyurethane, polyolefins, hydrogels, biological materials [e.g., pericardium or biological polymers such as collagen, gelatin, or hyaluronic acid derivatives], etc.).
  • a polymer material e.g., silicone, PTFE, ePTFE, polyurethane, polyolefins, hydrogels, biological materials [e.g., pericardium or biological polymers such as collagen, gelatin, or hyaluronic acid derivatives], etc.
  • the coating can be used to partially or fully encapsulate one or more of the vertically extending struts or posts 112 and/or non-vertically extending struts 114 on the frame 110 and/or to partially of fully fill-in one or more of the openings between the non-vertically extending struts 114 and/or vertically extending struts
  • the inner skirt 300 can be formed of a variety of flexible materials (e.g., polymer (e.g., polyethylene terephthalate (PET), polyester, nylon, Kevlar, silicon, etc.), composite material, metal, fabric material, etc.
  • the material used to partially or fully form the inner skirt 300 can be substantially non-elastic (i.e., substantially non-stretchable and non-compressible).
  • the material used to partially or fully form the inner skirt 300 can be a stretchable and/or compressible material (e.g., silicone, PTFE, ePTFE, polyurethane, polyolefins, hydrogels, biological materials [e.g., pericardium or biological polymers such as collagen, gelatin, or hyaluronic acid derivatives], etc.).
  • the inner skirt 300 can optionally be formed from a combination of a cloth or fabric material that is coated with a flexible material or with a stretchable and/or compressible material so as to provide additional structural integrity to the inner skirt 300.
  • the size, configuration and thickness of the inner skirt 300 is non limiting (e.g., thickness of 0.1-20 mils and all values and ranges therebetween).
  • the inner skirt 300 can be secured to the inside and/or outside of the frame 110 using various means (e.g., sutures, clips, clamp arrangement, etc.). [00184] The inner skirt 300 can be used to 1) at least partially seal and/or prevent perivalvular leakage, 2) at least partially secure the leaflet structure 200 to the frame 110, 3) at least partially protect one or more of the leaflets of the leaflet structure 200 from damage during the crimping process of the prosthetic heat valve 100, 4) at least partially protect one or more of the leaflets of the leaflet structure 200 form damage during the operation of the prosthetic heart valve 100 in the heart H.
  • various means e.g., sutures, clips, clamp arrangement, etc.
  • the prosthetic heart valve 100 can optionally include an outer skirt or sleeve (not shown) that is positioned at least partially about the exterior region of the frame 110.
  • the outer skirt or sleeve when used, generally is positioned completely around a portion of the outside of the frame 110. Generally, the outer skirt is positioned about the lower portion of the frame 110 and does not fully cover the upper portion of the frame 110; however, this is not required.
  • the outer skirt can be connected to the frame 110 by a variety of arrangements (e.g., sutures, adhesive, melted connection, clamping arrangement, etc.). At least a portion of the outer skirt can optionally be located on the interior surface of the frame 110; however, this is not required.
  • the outer skirt is formed of a more flexible and/or compressible material than the inner skirt 300; however, this is not required.
  • the outer skirt can be formed of a variety of a stretchable and/or compressible material (e.g., silicone, PTFE, ePTFE, polyurethane, polyolefins, hydrogels, biological materials [e.g., pericardium or biological polymers such as collagen, gelatin, or hyaluronic acid derivatives], etc.).
  • the outer skirt can optionally be formed from a combination of a cloth or fabric material that is coated with the stretchable and/or compressible material so as to provide additional structural integrity to the outer skirt.
  • the size, configuration and thickness of the outer skirt is non-limiting. The thickness of the outer skirt is generally 0.1-20 mils (and all values and ranges therebetween).
  • the leaflet structure 200 can be can be attached to the frame 110 and/or inner skirt 300.
  • the connection arrangement used to secure the leaflet structure 200 to the frame 110 and/or inner skirt 300 is non-limiting (e.g., sutures, melted bold, adhesive, clamp arrangement, etc.).
  • the material used to form the one or more leaflets of the leaflet structure 200 include, but are not limited to, bovine pericardial tissue, biocompatible synthetic materials, or various other suitable natural or synthetic materials.
  • the leaflet structure 200 can be comprised of two or more leaflets (e.g., 2, 3, 4, 5, 6, etc.). In one non-limiting arrangement, the leaflet structure 200 includes three leaflets that are arranged to collapse in a tricuspid arrangement. The size, shape and configuration of the one or more leaflets of the leaflet structure 200 are non-limiting. In one non-limiting arrangement, the leaflets have generally the same shape, size, configuration and thickness.
  • Two of more of the leaflets of the leaflet structure 200 can optionally be secured to one another at their adjacent sides to form commissures of the leaflet structure 200 (the edges where the leaflets come together).
  • the leaflet structure 200 can be secured to the frame 110 and/or inner skirt 300 by a variety of connection arrangement (e.g., sutures, adhesive, melted bond, clamping arrangement, etc.).
  • One or more leaflets of the leaflet structure 200 can optionally include reinforcing structures or strips to 1) facilitate in securing the leaflets together, 2) facilitate in securing the leaflets to the inner skirt 300 and/or frame 110, and/or 3) inhibit or prevent tearing or other types of damage to the leaflets.
  • the prosthetic heart valve 100 is configured to be radially collapsible to a collapsed or crimped state for introduction into the body on a delivery catheter (Fig. IB) and radially expandable to an expanded state for implanting the prosthetic heart valve 100 at a desired location in the heart H (e.g., the aortic valve A, etc.) (FIG. IE).
  • the frame 110 of the prosthetic heart valve 100 is made of a plastically-expandable material (e.g., refractory metal alloy) that permits crimping of the frame 110 to a smaller profile for delivery and expansion of the prosthetic heart valve 100 using an expansion device such as the balloon B of a balloon catheter C.
  • the prosthetic heart valve 100 is crimped into a portion of balloon B of the balloon catheter C.
  • Various type of crimping apparatus and techniques can be used to crimp the prosthetic heart valve on the balloon delivery catheter.
  • the process of crimping a prosthetic heart valve 100 using a crimping device is known in the art and will not be described herein. During a crimping procedure, damage to the leaflets of leaflet structure 200 should be avoided.
  • the balloon delivery catheter C is inserted through a blood vessel and to the location in the heart H wherein the prosthetic heart valve 100 is to be deployed (See FIG. 1C).
  • the balloon B on the balloon delivery catheter C is expanded to thereby cause the prosthetic heart valve 100 to be expanded and secured in a valve region A of the heart H (See FIG. ID).
  • the balloon B is deflated and the balloon delivery catheter C is removed from the patient (See FIG. IE).
  • the frame 110 of the prosthetic heart valve 100 can be configured such that it can be crimped onto a delivery catheter C so that the crimped prosthetic heart valve 100 can be inserted in heart valves that are less than 22 Fr.
  • Commercially available prior art prosthetic heart values can only be crimped to a diameter of about 24-27 FR (8-9 mm) due to the materials used to form the frame of such prosthetic heart valves.
  • the prosthetic heart valve 100 in accordance with the present disclosure can be inserted into smaller sized heart valves that could not previously be treated with prior art prosthetic heart valves.
  • the prosthetic heart valve 100 in accordance with the present disclosure can be sized and configured to be inserted in heart valves that are greater than 22 Fr.
  • the refractory metal alloy frame 110 of the prosthetic heart valve 100 and other types of expandable medical devices can be crimped to have a crimped outer diameter that is at least 5% and up to a 33% smaller (e.g., 5-33% smaller and all value and ranges therebetween) than a crimped outer diameter of a frame of the same size, configuration and shape that is formed of Co-Cr alloy (e.g., L605; MP35N; Phynox; Eligory; 35Co-35Ni-20Cr-10Mo; 40Co-20Cr- 16Fe- 15Ni7Mo; Co-20Cr-15W-10Ni; 15-30 wt.% Cr, 10-20 wt.% W, 5-35 wt.% Ni, 0-3 wt.% Fe, 0-2 wt.% Mn, 0-10 wt.% Mo, 0-1 wt.% Ti, 0.0.5 wt.%
  • Co-Cr alloy e.g., L605;
  • the refractory metal alloy frame 110 of the prosthetic heart valve 100 and other types of expandable medical devices can be crimped to have a crimped outer diameter that is at least 5% and up to a 50% smaller (e.g., 5-50% smaller and all value and ranges therebetween) than a crimped outer diameter of a frame of the same size, configuration and shape that is formed of stainless steel (e.g., 316, 316L).
  • expandable frames for prosthetic heart valves are only formed of certain cobalt-chromium alloys and NiTi alloys.
  • the present disclosure illustrates the many advantages for using a refractory metal alloy in accordance with the present disclosure in expandable medical devices, comparisons of the refractory metal alloy of the present disclosure to cobalt-chromium alloys and NiTi alloys will only be made in this disclosure when referring to expandable prosthetic heart valves such as, but not limited to TAVR devices.
  • the refractory metal alloy frame 110 of the prosthetic heart valve 100 and other types of expandable medical devices can be crimped to have a crimped outer diameter that is at least 5% and up to a 40% smaller (e.g., 5-40% smaller and all value and ranges therebetween) than a crimped outer diameter of a frame of the same size, configuration and shape that is formed of nitinol (self-expanding nickel titanium alloy - 49-60% wt.% Ni and 40-51 wt.% Ti).
  • the refractory metal alloy frame 110 of the prosthetic heart valve 100 and other types of expandable medical devices can be crimped to have a crimped outer diameter that is at least 5% and up to a 40% smaller (e.g., 5-40% smaller and all value and ranges therebetween) than a crimped outer diameter of a frame of the same size, configuration and shape that is formed of TiAlV alloys (e.g., Ti-6A1-4V; 5.5-6.5 wt.% Al, 3.5-4.5 wt.% V and balance Ti; 3.5-4.5 wt.% vanadium, 5.5-6.75 wt.% aluminum, 0.3 wt.% max iron, 0.2 wt.% max oxygen, 0.08 wt.% max carbon, 0.05 wt.% max nitrogen, 0.015 wt.% max hydrogen H, 0.05 wt.% max yttrium, balance titanium).
  • TiAlV alloys e.g., Ti-6A1-4V; 5.5-
  • EOA effective orifice area
  • a frame for a prosthetic heart device e.g., TAVR, etc.
  • a refractory metal alloy in accordance with the present disclosure has improved properties as compared to frames for prosthetic heart valves that are formed of MP35N or NiTi alloy.
  • the frame of the prosthetic heart valve that is formed of a refractory metal alloy has several advantages over frames for prosthetic heart valves that are formed of MP35N or NiTi alloy, namely 1) the outer diameter (OD) of the crimped prosthetic valve having a frame formed of refractory metal alloy is smaller than the OD crimped diameter of the crimped prosthetic valve having a frame formed of MP35N (e.g., cobalt-chromium alloy) or NiTi alloy, 2) the strut joint width on the frame (e.g., the location that the end of a strut is connected to another portion of the frame) that is formed of a refractory metal alloy can be less than the strut joint width on the frame formed of MP35N or NiTi alloy, 3) the strut width on the frame that is formed of a refractory metal alloy is less than
  • the strength of the refractory metal alloy is greater than a cobalt-chromium alloy, stainless steel, nickel -titanium alloy or a TiAlV alloy, thus the strut width and strut joints of expandable frames can be made smaller than frames formed of such other alloys, thereby a frame for a medical formed of a refractory metal alloy can be made smaller without sacrificing the strength of the frame.
  • the amount of recoil of a frame formed of refractory metal alloy when the frame is crimped or expanded from the crimped state is less than the amount of recoil of a frame formed of cobalt-chromium alloy, stainless steel, nickel -titanium alloy or a TiAlV alloy.

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  • Oral & Maxillofacial Surgery (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un dispositif médical qui est au moins partiellement constitué d'un alliage métallique réfractaire, et un procédé d'insertion du dispositif médical chez un patient.
PCT/US2022/038698 2021-07-28 2022-07-28 Dispositif médical comprenant un alliage métallique réfractaire WO2023009739A1 (fr)

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US202163226270P 2021-07-28 2021-07-28
US63/226,270 2021-07-28
US202163247540P 2021-09-23 2021-09-23
US63/247,540 2021-09-23
US17/512,174 2021-10-27
US17/512,174 US11504451B2 (en) 2014-06-24 2021-10-27 Metal alloys for medical devices
US17/586,270 2022-01-27
US17/586,270 US20230040416A1 (en) 2021-07-28 2022-01-27 Medical Device That Includes a Rhenium Metal Alloy
US202263316077P 2022-03-03 2022-03-03
US63/316,077 2022-03-03
US202263389481P 2022-07-15 2022-07-15
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US20060200224A1 (en) * 2005-03-03 2006-09-07 Icon Interventional Systems, Inc. Metal alloy for a stent
US20100023115A1 (en) * 2008-07-23 2010-01-28 Boston Scientific Scimed, Inc. Drug-eluting stent
US20140099279A1 (en) * 2005-03-03 2014-04-10 Icon Medical Corp. Metal alloys for medical devices
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US20140099279A1 (en) * 2005-03-03 2014-04-10 Icon Medical Corp. Metal alloys for medical devices
US20170273785A1 (en) * 2005-05-24 2017-09-28 Medtronic Corevalve Llc Prosthetic Valve System and Methods for Transluminal Delivery
US20100023115A1 (en) * 2008-07-23 2010-01-28 Boston Scientific Scimed, Inc. Drug-eluting stent
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