CA2152594C - Clad composite stent - Google Patents
Clad composite stentInfo
- Publication number
- CA2152594C CA2152594C CA002152594A CA2152594A CA2152594C CA 2152594 C CA2152594 C CA 2152594C CA 002152594 A CA002152594 A CA 002152594A CA 2152594 A CA2152594 A CA 2152594A CA 2152594 C CA2152594 C CA 2152594C
- Authority
- CA
- Canada
- Prior art keywords
- core
- case
- filament
- composite filament
- cold
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
- A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
-
- 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
-
- 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
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
-
- 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/18—Materials at least partially X-ray or laser opaque
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21F—WORKING OR PROCESSING OF METAL WIRE
- B21F45/00—Wire-working in the manufacture of other particular articles
- B21F45/008—Wire-working in the manufacture of other particular articles of medical instruments, e.g. stents, corneal rings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/0077—Special surfaces of prostheses, e.g. for improving ingrowth
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2210/00—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2210/0076—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof multilayered, e.g. laminated structures
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2220/00—Fixations or connections for prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2220/0008—Fixation appliances for connecting prostheses to the body
- A61F2220/0016—Fixation appliances for connecting prostheses to the body with sharp anchoring protrusions, e.g. barbs, pins, spikes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2220/00—Fixations or connections for prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2220/0025—Connections or couplings between prosthetic parts, e.g. between modular parts; Connecting elements
- A61F2220/0033—Connections or couplings between prosthetic parts, e.g. between modular parts; Connecting elements made by longitudinally pushing a protrusion into a complementary-shaped recess, e.g. held by friction fit
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2240/00—Manufacturing or designing of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2240/001—Designing or manufacturing processes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2250/00—Special features of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2250/0058—Additional features; Implant or prostheses properties not otherwise provided for
- A61F2250/0096—Markers and sensors for detecting a position or changes of a position of an implant, e.g. RF sensors, ultrasound markers
- A61F2250/0098—Markers and sensors for detecting a position or changes of a position of an implant, e.g. RF sensors, ultrasound markers radio-opaque, e.g. radio-opaque markers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—Metals or alloys
- A61F2310/00029—Cobalt-based alloys, e.g. Co-Cr alloys or Vitallium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M25/00—Catheters; Hollow probes
- A61M25/0009—Making of catheters or other medical or surgical tubes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S623/00—Prosthesis, i.e. artificial body members, parts thereof, or aids and accessories therefor
- Y10S623/924—Material characteristic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12819—Group VB metal-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12875—Platinum group metal-base component
Abstract
A body compatible stent (16) is formed of multiple filaments (18, 20) arranged in two sets of oppositely directed helical windings interwoven with one another in a braided configuration. Each of the filaments (18, 20) is a compodite including a central core (24) and a case (26) surrounding the core (24). In the more preferred version, the core (24) is formed of a radiopaque and relatively ductile rnaterial, e.g. tantalum or platinum. The outer case (26) is formed of a relatively resilient material, e.g. a cobalt/chromium based alloy. Favorable mechanical characteristics of the stent (16) are determined by the case (26), while the core (24) enables in vivo imaging of the stent (16). The composite filaments (18a) are formed by a drawn filled tubing process in which the core (24) is inserted into a tubular case (26) of a diameter substantially more than the intended final filament diameter. The composite filament (18a) is cold-worked in several steps to reduce its diameter, and annealed between successive cold-working steps. After the final cold working step, the composite filament (18a) is formed into the desired shape and age hardened. Alternative composite filaments (18a) employ an intermediate barrier layer (86) between the case (84) and core (82), a biocompatible cover layer (94) surrounding the case (92), and a radiopaque case (92) surrounding a structural core (90).
Description
WO94/16~ PCT~S93/1~62 21~2~9~
CLAD COMPOSITE STENT
Background of the Invention The present invention relates to body implantable medical devices, and more particularly to stents and other prostheses configured for high radio-opacity as well as favorable mechanical characteristics.
Recently several prostheses, typically of lattice work or open frame construction, have been developed for a variety of medical applications, e.g.
intravascular stents for treating stenosis, prostheses for maintaining openings in the urinary tracts, biliary prostheses, esophageal stents, renal stents, and vena cava filters to counter thrombosis. One particularly well accepted device is a self-expanding mesh stent disclosed in U.S. Patent No. 4,655,771 (Wallsten). The stent is a flexible tubular braided structure formed of helically wound thread elements. The thread elements can be constructed of a biocompatible plastic or metal, e.g. certain stainless steels, polypropylene, polyesters and polyurethanes.
Alternatively, stents and other prostheses can be expandable by plastic deformation, usually by expanding a dilation balloon surrounded by the prosthesis. For example, U.S. Patent No. 4,733,665 (Palmaz) discloses an intraluminal graft constructed of stainless steel strands, either woven or welded at their intersections with silver. U.S. Patent No. 4,886,062 (Wiktor) features a balloon expandable stent constructed of stainless steel, a copper alloy, titanium, or gold.
Regardless of whether the prosthesis is self-expanding or plastically expanded, accurate placement of the prosthesis is critical to its effective performance. Accordingly, there is a need to visually perceive the prosthesis as it is being placed within a W094/16~ PCT~S93/1~62 ,2~
blood vessel or other body cavity. Further, it is advantageous and sometimes necessary to visually locate and inspect a previously deployed prosthesis.
Fluoroscopy is the prevailing technique for such visualization, and it requires radio-opacity in the materials to be imaged. The preferred structural materials for prosthesis construction, e.g. stainless steels and cobalt-based alloys, are not highly radiopaque. Consequently, prostheses constructed of these materials do not lend themselves well to fluoroscopic imaging.
Several techniques have been proposed, in apparent recognition of this difficulty. For example, U.S.
Patent No. 4,681,110 (Wiktor) discloses a self-expanding blood vessel liner formed of woven plasticstrands, radially compressed for delivery within a tube. A metal ring around the tube is radiopaque.
Similarly, U.S. Patent No. 4,830,003 (Wolff) discusses confining a radially self-expanding stent within a delivery tube, and providing radiopaque markers on the delivery tube. This approach facilitates imaging only during deployment and initial placement.
To permit fluoroscopic imaging after placement, the stent itself must be radiopaque. The Wolff patent suggests that the stent can be formed of platinum or a platinum-iridium alloy for substantially greater radio-opacity. Such stent, however, lacks the required elasticity, and would exhibit poor resistance to fatigue. The Wiktor '110 patent teaches the attachment of metal staples to its blood vessel liner, to enhance radio-opacity. However, for many applications (e.g. in blood vessels), the stent is so small that such staples either would be too small to provide useful fluoroscopic imaging, or would adversely affect the ~ W094/16646 2 1 ~ 2 5 ~ ~ PCT~S93/11262 efficiency and safety of deploying the stent or other prosthesis. This Wiktor patent also suggests infusing its plastic strands with a suitable filler, e.g. gold or barium sulfate, to enhance radio-opacity. Wiktor provides no teaching as to how this might be done.
Further, given the small size of prostheses intended for blood vessel placement, this technique is unlikely to materially enhance radio-opacity, due to an insufficient amount and density of the gold or barium sulfate.
Therefore, it is an object of the present invention to provide a stent or other prosthesis with substantially enhanced radio-opacity, without any substantial reduction in the favorable mechanical properties of the prosthesis.
Another object is to provide a resilient body insertable composite filament having a high degree of radio-opacity and favorable structural characteristics, even for stents employing relatively small diameter filaments.
A further object is to provide a process for manufacturing a composite filament consisting essentially of a structural material for imparting desired mechanical characteristics, in combination with a radiopaque material to substantially enhance fluoroscopic imaging of the filament.
Yet another object is to provide a case composite prosthesis in which a highly radiopaque material and a structural material cooperate to provide mechanical ~0 stability and enhanced fluoroscopic imaging, and further are selectively matched for compatibility as to their crystalline structure, coefficients of thermal expansion, and annealing temperatures.
W094/16646 PCT~S93/1~62 ~
æ~52~9~
SummarY of the Invention To achieve these and other objects, there is provided a process for manufacturing a resilient body insertable composite filament. The process includes the following steps:
a. providing an elongate cylindrical core substantially uniform in lateral cross-section and having a core diameter, and an elongate tubular case or shell substantially uniform in lateral cross-section and having a case inside diameter, wherein one of the core and case is formed of a radiopaque material and the other is formed of a resilient material having an yield strength (0.2% offset) of at least 150,000 psi, wherein the core diameter is less than the interior diameter of the case, and the lateral cross-sectional area of the core and case is at most ten times the lateral cross-sectional area of the core;
b. inserting the core into the case to form an elongate composite filament in which the case surrounds the core;
c. cold-working the composite filament to reduce the lateral cross-sectional area of the composite filament by at least 15%, whereby the composite filament has a selected diameter less than an initial outside diameter of composite filament before cold-working;
d. annealing the composite filament after cold- working, to substantially remove strain hardening and other stresses induced by the cold-working step;
e. mechanically form~ng the annealed composite filament into a predetermined shape; and f. after the cold-working and annealing steps, and while maintaining the composite filament in the predetermined shape, age hardening the composite WO94/16~K PCT~S93/1~
CLAD COMPOSITE STENT
Background of the Invention The present invention relates to body implantable medical devices, and more particularly to stents and other prostheses configured for high radio-opacity as well as favorable mechanical characteristics.
Recently several prostheses, typically of lattice work or open frame construction, have been developed for a variety of medical applications, e.g.
intravascular stents for treating stenosis, prostheses for maintaining openings in the urinary tracts, biliary prostheses, esophageal stents, renal stents, and vena cava filters to counter thrombosis. One particularly well accepted device is a self-expanding mesh stent disclosed in U.S. Patent No. 4,655,771 (Wallsten). The stent is a flexible tubular braided structure formed of helically wound thread elements. The thread elements can be constructed of a biocompatible plastic or metal, e.g. certain stainless steels, polypropylene, polyesters and polyurethanes.
Alternatively, stents and other prostheses can be expandable by plastic deformation, usually by expanding a dilation balloon surrounded by the prosthesis. For example, U.S. Patent No. 4,733,665 (Palmaz) discloses an intraluminal graft constructed of stainless steel strands, either woven or welded at their intersections with silver. U.S. Patent No. 4,886,062 (Wiktor) features a balloon expandable stent constructed of stainless steel, a copper alloy, titanium, or gold.
Regardless of whether the prosthesis is self-expanding or plastically expanded, accurate placement of the prosthesis is critical to its effective performance. Accordingly, there is a need to visually perceive the prosthesis as it is being placed within a W094/16~ PCT~S93/1~62 ,2~
blood vessel or other body cavity. Further, it is advantageous and sometimes necessary to visually locate and inspect a previously deployed prosthesis.
Fluoroscopy is the prevailing technique for such visualization, and it requires radio-opacity in the materials to be imaged. The preferred structural materials for prosthesis construction, e.g. stainless steels and cobalt-based alloys, are not highly radiopaque. Consequently, prostheses constructed of these materials do not lend themselves well to fluoroscopic imaging.
Several techniques have been proposed, in apparent recognition of this difficulty. For example, U.S.
Patent No. 4,681,110 (Wiktor) discloses a self-expanding blood vessel liner formed of woven plasticstrands, radially compressed for delivery within a tube. A metal ring around the tube is radiopaque.
Similarly, U.S. Patent No. 4,830,003 (Wolff) discusses confining a radially self-expanding stent within a delivery tube, and providing radiopaque markers on the delivery tube. This approach facilitates imaging only during deployment and initial placement.
To permit fluoroscopic imaging after placement, the stent itself must be radiopaque. The Wolff patent suggests that the stent can be formed of platinum or a platinum-iridium alloy for substantially greater radio-opacity. Such stent, however, lacks the required elasticity, and would exhibit poor resistance to fatigue. The Wiktor '110 patent teaches the attachment of metal staples to its blood vessel liner, to enhance radio-opacity. However, for many applications (e.g. in blood vessels), the stent is so small that such staples either would be too small to provide useful fluoroscopic imaging, or would adversely affect the ~ W094/16646 2 1 ~ 2 5 ~ ~ PCT~S93/11262 efficiency and safety of deploying the stent or other prosthesis. This Wiktor patent also suggests infusing its plastic strands with a suitable filler, e.g. gold or barium sulfate, to enhance radio-opacity. Wiktor provides no teaching as to how this might be done.
Further, given the small size of prostheses intended for blood vessel placement, this technique is unlikely to materially enhance radio-opacity, due to an insufficient amount and density of the gold or barium sulfate.
Therefore, it is an object of the present invention to provide a stent or other prosthesis with substantially enhanced radio-opacity, without any substantial reduction in the favorable mechanical properties of the prosthesis.
Another object is to provide a resilient body insertable composite filament having a high degree of radio-opacity and favorable structural characteristics, even for stents employing relatively small diameter filaments.
A further object is to provide a process for manufacturing a composite filament consisting essentially of a structural material for imparting desired mechanical characteristics, in combination with a radiopaque material to substantially enhance fluoroscopic imaging of the filament.
Yet another object is to provide a case composite prosthesis in which a highly radiopaque material and a structural material cooperate to provide mechanical ~0 stability and enhanced fluoroscopic imaging, and further are selectively matched for compatibility as to their crystalline structure, coefficients of thermal expansion, and annealing temperatures.
W094/16646 PCT~S93/1~62 ~
æ~52~9~
SummarY of the Invention To achieve these and other objects, there is provided a process for manufacturing a resilient body insertable composite filament. The process includes the following steps:
a. providing an elongate cylindrical core substantially uniform in lateral cross-section and having a core diameter, and an elongate tubular case or shell substantially uniform in lateral cross-section and having a case inside diameter, wherein one of the core and case is formed of a radiopaque material and the other is formed of a resilient material having an yield strength (0.2% offset) of at least 150,000 psi, wherein the core diameter is less than the interior diameter of the case, and the lateral cross-sectional area of the core and case is at most ten times the lateral cross-sectional area of the core;
b. inserting the core into the case to form an elongate composite filament in which the case surrounds the core;
c. cold-working the composite filament to reduce the lateral cross-sectional area of the composite filament by at least 15%, whereby the composite filament has a selected diameter less than an initial outside diameter of composite filament before cold-working;
d. annealing the composite filament after cold- working, to substantially remove strain hardening and other stresses induced by the cold-working step;
e. mechanically form~ng the annealed composite filament into a predetermined shape; and f. after the cold-working and annealing steps, and while maintaining the composite filament in the predetermined shape, age hardening the composite WO94/16~K PCT~S93/1~
2~s2~
filament.
In one preferred version of the process, the radiopaque material has a linear attenuation coefficient, at 100 KeV, of at least 25 cm -1. The radiopaque material forms the core, and is at least as ductile as the case. The outside diameter of the composite filament, before cold-working, preferably is at most about six millimeters (about 0.25 inches). The cold-working step can include drawing the composite filament serially through several dies, with each die plastically deforming the composite filament to reduce the outside diameter. Whenever a stage including one or more cold-working dies has reduced the cross-sectional area by at least 25%, an annealing step should be performed before any further cold-working.
During each annealing step, the composite filament is heated to a temperature in the range of about 1900 - 2300 F. for a period depending on the filament diameter, typically in the range of several seconds to several minutes. The core material and cladding (case) materials preferably are selected to have overlapping annealing temperature ranges, and similar coefficients of thermal expansion. The core and case materials further can be selectively matched as to their crystalline structure and metallurgical compatibility.
In an alternative version of the process, the initial outside diameter of the composite structure (billet) typically is at least fifty millimeters (about two inches) in diameter. Then, before cold-working, the composite filament is subjected to temperatures in the annealing range while the outside diameter is substantially reduced, either by swaging or by pulltrusion, in successive increments until the outside diameter is at most about 6 millimeters (.25 inches).
W094/16~K PCT~S93/1~62 ~52~
The resulting filament is processed as before, in alternative cold-working and annealing stages.
Further according to the process, the composite filament can be severed into a plurality of strands.
Then, the strands are arranged in two oppositely directed sets of parallel helical windings about a cylindrical form, with the strands intertwined in a braided configuration to form multiple intersections.
Then, while the strands are maintained in a lo predetermined uniform tension, they are heated to a temperature in the range of about 700 - 1200 F., more preferably 900 - 1000 F., for a time sufficient to age harden the helical windings.
The result of this process is a resilient, body implantable prosthesis. The prosthesis has a plurality of resilient strands, helically wound in two oppositely directed sets of spaced apart and parallel strands, interwoven with one another in a braided configuration.
Each of the strands includes an elongate core and an elongate tubular case surrounding the core. A cross-sectional area of the core is at least ten percent of the cross-sectional area of the strand. The core is constructed of a first material having a linear attenuation coefficient of at least 25 cm -1 at 100 KeV.
The case is constructed of a resilient second material, less ductile than the first material.
More generally, the process can be employed to form a body compatible device comprising an elongate filament substantially uniform in lateral cross-section over its length and including an elongate cylindrical core and an elongate tubular case surrounding the core.
One of the core and case is constructed of a first material having an yield strength (0.2~ offset) of at least twice that of the second material. The other of W094/16~ PCT~S93/1~62 ~ Sg~
the core and case is constructed of a second material being radiopaque and at least as ductile as the first material.
In a highly preferred version of the invention, the core is constructed of tantalum for radio-opacity, and the case is constructed of a cobalt-based alloy, e.g. as available under the brand names "Elgiloy", "Phynox" and "MP35N". The "Elgiloy" and "Phynox"
alloys contain cobalt, chromium, nickel, and molybdenum, along with iron. Either of these alloys is well matched with tantalum, in terms of overlapping annealing temperature ranges, coefficients of thermal expansion and crystalline structure. The tantalum core and alloy case can be contiguous with one another, with virtually no formation of intermetallics.
When otherwise compatible core and case materials present the risk of intermetallic formation, an intermediate layer, e.g. of tantalum, niobium, or platinum, can be formed between the core and the case to provide a barrier against intermetallic formation.
Further, if the case itself is not sufficiently biocompatible, a biocompatible coating or film can surround the case. Tantalum, platinum, iridium and their alloys, or stainless steels can be used for this purpose.
While disclosed herein in connection with a radially self-expanding stent, the composite filaments can be employed in constructing other implantable medical devices, e.g. vena cava filters, blood filters and thrombosis coils. Thus, in accordance with the present invention there is provided a resilient, body compatible prosthesis which, despite being sufficiently small for placement within blood vessels and similarly sized body cavities, has sufficient radio-opacity for W094/16~K PCT~S93/1~62 ~
~iS~
fluoroscopic imaging based on the prosthesis materials themselves.
In the Drawings For a further understanding of the above and other features and advantages, reference is made to the following detailed description and to the drawings, in which:
Figure 1 is a side elevation of a self-expanding stent constructed according to the present invention;
Figure 2 is an end elevational view of the stent;
Figure 3 is an enlarged partial view of one of the composite filaments forming the stent;
Figure 4 is an enlarged sectional view taken along the line 4-4 in Figure 3;
Figures 5-9 schematically illustrate a process for manufacturing the stent;
Figure 10 schematically illustrates a swaging step of an alternative process for manufacturing the stent;
Figure 11 is an end elevational view of an alternative embodiment filament;
Figure 12 is an elevational view of several components of an alternative composite filament constructed according to the present invention;
Figure 13 is an end elevational view of the composite filament formed by the components shown in Figure 12; and Figure 14 is an end elevational view of another alternative embodiment composite filament.
Detailed Description of the Preferred Embodiment Turning now to the drawings, there is shown in Figures 1 and 2 a body implantable prosthesis 16, frequently referred to as a stent. Stent 16 is of open mesh or weave construction, consisting of two sets of oppositely directed, parallel and spaced apart WO94116~K PCT~S9311~62 ~ ~lS~S~
helically wound strands or filaments indicated at 18 and 20, respectively. The sets of strands are interwoven in an over and under braided configuration to form multiple intersections, one of which is indicated at 22.
Stent 16 is illustrated in its relaxed state, i.e.
in the configuration it assumes when subject to no external stresses. The filaments or strands of stent 16 are resilient, permitting a radial compression of the stent into a reduced-radius, extended-length configuration suitable for transluminal delivery of the stent to the intended placement site. As a typical example, stent 16 can have a diameter of about ten millimeters in the relaxed state, and is elastically compressed to a diameter of about 2 millimeters (.08 inches) and an axial length of about twice the axial length of the relaxed stent. However, different applications call for different diameters. Further, it is well known to predetermine the degree of axial elongation for a given radial compression, by selectively controlling the angle between the oppositely directed helical strands.
Inelastic open-weave prostheses, expandable for example by dilation balloons, provide an alternative to resilient prostheses. Resilient or self-expanding prostheses often are preferred, as they can be deployed without dilation balloons or other stent expanding means. Self-expanding stents can be preselected according to the diameter of the blood vessel or other intended fixation site. While their deployment requires skill in stent positioning, such deployment does not require the additional skill of carefully dilating the balloon to plastically expand the prosthesis to the appropriate diameter. Further, the WO94/16~ 9 ~ PCT~S9311~62 ~
self-expanding stent remains at least slightly elastically compressed after fixation, and thus has a restoring force which facilitates acute fixation. By contrast, a plastically expanded stent must rely on the restoring force of deformed tissue, or on hooks, barbs, or other independent fixation elements.
Accordingly, materials forming the strands for filaments must be strong and resilient, biocompatible, and resistant to fatigue and corrosion. Vascular applications require hemocompatibility as well.
Several materials meet these needs, including stainless "spring" steels, and certain cobalt-based alloys: more particularly two alloys including cobalt, chromium, iron, nickel and molybdenum sold under the brand names "Elgiloy" (available from Carpenter Technology Corporation of Reading, Pennsylvania) and "Phynox"
(available from Metal Imphy of Imphy, France), respectively. Another suitable cobalt-chromium alloy is available under the brand name "MP35N" from Carpenter Technology Corporation of Reading, Pennsylvania.
Further, it is advantageous to form a prosthesis with substantial open space to promote embedding of the stent into tissue, and fibrotic growth through the stent wall to enhance long-term fixation. A more open construction also enables substantial radial compression of the prosthesis for deployment. In a typical construction suitable for transluminal implantation, the filaments can have a diameter of about O.l millimeter (.004 inches), with adjacent parallel filaments spaced apart from one another by about 1-2 millimeters (.04-.08 inches) when the stent is in the relaxed state.
Fluoroscopic imaging of a conventional open weave WO94/16~K ~ 9 4 PCT~S93/1~62 prosthesis is extremely difficult. Due to their minute diameters and the materials involved, the filaments exhibit a relatively poor contrast to body tissue for fluoroscopic imaging purposes. The filaments also require a high degree of spatial resolution in the imaging equipment involved. Thus, a stent recognizable on X-ray film may not be distinguishable for real time imaging, due to the relatively poor spatial resolution of the video monitor as compared to X-ray film.
According to the present invention, however, prosthesis 16 is substantially more amenable to fluoroscopic imaging, due to the construction of strands 18 and 20. In particular, the strands cooperate to present a sufficiently radiopaque mass at the tangen~s of device 16 (parallel to the X-rays) for satisfactory real time imaging. As seen in Figures 3 and 4, a filament 18a of the prosthesis is of composite construction, with a radiopaque core 24 surrounded by and concentric with an annular resilient case 26. Core 24 is highly absorptive of X-rays, preferably having a linear attenuation coefficient of at least 25 (and more preferably at least 50) cm -1 at 100 KeV. Materials with relatively high atomic numbers and densities tend to have the necessary attenuation coefficients. More particularly, it has been found that materials with an atomic number (elements) or "effective" atomic number (based on a weighted average of elements in alloys or compounds) of at least fifty, and densities of at least 0.5 pounds per cubic inch, exhibit the required ability to absorb X-rays. Finally, core 24 is preferably a ductile material so that it readily conforms to the - shape of the case.
By contrast, case 26 is formed of a highly resilient material, preferably with a yield strength WO94/1~K PCT~S9311~62 2i5~59~ --(0.2% offset) of at least 150,000 psi. More preferably, the yield strength is at least 300,000 psi.
Consequently, the mechanical behavior of composite filament 18a in terms of elastic deformation in response to external stresses is, essentially, the behavior of case 26.
In addition to individual characteristics of the core and case, it is desirable to selectively match core and case materials based on certain common characteristics. The core and case materials should have the same or substantially the same linear coefficients of thermal expansion. Similarity of core and case materials in their crystalline structure is also an advantage. Finally, the core and case materials should have an overlap in their annealing temperature ranges, to facilitate manufacture of the filaments according to the process to be explained.
In a highly preferred embodiment, core 24 is formed of tantalum, and case 26 is formed of a cobalt-based alloy, more particularly Elgiloy (brand) alloy.
Tantalum is a ductile metal having an atomic number of 73 and a density of about 0.6 pounds per cubic inch.
Its linear attenuation coefficient, at lO0 KeV, is 69.7 cm -1 The Elgiloy alloy includes principally cobalt and chromium, and has an effective atomic number of less than thirty and a density substantially less than 0.5 pounds per cubic inch. However, the alloy is body compatible, hemocompatible and highly resilient, with 30 a yield strength (0.2% offset) of at least 350,000 psi, after cold working and age hardening.
Case 26 and core 24 thus cooperate to provide a prosthesis that can be viewed in vivo, and in real time. Of course, the amount of core material in W094/16646 PCT~S93/11262 2l52s~
relation to the amount of case material must be sufficient to insure radio-opacity while maintaining the favorable mechanical characteristics of stent 16.
It has been found that the area of core 24, taken along a transverse or lateral plane as illustrated in Figure 4, should be within the range of about ten percent to forty-six percent of the filament lateral cross-sectional area, i.e. the area of the combined case and core.
Tantalum and the Elgiloy alloy are well matched, in that the materials have similar linear coefficients of thermal expansion (3.6 x 10-6 per degree F. and 8.4 x 10-6 per degree F., respectively), similar crystalline structures, and annealing temperatures in the range of 1900 - 2300 F. Further, there is virtually no tendency for the formation of intermetallic compounds along the tantalum/Elgiloy alloy interface.
Platinum and platinum alloys (e.g. platinum iridium) also are suitable as materials for core 24.
The atomic number of platinum is 78, and its density is 0.775 pounds per cubic inch. Its linear attenuation coefficient at 100 KeV is 105 cm -1. The linear coefficient of thermal expansion for platinum is about 4.9 x 10-6 per degree F.
Thus, as compared to tantalum, platinum is structurally more compatible with the Elgiloy alloy, and more effectively absorbs X-rays. Accordingly, platinum is particularly well suited for use in prostheses formed of small diameter filaments. The primary disadvantage of platinum, with respect to tantalum, is its higher cost.
- Further materials suitable for radiopaque core 24 include gold, tungsten, iridium, rhenium, ruthenium, and depleted uranium.
WO94/16~ ~ PCT~S9311~62 21 ~S~
Other materials suitable for case 26 include other cobalt-based alloys, e.g. the Phynox and MP35N brand alloys. Cobalt-chromium and cobalt-chromium-molybdenum orthopedic type alloys also can be employed, as well as alloys of titanium-aluminum-vanadium. The MP35N alloy is widely available, and has a potential for better fatigue strength due to improved manufacturing techn;ques, particularly as to the vacuum melting process. The titanium-aluminum-vanadium alloys are highly biocompatible, and have more moderate stress/strain responses, i.e. lower elastic moduli.
Composite filaments such as filament 18a are manufactured by a drawn filled tubing (DFT) process illustrated schematically in Figures 7-9. The DFT
process can be performed, for example, by Fort Wayne Metals Research Products Corporation of Ft. Wayne, Indiana. The process begins with insertion of a solid cylinder or wire 28 of the core material into a central opening 30 of a tube 32 of the case material. Core wire 28 and tubing 32 are substantially uniform in transverse or lateral sections, i.e. sections taken perpendicular to the longitudinal or axial dimension.
For example, tube 32 can have an outer diameter d. of about 0.102 inch (2.6 mm) and an inner diameter d2 (diameter of opening 30) of about .056 inches (1.42 mm). Core or wire 28 has an outer diameter d3 slightly less than the tube inner diameter, e.g. .046 inches (1.17 mm). In general, the wire outer diameter is sufficiently close to the tubing inner diameter to insure that core or wire 28, upon being inserted into opening 30, is substantially radially centered within the tubing. At the same time, the interior tubing diameter must exceed the core outside diameter sufficiently to facilitate insertion of the wire into WO94/16~K PCT~S93tl~62 g~
an extended length of wire and tubing, e.g. at least twenty feet.
The values of the tubing inner diameter and the core outer diameter vary with the materials involved.
For example, platinum as compared to tantalum has a smoother exterior finish when formed into the elongate wire or core. As a result, the outer diameter of a platinum wire can more closely approximate the inner diameter of the tube. Thus it is to be appreciated that the optimum diameter values vary with the materials involved, and the expected length of the composite filament.
In any event, insertion of the core into the tube forms a composite filament 34, which then is directed through a series of alternating cold-working and annealing steps, as indicated schematically in Figure 6. More particularly, composite filament 34 is drawn through three dies, indicated at 36, 38, and 40, respectively. In each of the dies, composite filament 34 is cold-worked in radial compression~ causing the case tube 32 and the tantalum core wire 28 to cold flow in a manner that elongates the filament while reducing its diameter. Initially, case tube 32 is elongated and radially reduced to a greater extent than core wire 28, due to the minute radial gap that allowed the insertion of the core into the tube. However, the radial gap is closed rapidly as the filament is drawn through die 36, with subsequent pressure within die 36 and the remaining dies cold-working both the core and case together as if they were a single, solid filament. In fact, upon closure of the radial gap, the cold-working within all dies forms a pressure weld along the entire interface of the core and case, to form a bond between the core and case material.
WO94/16~K PCT~S9311~62 ~
~2~
As composite filament 34 is drawn through each die, the cold-working induces strain hardening and other stresses within the filament. Accordingly, one or more heating stages are provided, e.g. furnace 42.
At each annealing stage, composite filament 34 is heated to a temperature in the range of from about l900 to about 2300 F., or more preferably 2000 - 2150 F.
At each annealing stage, substantially all of the induced stresses are removed from the case and core, to permit further cold-working. Each annealing step is accomplished in a brief time, e.g. in as few as one to fifteen seconds at annealing temperature, depending on the size of composite filament 34.
While Figure 6 illustrates one cold-working stage and annealing stage, it is to be understood that the appropriate number of stages is selected in accordance with the desired final filament size, the desired degree of cross-sectional area reduction during the final cold-working stage, and the initial filament size prior to cold-working. In connection with composite filament 34, a reduction of lateral cross-sectional area in the range of about forty percent to eighty percent is preferred, and a range of about fifty-five percent to sixty-five percent is highly preferred.
The successive cold-working and annealing steps give rise to the need for matching the core and case materials, particularly as to their coefficients of thermal expansion, elastic moduli in tension, annealing temperature ranges, total elongation capacities, and also as to their crystalline structure. A good match of elastic moduli, elongation, and thermal expansion coefficients minimizes the tendency for any ruptures or discontinuities along the core/case interface as the composite filament is processed. Crystalline WO94/16~K PCT~S93/1~
~ 2~
structures should be considered in matching core and case materials. The Elgiloy alloy, and other materials used to form case tube 32, commonly experience a transformation between the cold-working and aging steps, from a face centered cubic crystalline structure to a hexagonal close packed crystalline structure. The Elgiloy alloy experiences shrinkage as it undergoes this transformation. Accordingly, the core material must either experience a similar reduction, or be sufficiently ductile to accommodate reduction of the case.
There is no annealing after the final cold-working stage. At this point, composite filament 34 is formed into the shape intended for the device incorporating the filament. In Figure 8, several filaments or strands 34a-e are helically wound about a cylindrical form 48 and held in place at their opposite ends by sets of bobbins 50a-e and 52a-e. Strands 34a-e can be individually processed, or individual segments of a single annealed and cold-worked composite filament, cut after the final cold-working stage. In either event, the filaments cooperate to form one of the two oppositely directed sets of spaced apart and parallel filaments that form a device such as stent 16. While only one set of filaments is shown, it is to be understood that a corresponding group of filaments, helically wound and intertwined about form 48 in the opposite direction, are supported by corresponding bobbins at the opposite filament ends.
A useful prosthesis depends, in part, upon correctly supporting the filaments. The filaments are maintained in tension, and it is important to select the appropriate tensile force and apply the tensile force uniformly to all filaments. Insufficient tensile WO94/16~KPCT~S93/1~62 2i~ 4 force may allow wire cast or lift effects to cause the individual filaments to depart from their helical configuration when released from the bobbins, and the braided structure of the stent may unravel.
5Figure 9 illustrates two filaments 34a and 54a, one from each of the oppositely wound filament sets, supported by respective bobbins 50a/52a and 56a/58a in a furnace 60 for age hardening in a vacuum or protective atmosphere. Age hardening is accomplished at temperatures substantially lower than annealing, e.g. in the range of about 700 - 1200 F, more preferably 900 - 1000 F. The filaments overlie one another to form several intersections, one of which is indicated at 62. When the filaments are properly tensioned, a slight impression is formed in the overlying filament at each intersection. These impressions, or saddles, tend to positionally lock the filaments relative to one another at the intersections, maintaining the prosthesis configuration without the need for welding or other bonding of filaments at their intersections.
While only two oppositely directed filaments are illustrated as a matter of convenience, it is to be appreciated that the age hardening stage is performed after the tensioning and winding of all filaments, i.e.
both oppositely directed sets. Accordingly, during age hardening, the filaments are locked relative to one another at multiple intersections. The preferred time for age hardening is about 1-5 hours. This age hardening step is critical to forming satisfactory self-expanding prosthesis, as it substantially enhances elasticity, yield strength, and tensile strength.
Typically, the elastic modulus is increased by at least 10 percent, and the yield strength (0.2% offset) and WO94/16646 PCT~S93/11262 ~9,, tensile strength are each increased at least 20 percent.
As an alternative to the process just explained, a substantially larger and shorter composite structure 64 (e.g. six inches long with a diameter of approximately two inches) can be subjected to a series of elongation and diameter reduction steps. Figure 10 schematically illustrates two swaging dies 66 and 68, which may be used in the course of a hot working billet reduction process. Of course, any appropriate number of swaging dies may be employed. Alternatively, the diameter reduction can be accomplished by extrusion/pulltrusion at each stage. When a sufficient number of swaging steps have reduced the composite structure diameter to about 6 millimeters (.25 inches).
The composite structure or filament can be further processed by drawing it through dies and annealing, as illustrated in Figure 6 for the previously discussed process. As before, the composite filament is ready for selective shaping and age hardening after the final cold-working stage.
As compared to the process depicted in Figures 5-7, the swaging or pulltrusion approach involves substantially increased hot and cold-working of the composite structure or filament, and the initial assembling of the core into the case or shell tubing is easier. Given the much larger initial composite structure size, the structure is subjected to annealing temperatures for a substantially longer time, e.g. half an hour to an hour, as opposed to the one to fifteen second anneal times associated with the process depicted in Figure 6. Consequently, particular care must be taken to avoid combinations of core and case materials with tendencies for intermetallic formation WO94/16~ PCT~S93/1~62 21~5~
along the core/case interface. Further, the required hot working of the larger billet may not afford the same degree of metallurgical grain refinement.
Figure 11 is an end elevation of a composite filament 74 including a central core 76 of a structural material such as the Elgiloy alloy, surrounded by a radiopaque case 78, thus reversing the respective functions of the core and case as compared to composite filament 34. Composite filament 74, as compared to filament 34, presents a larger and less refractive radiopaque profile for a given composite filament diameter. Composite filament 74, however, may be more difficult to manufacture than filaments that employ the structural material as the case.
Figures 12 and 13 show a further alternative composite filament 80, consisting of a central radiopaque core 82, an outer annular structural case 84, and an intermediate annular layer 86 between the core and the case. Intermediate layer 86 provides a barrier between the core and case, and is particularly useful in composite filaments employing core and case materials that would be incompatible if contiguous, e.g. due to a tendency to form intermetallics.
Materials suitable for barrier layer 86 include tantalum, niobium and platinum. As suggested by Figure 12, the core, barrier layer and case can be provided as a cylinder and two tubes, inserted into one another for manufacture of the composite filament as explained above.
Figure 14 illustrates another alternative embodiment composite filament 88 having a central radiopaque core 90, a structural case 92, and a relatively thin annular outer cover layer 94.
Composite filament 88 is particularly useful when the WO94/16~K PCT~S93/1~
selected mechanical structure lacks satisfactory biocompatibility, hemocompatibility, or both. Suitable materials for cover layer 94 include tantalum, platinum, iridium, niobium, titanium and stainless steel. Thè composite filament can be manufactured as explained above, beginning with insertion of the radiopaque core into the structural case, and in turn, inserting the case into a tube formed of the cover material. Alternatively, cover layer 94 can be applied by a vacuum deposition process, as a thin layer (e.g.
from ten to a few hundred microns) is all that is required.
The following examples illustrate formation of composite filaments according to the above-disclosed processes.
Example 1 An elongate tantalum core having a diameter of .046 inches (1.17 mm) was assembled into an Elgiloy alloy case having an outer diameter of 0.102 inches (2.6 mm) and an inner diameter of .056 inches (1.42 mm). Accordingly, the lateral cross-sectional area of the tantalum core was about 25% of the composite filament lateral cross-sectional area. Composite filaments so constructed were subjected to 5-6 alternating stages of cold-working and annealing, to reduce the outer diameters of the composite filaments to values within the range of .004-.0067 inches. The tantalum core diameters were reduced to values in the range of .002-.0034 inches. The composite filaments were formed into a stent suitable for biliary applications, and age hardened for up to five hours, at temperatures in the range of 900-1000 F.
Example 2 Elongate cores of a platinum iridium alloy (20% by WO94/16~K PCT~S93/1~62 ~
2~ 9 weight iridium), with initial core outer diameters of .088 inches, were inserted into annular Elgiloy cases with outer diameters of .098 inches and inside diameters of .044 inches. The resulting composite filaments were processed through about six cold-working and annealing cycles as in the first example, to reduce the outer filament diameter to values within the range of .00276 inches - .0039 inches, and reducing the core outer diameter to values in the range of .0018-.0026 inches. The core thus constituted 43% of the filament lateral cross-sectional area. The resulting filaments were formed into a small vascular stent, and age hardened for approximately three hours.
Example 3 Composite filaments were constructed and processed substantially as in example 2, except that the core was formed of a platinum nickel alloy, with nickel 10% by weight.
Example 4 The composite filaments were constructed and processed as in examples 2 and 3, except that the core was formed of tantalum, and the case was formed of MP35N alloy, and the cold-working stages reduced the filament outer diameter to values in the range of .00276-.0047 inches.
In the case of all examples above, the resulting stents exhibited satisfactory elasticity and were readily fluoroscopically imaged in real time.
Each of the above described composite filaments combines the desired structural stability and resiliency, with radio-opacity that allows in vivo imaging of the device composed of the filaments, during deployment and after device fixation. This result is achieved by a drawn filled tubing process that cold W094/16~6 PCT~S93/11262 ~ ~S$q works a central core and its surrounding case, to positively bond the core and case together such that the composite filament behaves as a continuous, solid structure. Performance of the filament and resulting device is further enhanced by a selective matching of the core and case materials, as to linear thermal expansion coefficient, annealing temperature, and crystalline structure.
filament.
In one preferred version of the process, the radiopaque material has a linear attenuation coefficient, at 100 KeV, of at least 25 cm -1. The radiopaque material forms the core, and is at least as ductile as the case. The outside diameter of the composite filament, before cold-working, preferably is at most about six millimeters (about 0.25 inches). The cold-working step can include drawing the composite filament serially through several dies, with each die plastically deforming the composite filament to reduce the outside diameter. Whenever a stage including one or more cold-working dies has reduced the cross-sectional area by at least 25%, an annealing step should be performed before any further cold-working.
During each annealing step, the composite filament is heated to a temperature in the range of about 1900 - 2300 F. for a period depending on the filament diameter, typically in the range of several seconds to several minutes. The core material and cladding (case) materials preferably are selected to have overlapping annealing temperature ranges, and similar coefficients of thermal expansion. The core and case materials further can be selectively matched as to their crystalline structure and metallurgical compatibility.
In an alternative version of the process, the initial outside diameter of the composite structure (billet) typically is at least fifty millimeters (about two inches) in diameter. Then, before cold-working, the composite filament is subjected to temperatures in the annealing range while the outside diameter is substantially reduced, either by swaging or by pulltrusion, in successive increments until the outside diameter is at most about 6 millimeters (.25 inches).
W094/16~K PCT~S93/1~62 ~52~
The resulting filament is processed as before, in alternative cold-working and annealing stages.
Further according to the process, the composite filament can be severed into a plurality of strands.
Then, the strands are arranged in two oppositely directed sets of parallel helical windings about a cylindrical form, with the strands intertwined in a braided configuration to form multiple intersections.
Then, while the strands are maintained in a lo predetermined uniform tension, they are heated to a temperature in the range of about 700 - 1200 F., more preferably 900 - 1000 F., for a time sufficient to age harden the helical windings.
The result of this process is a resilient, body implantable prosthesis. The prosthesis has a plurality of resilient strands, helically wound in two oppositely directed sets of spaced apart and parallel strands, interwoven with one another in a braided configuration.
Each of the strands includes an elongate core and an elongate tubular case surrounding the core. A cross-sectional area of the core is at least ten percent of the cross-sectional area of the strand. The core is constructed of a first material having a linear attenuation coefficient of at least 25 cm -1 at 100 KeV.
The case is constructed of a resilient second material, less ductile than the first material.
More generally, the process can be employed to form a body compatible device comprising an elongate filament substantially uniform in lateral cross-section over its length and including an elongate cylindrical core and an elongate tubular case surrounding the core.
One of the core and case is constructed of a first material having an yield strength (0.2~ offset) of at least twice that of the second material. The other of W094/16~ PCT~S93/1~62 ~ Sg~
the core and case is constructed of a second material being radiopaque and at least as ductile as the first material.
In a highly preferred version of the invention, the core is constructed of tantalum for radio-opacity, and the case is constructed of a cobalt-based alloy, e.g. as available under the brand names "Elgiloy", "Phynox" and "MP35N". The "Elgiloy" and "Phynox"
alloys contain cobalt, chromium, nickel, and molybdenum, along with iron. Either of these alloys is well matched with tantalum, in terms of overlapping annealing temperature ranges, coefficients of thermal expansion and crystalline structure. The tantalum core and alloy case can be contiguous with one another, with virtually no formation of intermetallics.
When otherwise compatible core and case materials present the risk of intermetallic formation, an intermediate layer, e.g. of tantalum, niobium, or platinum, can be formed between the core and the case to provide a barrier against intermetallic formation.
Further, if the case itself is not sufficiently biocompatible, a biocompatible coating or film can surround the case. Tantalum, platinum, iridium and their alloys, or stainless steels can be used for this purpose.
While disclosed herein in connection with a radially self-expanding stent, the composite filaments can be employed in constructing other implantable medical devices, e.g. vena cava filters, blood filters and thrombosis coils. Thus, in accordance with the present invention there is provided a resilient, body compatible prosthesis which, despite being sufficiently small for placement within blood vessels and similarly sized body cavities, has sufficient radio-opacity for W094/16~K PCT~S93/1~62 ~
~iS~
fluoroscopic imaging based on the prosthesis materials themselves.
In the Drawings For a further understanding of the above and other features and advantages, reference is made to the following detailed description and to the drawings, in which:
Figure 1 is a side elevation of a self-expanding stent constructed according to the present invention;
Figure 2 is an end elevational view of the stent;
Figure 3 is an enlarged partial view of one of the composite filaments forming the stent;
Figure 4 is an enlarged sectional view taken along the line 4-4 in Figure 3;
Figures 5-9 schematically illustrate a process for manufacturing the stent;
Figure 10 schematically illustrates a swaging step of an alternative process for manufacturing the stent;
Figure 11 is an end elevational view of an alternative embodiment filament;
Figure 12 is an elevational view of several components of an alternative composite filament constructed according to the present invention;
Figure 13 is an end elevational view of the composite filament formed by the components shown in Figure 12; and Figure 14 is an end elevational view of another alternative embodiment composite filament.
Detailed Description of the Preferred Embodiment Turning now to the drawings, there is shown in Figures 1 and 2 a body implantable prosthesis 16, frequently referred to as a stent. Stent 16 is of open mesh or weave construction, consisting of two sets of oppositely directed, parallel and spaced apart WO94116~K PCT~S9311~62 ~ ~lS~S~
helically wound strands or filaments indicated at 18 and 20, respectively. The sets of strands are interwoven in an over and under braided configuration to form multiple intersections, one of which is indicated at 22.
Stent 16 is illustrated in its relaxed state, i.e.
in the configuration it assumes when subject to no external stresses. The filaments or strands of stent 16 are resilient, permitting a radial compression of the stent into a reduced-radius, extended-length configuration suitable for transluminal delivery of the stent to the intended placement site. As a typical example, stent 16 can have a diameter of about ten millimeters in the relaxed state, and is elastically compressed to a diameter of about 2 millimeters (.08 inches) and an axial length of about twice the axial length of the relaxed stent. However, different applications call for different diameters. Further, it is well known to predetermine the degree of axial elongation for a given radial compression, by selectively controlling the angle between the oppositely directed helical strands.
Inelastic open-weave prostheses, expandable for example by dilation balloons, provide an alternative to resilient prostheses. Resilient or self-expanding prostheses often are preferred, as they can be deployed without dilation balloons or other stent expanding means. Self-expanding stents can be preselected according to the diameter of the blood vessel or other intended fixation site. While their deployment requires skill in stent positioning, such deployment does not require the additional skill of carefully dilating the balloon to plastically expand the prosthesis to the appropriate diameter. Further, the WO94/16~ 9 ~ PCT~S9311~62 ~
self-expanding stent remains at least slightly elastically compressed after fixation, and thus has a restoring force which facilitates acute fixation. By contrast, a plastically expanded stent must rely on the restoring force of deformed tissue, or on hooks, barbs, or other independent fixation elements.
Accordingly, materials forming the strands for filaments must be strong and resilient, biocompatible, and resistant to fatigue and corrosion. Vascular applications require hemocompatibility as well.
Several materials meet these needs, including stainless "spring" steels, and certain cobalt-based alloys: more particularly two alloys including cobalt, chromium, iron, nickel and molybdenum sold under the brand names "Elgiloy" (available from Carpenter Technology Corporation of Reading, Pennsylvania) and "Phynox"
(available from Metal Imphy of Imphy, France), respectively. Another suitable cobalt-chromium alloy is available under the brand name "MP35N" from Carpenter Technology Corporation of Reading, Pennsylvania.
Further, it is advantageous to form a prosthesis with substantial open space to promote embedding of the stent into tissue, and fibrotic growth through the stent wall to enhance long-term fixation. A more open construction also enables substantial radial compression of the prosthesis for deployment. In a typical construction suitable for transluminal implantation, the filaments can have a diameter of about O.l millimeter (.004 inches), with adjacent parallel filaments spaced apart from one another by about 1-2 millimeters (.04-.08 inches) when the stent is in the relaxed state.
Fluoroscopic imaging of a conventional open weave WO94/16~K ~ 9 4 PCT~S93/1~62 prosthesis is extremely difficult. Due to their minute diameters and the materials involved, the filaments exhibit a relatively poor contrast to body tissue for fluoroscopic imaging purposes. The filaments also require a high degree of spatial resolution in the imaging equipment involved. Thus, a stent recognizable on X-ray film may not be distinguishable for real time imaging, due to the relatively poor spatial resolution of the video monitor as compared to X-ray film.
According to the present invention, however, prosthesis 16 is substantially more amenable to fluoroscopic imaging, due to the construction of strands 18 and 20. In particular, the strands cooperate to present a sufficiently radiopaque mass at the tangen~s of device 16 (parallel to the X-rays) for satisfactory real time imaging. As seen in Figures 3 and 4, a filament 18a of the prosthesis is of composite construction, with a radiopaque core 24 surrounded by and concentric with an annular resilient case 26. Core 24 is highly absorptive of X-rays, preferably having a linear attenuation coefficient of at least 25 (and more preferably at least 50) cm -1 at 100 KeV. Materials with relatively high atomic numbers and densities tend to have the necessary attenuation coefficients. More particularly, it has been found that materials with an atomic number (elements) or "effective" atomic number (based on a weighted average of elements in alloys or compounds) of at least fifty, and densities of at least 0.5 pounds per cubic inch, exhibit the required ability to absorb X-rays. Finally, core 24 is preferably a ductile material so that it readily conforms to the - shape of the case.
By contrast, case 26 is formed of a highly resilient material, preferably with a yield strength WO94/1~K PCT~S9311~62 2i5~59~ --(0.2% offset) of at least 150,000 psi. More preferably, the yield strength is at least 300,000 psi.
Consequently, the mechanical behavior of composite filament 18a in terms of elastic deformation in response to external stresses is, essentially, the behavior of case 26.
In addition to individual characteristics of the core and case, it is desirable to selectively match core and case materials based on certain common characteristics. The core and case materials should have the same or substantially the same linear coefficients of thermal expansion. Similarity of core and case materials in their crystalline structure is also an advantage. Finally, the core and case materials should have an overlap in their annealing temperature ranges, to facilitate manufacture of the filaments according to the process to be explained.
In a highly preferred embodiment, core 24 is formed of tantalum, and case 26 is formed of a cobalt-based alloy, more particularly Elgiloy (brand) alloy.
Tantalum is a ductile metal having an atomic number of 73 and a density of about 0.6 pounds per cubic inch.
Its linear attenuation coefficient, at lO0 KeV, is 69.7 cm -1 The Elgiloy alloy includes principally cobalt and chromium, and has an effective atomic number of less than thirty and a density substantially less than 0.5 pounds per cubic inch. However, the alloy is body compatible, hemocompatible and highly resilient, with 30 a yield strength (0.2% offset) of at least 350,000 psi, after cold working and age hardening.
Case 26 and core 24 thus cooperate to provide a prosthesis that can be viewed in vivo, and in real time. Of course, the amount of core material in W094/16646 PCT~S93/11262 2l52s~
relation to the amount of case material must be sufficient to insure radio-opacity while maintaining the favorable mechanical characteristics of stent 16.
It has been found that the area of core 24, taken along a transverse or lateral plane as illustrated in Figure 4, should be within the range of about ten percent to forty-six percent of the filament lateral cross-sectional area, i.e. the area of the combined case and core.
Tantalum and the Elgiloy alloy are well matched, in that the materials have similar linear coefficients of thermal expansion (3.6 x 10-6 per degree F. and 8.4 x 10-6 per degree F., respectively), similar crystalline structures, and annealing temperatures in the range of 1900 - 2300 F. Further, there is virtually no tendency for the formation of intermetallic compounds along the tantalum/Elgiloy alloy interface.
Platinum and platinum alloys (e.g. platinum iridium) also are suitable as materials for core 24.
The atomic number of platinum is 78, and its density is 0.775 pounds per cubic inch. Its linear attenuation coefficient at 100 KeV is 105 cm -1. The linear coefficient of thermal expansion for platinum is about 4.9 x 10-6 per degree F.
Thus, as compared to tantalum, platinum is structurally more compatible with the Elgiloy alloy, and more effectively absorbs X-rays. Accordingly, platinum is particularly well suited for use in prostheses formed of small diameter filaments. The primary disadvantage of platinum, with respect to tantalum, is its higher cost.
- Further materials suitable for radiopaque core 24 include gold, tungsten, iridium, rhenium, ruthenium, and depleted uranium.
WO94/16~ ~ PCT~S9311~62 21 ~S~
Other materials suitable for case 26 include other cobalt-based alloys, e.g. the Phynox and MP35N brand alloys. Cobalt-chromium and cobalt-chromium-molybdenum orthopedic type alloys also can be employed, as well as alloys of titanium-aluminum-vanadium. The MP35N alloy is widely available, and has a potential for better fatigue strength due to improved manufacturing techn;ques, particularly as to the vacuum melting process. The titanium-aluminum-vanadium alloys are highly biocompatible, and have more moderate stress/strain responses, i.e. lower elastic moduli.
Composite filaments such as filament 18a are manufactured by a drawn filled tubing (DFT) process illustrated schematically in Figures 7-9. The DFT
process can be performed, for example, by Fort Wayne Metals Research Products Corporation of Ft. Wayne, Indiana. The process begins with insertion of a solid cylinder or wire 28 of the core material into a central opening 30 of a tube 32 of the case material. Core wire 28 and tubing 32 are substantially uniform in transverse or lateral sections, i.e. sections taken perpendicular to the longitudinal or axial dimension.
For example, tube 32 can have an outer diameter d. of about 0.102 inch (2.6 mm) and an inner diameter d2 (diameter of opening 30) of about .056 inches (1.42 mm). Core or wire 28 has an outer diameter d3 slightly less than the tube inner diameter, e.g. .046 inches (1.17 mm). In general, the wire outer diameter is sufficiently close to the tubing inner diameter to insure that core or wire 28, upon being inserted into opening 30, is substantially radially centered within the tubing. At the same time, the interior tubing diameter must exceed the core outside diameter sufficiently to facilitate insertion of the wire into WO94/16~K PCT~S93tl~62 g~
an extended length of wire and tubing, e.g. at least twenty feet.
The values of the tubing inner diameter and the core outer diameter vary with the materials involved.
For example, platinum as compared to tantalum has a smoother exterior finish when formed into the elongate wire or core. As a result, the outer diameter of a platinum wire can more closely approximate the inner diameter of the tube. Thus it is to be appreciated that the optimum diameter values vary with the materials involved, and the expected length of the composite filament.
In any event, insertion of the core into the tube forms a composite filament 34, which then is directed through a series of alternating cold-working and annealing steps, as indicated schematically in Figure 6. More particularly, composite filament 34 is drawn through three dies, indicated at 36, 38, and 40, respectively. In each of the dies, composite filament 34 is cold-worked in radial compression~ causing the case tube 32 and the tantalum core wire 28 to cold flow in a manner that elongates the filament while reducing its diameter. Initially, case tube 32 is elongated and radially reduced to a greater extent than core wire 28, due to the minute radial gap that allowed the insertion of the core into the tube. However, the radial gap is closed rapidly as the filament is drawn through die 36, with subsequent pressure within die 36 and the remaining dies cold-working both the core and case together as if they were a single, solid filament. In fact, upon closure of the radial gap, the cold-working within all dies forms a pressure weld along the entire interface of the core and case, to form a bond between the core and case material.
WO94/16~K PCT~S9311~62 ~
~2~
As composite filament 34 is drawn through each die, the cold-working induces strain hardening and other stresses within the filament. Accordingly, one or more heating stages are provided, e.g. furnace 42.
At each annealing stage, composite filament 34 is heated to a temperature in the range of from about l900 to about 2300 F., or more preferably 2000 - 2150 F.
At each annealing stage, substantially all of the induced stresses are removed from the case and core, to permit further cold-working. Each annealing step is accomplished in a brief time, e.g. in as few as one to fifteen seconds at annealing temperature, depending on the size of composite filament 34.
While Figure 6 illustrates one cold-working stage and annealing stage, it is to be understood that the appropriate number of stages is selected in accordance with the desired final filament size, the desired degree of cross-sectional area reduction during the final cold-working stage, and the initial filament size prior to cold-working. In connection with composite filament 34, a reduction of lateral cross-sectional area in the range of about forty percent to eighty percent is preferred, and a range of about fifty-five percent to sixty-five percent is highly preferred.
The successive cold-working and annealing steps give rise to the need for matching the core and case materials, particularly as to their coefficients of thermal expansion, elastic moduli in tension, annealing temperature ranges, total elongation capacities, and also as to their crystalline structure. A good match of elastic moduli, elongation, and thermal expansion coefficients minimizes the tendency for any ruptures or discontinuities along the core/case interface as the composite filament is processed. Crystalline WO94/16~K PCT~S93/1~
~ 2~
structures should be considered in matching core and case materials. The Elgiloy alloy, and other materials used to form case tube 32, commonly experience a transformation between the cold-working and aging steps, from a face centered cubic crystalline structure to a hexagonal close packed crystalline structure. The Elgiloy alloy experiences shrinkage as it undergoes this transformation. Accordingly, the core material must either experience a similar reduction, or be sufficiently ductile to accommodate reduction of the case.
There is no annealing after the final cold-working stage. At this point, composite filament 34 is formed into the shape intended for the device incorporating the filament. In Figure 8, several filaments or strands 34a-e are helically wound about a cylindrical form 48 and held in place at their opposite ends by sets of bobbins 50a-e and 52a-e. Strands 34a-e can be individually processed, or individual segments of a single annealed and cold-worked composite filament, cut after the final cold-working stage. In either event, the filaments cooperate to form one of the two oppositely directed sets of spaced apart and parallel filaments that form a device such as stent 16. While only one set of filaments is shown, it is to be understood that a corresponding group of filaments, helically wound and intertwined about form 48 in the opposite direction, are supported by corresponding bobbins at the opposite filament ends.
A useful prosthesis depends, in part, upon correctly supporting the filaments. The filaments are maintained in tension, and it is important to select the appropriate tensile force and apply the tensile force uniformly to all filaments. Insufficient tensile WO94/16~KPCT~S93/1~62 2i~ 4 force may allow wire cast or lift effects to cause the individual filaments to depart from their helical configuration when released from the bobbins, and the braided structure of the stent may unravel.
5Figure 9 illustrates two filaments 34a and 54a, one from each of the oppositely wound filament sets, supported by respective bobbins 50a/52a and 56a/58a in a furnace 60 for age hardening in a vacuum or protective atmosphere. Age hardening is accomplished at temperatures substantially lower than annealing, e.g. in the range of about 700 - 1200 F, more preferably 900 - 1000 F. The filaments overlie one another to form several intersections, one of which is indicated at 62. When the filaments are properly tensioned, a slight impression is formed in the overlying filament at each intersection. These impressions, or saddles, tend to positionally lock the filaments relative to one another at the intersections, maintaining the prosthesis configuration without the need for welding or other bonding of filaments at their intersections.
While only two oppositely directed filaments are illustrated as a matter of convenience, it is to be appreciated that the age hardening stage is performed after the tensioning and winding of all filaments, i.e.
both oppositely directed sets. Accordingly, during age hardening, the filaments are locked relative to one another at multiple intersections. The preferred time for age hardening is about 1-5 hours. This age hardening step is critical to forming satisfactory self-expanding prosthesis, as it substantially enhances elasticity, yield strength, and tensile strength.
Typically, the elastic modulus is increased by at least 10 percent, and the yield strength (0.2% offset) and WO94/16646 PCT~S93/11262 ~9,, tensile strength are each increased at least 20 percent.
As an alternative to the process just explained, a substantially larger and shorter composite structure 64 (e.g. six inches long with a diameter of approximately two inches) can be subjected to a series of elongation and diameter reduction steps. Figure 10 schematically illustrates two swaging dies 66 and 68, which may be used in the course of a hot working billet reduction process. Of course, any appropriate number of swaging dies may be employed. Alternatively, the diameter reduction can be accomplished by extrusion/pulltrusion at each stage. When a sufficient number of swaging steps have reduced the composite structure diameter to about 6 millimeters (.25 inches).
The composite structure or filament can be further processed by drawing it through dies and annealing, as illustrated in Figure 6 for the previously discussed process. As before, the composite filament is ready for selective shaping and age hardening after the final cold-working stage.
As compared to the process depicted in Figures 5-7, the swaging or pulltrusion approach involves substantially increased hot and cold-working of the composite structure or filament, and the initial assembling of the core into the case or shell tubing is easier. Given the much larger initial composite structure size, the structure is subjected to annealing temperatures for a substantially longer time, e.g. half an hour to an hour, as opposed to the one to fifteen second anneal times associated with the process depicted in Figure 6. Consequently, particular care must be taken to avoid combinations of core and case materials with tendencies for intermetallic formation WO94/16~ PCT~S93/1~62 21~5~
along the core/case interface. Further, the required hot working of the larger billet may not afford the same degree of metallurgical grain refinement.
Figure 11 is an end elevation of a composite filament 74 including a central core 76 of a structural material such as the Elgiloy alloy, surrounded by a radiopaque case 78, thus reversing the respective functions of the core and case as compared to composite filament 34. Composite filament 74, as compared to filament 34, presents a larger and less refractive radiopaque profile for a given composite filament diameter. Composite filament 74, however, may be more difficult to manufacture than filaments that employ the structural material as the case.
Figures 12 and 13 show a further alternative composite filament 80, consisting of a central radiopaque core 82, an outer annular structural case 84, and an intermediate annular layer 86 between the core and the case. Intermediate layer 86 provides a barrier between the core and case, and is particularly useful in composite filaments employing core and case materials that would be incompatible if contiguous, e.g. due to a tendency to form intermetallics.
Materials suitable for barrier layer 86 include tantalum, niobium and platinum. As suggested by Figure 12, the core, barrier layer and case can be provided as a cylinder and two tubes, inserted into one another for manufacture of the composite filament as explained above.
Figure 14 illustrates another alternative embodiment composite filament 88 having a central radiopaque core 90, a structural case 92, and a relatively thin annular outer cover layer 94.
Composite filament 88 is particularly useful when the WO94/16~K PCT~S93/1~
selected mechanical structure lacks satisfactory biocompatibility, hemocompatibility, or both. Suitable materials for cover layer 94 include tantalum, platinum, iridium, niobium, titanium and stainless steel. Thè composite filament can be manufactured as explained above, beginning with insertion of the radiopaque core into the structural case, and in turn, inserting the case into a tube formed of the cover material. Alternatively, cover layer 94 can be applied by a vacuum deposition process, as a thin layer (e.g.
from ten to a few hundred microns) is all that is required.
The following examples illustrate formation of composite filaments according to the above-disclosed processes.
Example 1 An elongate tantalum core having a diameter of .046 inches (1.17 mm) was assembled into an Elgiloy alloy case having an outer diameter of 0.102 inches (2.6 mm) and an inner diameter of .056 inches (1.42 mm). Accordingly, the lateral cross-sectional area of the tantalum core was about 25% of the composite filament lateral cross-sectional area. Composite filaments so constructed were subjected to 5-6 alternating stages of cold-working and annealing, to reduce the outer diameters of the composite filaments to values within the range of .004-.0067 inches. The tantalum core diameters were reduced to values in the range of .002-.0034 inches. The composite filaments were formed into a stent suitable for biliary applications, and age hardened for up to five hours, at temperatures in the range of 900-1000 F.
Example 2 Elongate cores of a platinum iridium alloy (20% by WO94/16~K PCT~S93/1~62 ~
2~ 9 weight iridium), with initial core outer diameters of .088 inches, were inserted into annular Elgiloy cases with outer diameters of .098 inches and inside diameters of .044 inches. The resulting composite filaments were processed through about six cold-working and annealing cycles as in the first example, to reduce the outer filament diameter to values within the range of .00276 inches - .0039 inches, and reducing the core outer diameter to values in the range of .0018-.0026 inches. The core thus constituted 43% of the filament lateral cross-sectional area. The resulting filaments were formed into a small vascular stent, and age hardened for approximately three hours.
Example 3 Composite filaments were constructed and processed substantially as in example 2, except that the core was formed of a platinum nickel alloy, with nickel 10% by weight.
Example 4 The composite filaments were constructed and processed as in examples 2 and 3, except that the core was formed of tantalum, and the case was formed of MP35N alloy, and the cold-working stages reduced the filament outer diameter to values in the range of .00276-.0047 inches.
In the case of all examples above, the resulting stents exhibited satisfactory elasticity and were readily fluoroscopically imaged in real time.
Each of the above described composite filaments combines the desired structural stability and resiliency, with radio-opacity that allows in vivo imaging of the device composed of the filaments, during deployment and after device fixation. This result is achieved by a drawn filled tubing process that cold W094/16~6 PCT~S93/11262 ~ ~S$q works a central core and its surrounding case, to positively bond the core and case together such that the composite filament behaves as a continuous, solid structure. Performance of the filament and resulting device is further enhanced by a selective matching of the core and case materials, as to linear thermal expansion coefficient, annealing temperature, and crystalline structure.
Claims (37)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A body compatible device comprising:
an elongate filament substantially uniform in lateral cross-section over its length and including an elongate cylindrical core and an elongate tubular case surrounding the core at least substantially over the length of the filament, a lateral cross-sectional area of the core being at least about ten percent of a lateral cross-sectional area of the filament;
wherein one of the core and case is constructed of a first material having a linear attenuation coefficient of at least 25 cm-1 at 100 KeV, the other of the core and case is constructed of a second material, and the first material is more radiopaque than the second material; and wherein the filament, due at least in part to an age hardening of the filament after a final annealing during its production process, exhibits (a) an at least 10 percent greater modulus of elasticity; (b) a greater yield strength at 0.2 percent offset; and (c) a greater tensile strength, as compared to an otherwise identical filament which has not been age hardened after a final annealing.
an elongate filament substantially uniform in lateral cross-section over its length and including an elongate cylindrical core and an elongate tubular case surrounding the core at least substantially over the length of the filament, a lateral cross-sectional area of the core being at least about ten percent of a lateral cross-sectional area of the filament;
wherein one of the core and case is constructed of a first material having a linear attenuation coefficient of at least 25 cm-1 at 100 KeV, the other of the core and case is constructed of a second material, and the first material is more radiopaque than the second material; and wherein the filament, due at least in part to an age hardening of the filament after a final annealing during its production process, exhibits (a) an at least 10 percent greater modulus of elasticity; (b) a greater yield strength at 0.2 percent offset; and (c) a greater tensile strength, as compared to an otherwise identical filament which has not been age hardened after a final annealing.
2. The device of claim 1 wherein the other of the core and case which is constructed of a second material has a yield strength of at least 150,000 psi at 0.2 percent offset and the first and second materials have about the same linear coefficients of thermal expansion.
3. The device of claim 1 or 2, wherein the core is constructed of the first material and the case is constructed of the second material.
4. The device of claim 1 or 2, wherein the case is constructed of the first material and the core is constructed of the second material.
5. The device of claim 1 or 2, wherein the first material has a direct or equivalent atomic number of at least fifty and a density of at least 0.5 pounds per cubic inch.
6. The device of claim 5 wherein the first material is at least one member selected from the group consisting of tantalum, platinum, gold, iridium, rhenium, tungsten, ruthenium and depleted uranium.
7. The device of claim 1, 2, 5 or 6, wherein the second material is at least one member selected from the group consisting of cobalt, chromium, titanium, aluminum, vanadium, nickel, molybdenum and iron.
8. The device of claim 7 wherein the second material consists essentially of a cobalt-based alloy.
9. The device of claim 8 wherein the cobalt-based alloy consists essentially of cobalt, chromium, iron, nickel, and molybdenum.
10. The device of claim 1 wherein a lateral cross-sectional area of the core is in the range of from ten to forty-six percent of the lateral cross-sectional area of the length of filament.
11. The device of claim 2 wherein both the first material and the second material have linear coefficients of thermal expansion within the range of about 3 x 10-6 per degree F. to about 9 x 10-6 per degree F.
12. The device of claim 1 wherein the filament, as compared to the non-age hardened length of filament, has a yield strength at 0.2 percent offset at least about 20 percent greater and a tensile strength at least about 20 percent greater.
13. The device of claim 1 wherein the greater modulus of elasticity is due at least in part to the age hardening while the length of filament is in a selected shape.
14. The device of claim 13 wherein the enhanced modulus of elasticity is due at least in part to an age hardening of the length of filament to a temperature of about 700°F to about 1200°F after a final annealing.
15. The device of claim 14 wherein both the first material and the second material have linear coefficients of thermal expansion within the range of about 3 x 10-6 per degree F. to about 9 x 10-6 per degree F.
16. The device of claim 2 wherein the core is constructed of a platinum-nickel alloy.
17. The device of claim 16 wherein the platinum-nickel alloy contains about 10 weight percent nickel.
18. The device of any one of claims 1 to 17 which comprises a plurality of the elongate filaments helically wound in at least two oppositely directed sets of strands interwoven with one another in a braided configuration.
19. The device of claim 18 wherein the oppositely directed sets are spaced apart from one another.
20. The device of claim 19 wherein the braided configuration of the helically wound strands is radially self-expanding.
21. The device of any one of claims 1 to 17 comprising a further layer surrounding the core and intermediate the core and case.
22. The device of claim 21 wherein the further layer provides a barrier between the core and case throughout the filament.
23. A process for manufacturing a resilient body-insertable composite filament, which comprises:
a) providing an elongate cylindrical core substantially uniform in lateral cross-section and having a core diameter, and an elongate tubular case substantially uniform in lateral cross-section and having a case inside diameter, wherein one of the core and case is formed of a radiopaque material and the other is formed of a resilient material having an elastic limit of at least 150,000 psi (0.2 percent offset), wherein the core diameter is slightly less than the inside diameter of the case, and the lateral cross-sectional area of the case and core is at most ten times the lateral cross-sectional area of the core;
(b) inserting the core into the case to form an elongate composite filament in which the case surrounds the core;
(c) cold working the composite filament to reduce an outside diameter of the composite filament by at least fifteen percent, to a selected diameter;
(d) annealing the composite filament, to substantially remove strain hardening and other stresses induced by the cold-working step;
(e) repeating the cold-working step (c) and the annealing step (d) until a desired composite filament diameter is obtained after a final cold working step (c);
(f) forming the unannealed composite filament into a shape after the final cold-working step; and (g) while maintaining the cold-worked composite filament in the shape, age hardening the composite filament.
a) providing an elongate cylindrical core substantially uniform in lateral cross-section and having a core diameter, and an elongate tubular case substantially uniform in lateral cross-section and having a case inside diameter, wherein one of the core and case is formed of a radiopaque material and the other is formed of a resilient material having an elastic limit of at least 150,000 psi (0.2 percent offset), wherein the core diameter is slightly less than the inside diameter of the case, and the lateral cross-sectional area of the case and core is at most ten times the lateral cross-sectional area of the core;
(b) inserting the core into the case to form an elongate composite filament in which the case surrounds the core;
(c) cold working the composite filament to reduce an outside diameter of the composite filament by at least fifteen percent, to a selected diameter;
(d) annealing the composite filament, to substantially remove strain hardening and other stresses induced by the cold-working step;
(e) repeating the cold-working step (c) and the annealing step (d) until a desired composite filament diameter is obtained after a final cold working step (c);
(f) forming the unannealed composite filament into a shape after the final cold-working step; and (g) while maintaining the cold-worked composite filament in the shape, age hardening the composite filament.
24. The process of claim 23 wherein the radiopaque material has a linear attenuation coefficient of at least 25 cm-1 at 100 KeV, is ductile, and forms said core.
25. The process of claim 23 or 24, wherein the outside diameter of the composite filament, prior to the cold-working, is at most 6.35 mm (0.250 inches).
26. The process of claim 25 wherein the cold-working includes drawing the composite filament serially through several dies, each die plastically deforming the composite filament to reduce the outside diameter.
27. The process of claim 26 wherein the annealing includes heating the composite filament to a temperature in the range of about 1900°-2300° F. for a period in the range of about 1-15 seconds, after the filament exits one of the dies.
28. The process of any one of claims 23 to 27, wherein the elongate core and case are constructed of such materials that the core and case are capable of being annealed within a single temperature range, and the two materials have about the same coefficient of thermal expansion within the temperature range.
29. The process of claim 28 wherein the materials constituting the core and case have such crystalline structures that minimize tendency for rupture or discontinuities along the core/case interface during subsequent steps.
30. The process of any one of claims 23 to 29, wherein the age hardening includes heating the composite filament to a temperature in the range of about 900°-1000° F. for a period of from about 1 to about 5 hours.
31. The process of any one of claims 23 to 30, further including after forming the composite filament and prior to the cold-working, plastically deforming the composite filament and subjecting the composite filament to annealing temperatures, to substantially reduce the outside diameter of the composite filament from an initial value of at least about 25 mm to an intermediate value of at most about 6.35 mm.
32. The process of claim 31 wherein the cold-working of the composite filament comprises either swaging of the composite filament or pultrusion of the composite filament to reduce the outside diameter in successive increments.
33. The process of claim 24, wherein:
(a) the forming of the composite filament includes the following steps:
(1) severing the annealed composite filament into a plurality of strands; and (2) winding the strands helically about a cylindrical form in two oppositely directed sets of parallel spaced apart strands, with the strands in overlying relation to one another to form multiple intersections; and (b) maintaining the strands in tension while they are so wound, while heating the strands to a temperature in the range of about 900°C-1000° F. to age harden the helical windings.
(a) the forming of the composite filament includes the following steps:
(1) severing the annealed composite filament into a plurality of strands; and (2) winding the strands helically about a cylindrical form in two oppositely directed sets of parallel spaced apart strands, with the strands in overlying relation to one another to form multiple intersections; and (b) maintaining the strands in tension while they are so wound, while heating the strands to a temperature in the range of about 900°C-1000° F. to age harden the helical windings.
34. The process of claim 33 wherein the heating step comprises heating the helical strands for a period of about one to about five hours.
35. The device of any one of claims 1 to 22, wherein the first and second materials are selected such that there is substantially no tendency of intermetallic formation.
36. The device of any one of claims 1 to 22, which further comprises an intermediate barrier against intermetallic formation between the core and the case, wherein the core and the case are constructed of materials that have tendency of intermetallic formation.
37. The process of any one of claims 23 to 34, wherein the core and the case are constructed of materials selected such that there is substantially no tendency of intermetallic formation.
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US6309487B1 (en) * | 1989-11-28 | 2001-10-30 | Robert M. Herrin | Disposable garments and method and apparatus for making |
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-
1993
- 1993-11-23 CA CA002152594A patent/CA2152594C/en not_active Expired - Fee Related
- 1993-11-23 BR BR9307814A patent/BR9307814A/en not_active Application Discontinuation
- 1993-11-23 DE DE69331069T patent/DE69331069T2/en not_active Expired - Lifetime
- 1993-11-23 KR KR1019950702932A patent/KR0147482B1/en active
- 1993-11-23 JP JP6516995A patent/JP2746755B2/en not_active Expired - Fee Related
- 1993-11-23 KR KR1019950702932A patent/KR960700025A/en not_active IP Right Cessation
- 1993-11-23 AU AU56726/94A patent/AU673878B2/en not_active Ceased
- 1993-11-23 AT AT94902318T patent/ATE207728T1/en not_active IP Right Cessation
- 1993-11-23 ES ES94902318T patent/ES2166370T3/en not_active Expired - Lifetime
- 1993-11-23 EP EP94902318A patent/EP0773751B1/en not_active Expired - Lifetime
- 1993-11-23 WO PCT/US1993/011262 patent/WO1994016646A1/en active IP Right Grant
- 1993-11-26 TW TW082109981A patent/TW234689B/zh active
-
1994
- 1994-01-13 IL IL10832594A patent/IL108325A/en not_active IP Right Cessation
- 1994-01-18 ZA ZA94334A patent/ZA94334B/en unknown
-
1995
- 1995-06-06 US US08/469,810 patent/US5824077A/en not_active Expired - Lifetime
- 1995-06-07 US US08/485,626 patent/US5800511A/en not_active Expired - Lifetime
- 1995-06-07 US US08/480,121 patent/US5628787A/en not_active Expired - Lifetime
- 1995-07-18 NO NO952852A patent/NO952852D0/en unknown
- 1995-07-18 FI FI953472A patent/FI953472A0/en unknown
-
1996
- 1996-12-12 US US08/764,130 patent/US5679470A/en not_active Expired - Lifetime
-
1997
- 1997-02-28 AU AU15014/97A patent/AU689739B2/en not_active Ceased
-
1998
- 1998-12-07 IL IL12741898A patent/IL127418A0/en unknown
-
2002
- 2002-06-19 US US10/175,254 patent/US20030009215A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US5628787A (en) | 1997-05-13 |
IL108325A0 (en) | 1994-04-12 |
AU1501497A (en) | 1997-05-29 |
NO952852L (en) | 1995-07-18 |
US5800511A (en) | 1998-09-01 |
BR9307814A (en) | 1995-11-14 |
FI953472A (en) | 1995-07-18 |
EP0773751B1 (en) | 2001-10-31 |
US5824077A (en) | 1998-10-20 |
AU673878B2 (en) | 1996-11-28 |
ZA94334B (en) | 1995-07-18 |
FI953472A0 (en) | 1995-07-18 |
DE69331069T2 (en) | 2002-07-04 |
KR0147482B1 (en) | 1998-08-01 |
NO952852D0 (en) | 1995-07-18 |
IL108325A (en) | 2000-02-17 |
TW234689B (en) | 1994-11-21 |
CA2152594A1 (en) | 1994-08-04 |
JP2746755B2 (en) | 1998-05-06 |
WO1994016646A1 (en) | 1994-08-04 |
JPH08502436A (en) | 1996-03-19 |
ES2166370T3 (en) | 2002-04-16 |
AU5672694A (en) | 1994-08-15 |
AU689739B2 (en) | 1998-04-02 |
US20030009215A1 (en) | 2003-01-09 |
KR960700025A (en) | 1996-01-19 |
DE69331069D1 (en) | 2001-12-06 |
US5679470A (en) | 1997-10-21 |
EP0773751A1 (en) | 1997-05-21 |
IL127418A0 (en) | 1999-10-28 |
ATE207728T1 (en) | 2001-11-15 |
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