US20020084178A1 - Method and apparatus for manufacturing polymer fiber shells via electrospinning - Google Patents

Method and apparatus for manufacturing polymer fiber shells via electrospinning Download PDF

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Publication number
US20020084178A1
US20020084178A1 US09/982,017 US98201701A US2002084178A1 US 20020084178 A1 US20020084178 A1 US 20020084178A1 US 98201701 A US98201701 A US 98201701A US 2002084178 A1 US2002084178 A1 US 2002084178A1
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US
United States
Prior art keywords
electrode
precipitation electrode
precipitation
subsidiary
polymer
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.)
Abandoned
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US09/982,017
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English (en)
Inventor
Alexander Dubson
Eli Bar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nicast Ltd
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Nicast Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nicast Ltd filed Critical Nicast Ltd
Priority to US09/982,017 priority Critical patent/US20020084178A1/en
Assigned to NICAST LTD. reassignment NICAST LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAR, ELI, DUBSON, ALEXANDER
Priority to JP2002551015A priority patent/JP2005507464A/ja
Priority to MXPA03005551A priority patent/MXPA03005551A/es
Priority to CNA018227031A priority patent/CN1635861A/zh
Priority to CNA018226612A priority patent/CN1489513A/zh
Priority to IL15651201A priority patent/IL156512A0/xx
Priority to AU2002222494A priority patent/AU2002222494A1/en
Priority to AT01271232T priority patent/ATE460903T1/de
Priority to CA2432164A priority patent/CA2432164C/fr
Priority to EP01271185A priority patent/EP1353606B1/fr
Priority to AU2002216342A priority patent/AU2002216342A1/en
Priority to US10/433,620 priority patent/US20040030377A1/en
Priority to US10/433,621 priority patent/US7112293B2/en
Priority to CA002432156A priority patent/CA2432156A1/fr
Priority to AU2002222494A priority patent/AU2002222494A8/xx
Priority to EP01271184A priority patent/EP1578306A2/fr
Priority to CA002432159A priority patent/CA2432159A1/fr
Priority to EP01271232A priority patent/EP1355677B1/fr
Priority to AT01271185T priority patent/ATE462371T1/de
Priority to DE60141710T priority patent/DE60141710D1/de
Priority to AU2002216340A priority patent/AU2002216340A1/en
Priority to IL15651401A priority patent/IL156514A0/xx
Priority to IL15651301A priority patent/IL156513A0/xx
Priority to PCT/IL2001/001171 priority patent/WO2002049535A2/fr
Priority to JP2002550881A priority patent/JP2004532665A/ja
Priority to DE60141607T priority patent/DE60141607D1/de
Priority to CNA018226671A priority patent/CN1599582A/zh
Priority to PCT/IL2001/001172 priority patent/WO2002049536A2/fr
Priority to MXPA03005552A priority patent/MXPA03005552A/es
Priority to PCT/IL2001/001168 priority patent/WO2002049678A2/fr
Priority to JP2002550882A priority patent/JP4145143B2/ja
Priority to MXPA03005553A priority patent/MXPA03005553A/es
Priority to US10/433,622 priority patent/US7115220B2/en
Priority to US10/471,277 priority patent/US7244116B2/en
Priority to US10/471,276 priority patent/US7276271B2/en
Priority to JP2002572903A priority patent/JP2004530054A/ja
Priority to JP2002572904A priority patent/JP2004531652A/ja
Priority to JP2002572905A priority patent/JP4130364B2/ja
Priority to AU2002241221A priority patent/AU2002241221A1/en
Priority to EP02707069A priority patent/EP1377419A4/fr
Priority to PCT/IL2002/000220 priority patent/WO2002074191A2/fr
Priority to DE60236919T priority patent/DE60236919D1/de
Priority to PCT/IL2002/000219 priority patent/WO2002074190A2/fr
Priority to AT02707070T priority patent/ATE473082T1/de
Priority to AU2002242929A priority patent/AU2002242929A1/en
Priority to EP02708603A priority patent/EP1377421A4/fr
Priority to US10/471,278 priority patent/US7794219B2/en
Priority to PCT/IL2002/000218 priority patent/WO2002074189A2/fr
Priority to AU2002241222A priority patent/AU2002241222A1/en
Priority to EP02707070A priority patent/EP1377420B1/fr
Publication of US20020084178A1 publication Critical patent/US20020084178A1/en
Priority to IL156514A priority patent/IL156514A/en
Priority to IL156513A priority patent/IL156513A/en
Priority to HK06100173.3A priority patent/HK1080347A1/zh
Priority to US11/398,573 priority patent/US20070031607A1/en
Abandoned legal-status Critical Current

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    • 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
    • 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
    • A61F2/02—Prostheses implantable into the body
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    • A61F2/06—Blood vessels
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    • 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
    • A61F2/91—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 made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D04H3/07—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments otherwise than in a plane, e.g. in a tubular way
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • 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
    • A61F2/02—Prostheses implantable into the body
    • A61F2/04—Hollow or tubular parts of organs, e.g. bladders, tracheae, bronchi or bile ducts
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    • 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
    • A61F2/02—Prostheses implantable into the body
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    • 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
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    • A—HUMAN NECESSITIES
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    • 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
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    • 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
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    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1372—Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes
    • 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
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    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • 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
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y10T428/1393—Multilayer [continuous layer]
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608—Including strand or fiber material which is of specific structural definition
    • Y10T442/614—Strand or fiber material specified as having microdimensions [i.e., microfiber]

Definitions

  • the present invention relates to a method and apparatus for manufacturing polymer fiber shells via electrospinning.
  • Polymer fiber shells such as tubular shaped products, are used in the medical industry for various utilities including esophageal grafts, vascular grafts, stent coats and like.
  • Vascular grafts known in the art typically have a microporous structure that in general allows tissue growth and cell endothelization, thus contributing to long term engraftment and patency of the graft.
  • tissue ingrowth and cell endothelization is typically enhanced with increased in grafts exhibiting increased porosity.
  • increasing the porosity of vascular grafts leads to a considerable reduction of the mechanical and tensile strength of the graft, and as a consequence to a reduction in the functionality thereof.
  • Electrospinning has been used for generating various products for medical applications, e.g., wound dressings, prosthetic devices, and vascular grafts as well as for industrial use, e.g., electrolytic cell diaphragms, battery separators, and fuel cell components. It has already been proposed to produce by electrospinning products having the appearance of shells.
  • U.S. Pat. No. 4,323,525 discloses a method of preparing a tubular product by electrostatically spinning a fiber forming material and collecting the resulting spun fibers on a rotating mandrel.
  • 4,552,707 discloses a varying rotation rate mandrel which controls the “anisotropy extent” of fiber orientation of the final product. Additional examples of tubular shaped products and a like are disclosed, e.g., in U.S. Pat. Nos. 4,043,331, 4,127,706, 4,143,196, 4,223,101, 4,230,650 and 4,345,414.
  • the process of electrospinning creates a fine stream or jet of liquid that upon proper evaporation yields a non-woven fiber structure.
  • the fine stream of liquid is produced by pulling a small amount of a liquefied polymer (either polymer dissolved in solvent (polymer solution) or melted polymer) through space using electrical forces.
  • the produced fibers are then collected on a suitably located precipitation device, such as a mandrel to form tubular structures.
  • a precipitation device such as a mandrel to form tubular structures.
  • the hardening procedure may be mere cooling, however other procedures such as chemical hardening or evaporation of solvent may also be employed.
  • an electric field with high filed lines density may results in a corona discharge near the precipitation device, and consequently prevent fibers from being collected by the precipitation device.
  • the filed lines density of an electric field is determined inter alia by the geometry of the precipitation device; in particular, sharp edges on the precipitation device increase the effect of corona discharge.
  • electrospinning can be efficiently used for generating large diameter shells, the nature of the electrospinning process prevents efficient generation of products having an intricate profile and/or small diameter, such as vascular grafts.
  • porosity and radial strength are conflicting, prior art electrospinning methods cannot be effectively used for manufacturing vascular grafts having both characteristics.
  • an apparatus for manufacturing polymer fiber shells from liquefied polymer comprising: (a) a precipitation electrode being for generating the polymer fiber shell thereupon; (b) a dispenser, being at a first potential relative to the precipitation electrode so as to generate an electric field between the precipitation electrode and the dispenser, the dispenser being for: (i) charging the liquefied polymer thereby providing a charged liquefied polymer; and (ii) dispensing the charged liquefied polymer in a direction of the precipitation electrode; and (c) a subsidiary electrode being at a second potential relative to the precipitation electrode, the subsidiary electrode being for modifying the electric field between the precipitation electrode and the dispenser.
  • a method for forming a liquefied polymer into a non-woven polymer fiber shells comprising: (a) charging the liquefied polymer thereby producing a charged liquefied polymer; (b) subjecting the charged liquefied polymer to a first electric field; (c) dispensing the charged liquefied polymer within the first electric field in a direction of a precipitation electrode, the precipitation electrode being designed and configured for generating the polymer fiber shell; (d) providing a second electric field being for modifying the first electric field; and (e) using the precipitation electrode to collect the charged liquefied polymer thereupon, thereby forming the non-woven polymer fiber shell.
  • the first electric field is defined between the precipitation electrode and a dispensing electrode being at a first potential relative to the precipitation electrode.
  • step (c) is effected by dispensing the charged liquefied polymer from the dispensing electrode.
  • the second electric field is defined by a subsidiary electrode being at a second potential relative to the precipitation electrode.
  • the subsidiary electrode serves for reducing non-uniformities in the first electric field.
  • the subsidiary electrode serves for controlling fiber orientation of the polymer fiber shell generated upon the precipitation electrode.
  • the subsidiary electrode serves to minimize a volume charge generated between the dispenser and the precipitation electrode.
  • the method further comprising moving the subsidiary electrode along the precipitation electrode during step (e).
  • the method further comprising moving the dispensing electrode along the precipitation electrode during step (c).
  • the method further comprising synchronizing the motion of the dispensing electrode and the subsidiary electrode along the precipitation electrode.
  • the dispenser comprises a mechanism for forming a jet of the charged liquefied polymer.
  • the apparatus further comprising a bath for holding the liquefied polymer.
  • the mechanism for forming a jet of the charged liquefied polymer includes a dispensing electrode.
  • the dispenser is operative to move along a length of the precipitation electrode.
  • the precipitation electrode includes at least one rotating mandrel.
  • the rotating mandrel is a cylindrical mandrel.
  • the rotating mandrel is an intricate-profile mandrel.
  • the intricate-profile mandrel includes sharp structural elements.
  • the cylindrical mandrel is of a diameter selected from a range of 0.1 to 20 millimeters.
  • the precipitation electrode includes at least one structural element selected from the group consisting of a protrusion, an orifice, a groove, and a grind.
  • the subsidiary electrode is of a shape selected from the group consisting of a plane, a cylinder, a torus and a wire.
  • the subsidiary electrode is operative to move along a length of the precipitation electrode.
  • the subsidiary electrode is tilted at angle with respect to a longitudinal axis of the precipitation electrode, the angle is ranging between 45 and 90 degrees.
  • the subsidiary electrode is positioned at a distance of 5-70 millimeters from the precipitation electrode.
  • the subsidiary electrode is positioned at a distance ⁇ from the precipitation electrode, ⁇ being equal to 12 ⁇ R(1 ⁇ V 2 /V 1 ), where ⁇ is a constant ranging between about 0.7 and about 0.9, R is the curvature-radius of the polymer fiber shell formed on the precipitation electrode, V 1 is the first potential and V 2 is the second potential.
  • an apparatus for manufacturing a polymer fiber shells from liquefied polymer comprising: (a) a dispenser, for: (i) charging the liquefied polymer thereby providing a charged liquefied polymer; and (ii) dispensing the charged liquefied polymer; and (b) a precipitation electrode being at a potential relative to the dispenser thereby generating an electric field between the precipitation electrode and the dispenser, the precipitation electrode being for collecting the charged liquefied polymer drawn by the electric field, to thereby form the polymer fiber shell thereupon, wherein the precipitation electrode is designed so as to reduce non-uniformities in the electric field.
  • the precipitation electrode is formed from a combination of electroconductive and non-electroconductive materials.
  • a surface of the precipitation electrode is formed by a predetermined pattern of the electroconductive and non-electroconductive materials.
  • the precipitation electrode is formed from at least two layers.
  • the at least two layers include an electroconductive layer and a partial electroconductive layer.
  • partial electroconductive layer is partial electroconductive layer is formed from a combination of an electroconductive material and at least one dielectric material.
  • the dielectric material is selected from a group consisting of polyamide and polyacrylonitrile and polytetrafluoroethylene.
  • the dielectric material is Titanium Nitride.
  • the partial electroconductive layer is selected of a thickness ranging between 0.1 to 90 microns.
  • the present invention successfully addresses the shortcomings of the presently known configurations by providing an electrospinning apparatus and method capable of fabricating a non-woven polymer fiber shell which can be used in vascular grafts.
  • FIG. 1 is a schematic illustration of a prior art electrospinning apparatus
  • FIG. 2 is a schematic illustration of an electrospinning apparatus which includes a subsidiary electrode according to the teachings of the present invention
  • FIG. 3 is a schematic illustration of an electrospinning apparatus which includes a planar subsidiary electrode according to the teachings of the present invention
  • FIG. 4 is a schematic illustration of an electrospinning apparatus which includes a cylindrical subsidiary electrode according to the teachings of the present invention
  • FIG. 5 is a schematic illustration of an electrospinning apparatus which includes a linear subsidiary electrode according to the teachings of the present invention
  • FIG. 6 is a schematic illustration of an electrospinning apparatus which includes a composite subsidiary electrode according to the teachings of the present invention
  • FIG. 7 is an electron microscope image of material spun using conventional electrospinning techniques
  • FIG. 8 is an electron microscope image of material spun using an apparatus which incorporates a flat subsidiary electrode, positioned 20 millimeters from the mandrel, according to the teachings of the present invention
  • FIG. 9 is an electron microscope image of material spun using an apparatus which incorporates a flat subsidiary electrode, positioned 9 millimeters from the mandrel, according to the teachings of the present invention.
  • FIG. 10 is an electron microscope image of polar-oriented material spun using an apparatus which incorporates a linear subsidiary electrode according to the teachings of the present invention.
  • the present invention is of a method and an apparatus for manufacturing a polymer fiber shell using electrospinning. Specifically, the present invention can be used to manufacture intricate-profile products and vascular grafts of small to large diameter via electrospinning.
  • FIGS. 2 - 10 of the drawings For purposes of better understanding the present invention, as illustrated in FIGS. 2 - 10 of the drawings, reference is first made to the construction and operation of a conventional (i.e., prior art) electrospinning apparatus as illustrated in FIG. 1.
  • FIG. 1 illustrates an apparatus for manufacturing a tubular structure using a conventional electrospinning apparatus, which is referred to herein as apparatus 10 .
  • Apparatus 10 includes a dispenser 12 which can be, for example, a bath provided with capillary apertures 14 .
  • Dispenser 12 serves for storing the polymer to be spun in a liquid form.
  • Dispenser 12 is positioned at a predetermined distance from a precipitation electrode 16 .
  • Precipitation electrode 16 serves for generating the tubular structure thereupon.
  • Precipitation electrode 16 is typically manufactured in the form of a mandrel or any other cylindrical structure.
  • Precipitation electrode 16 is rotated by a mechanism such that a tubular structure is formed when coated with the polymer.
  • Dispenser 12 is typically grounded, while precipitation electrode 16 is connected to a source of high voltage preferably of negative polarity, thus forming an electric field between dispenser 12 and precipitation electrode 16 .
  • precipitation electrode 16 can be grounded while dispenser 12 is connected to a source of high voltage, preferably with positive polarity.
  • a liquefied polymer e.g., melted polymer or dissolved polymer
  • a process of solvent evaporation or cooling starts which is accompanied by the creation of capsules with a semi-rigid envelope or crust.
  • An electric field occasionally accompanied a by unipolar corona discharge in the area of dispenser 12 , is generated by the potential difference between dispenser 12 and precipitation electrode 16 . Because the liquefied polymer possesses a certain degree of electrical conductivity, the above-described capsules become charged.
  • the charges tend to distribute along the jets, thus preventing existence of any non-zero component of electric field inside the jet.
  • a conduction current flows along the jets, which results in the accumulation of (different sign) free charges on the liquefied polymer surface.
  • the jets depart from the dispenser 12 and travel towards the opposite polarity electrode, i.e., precipitation electrode 16 .
  • the jet cools or solvent therein evaporates, thus forming fibers which are collected on the surface of precipitation electrode 16 . Since electrode 16 is rotating the charged fibers form a tubular shape.
  • the orientation of the electric field maximal strength vector is such that precipitation electrode 16 is coated coaxially by the fibers.
  • small diameter products have limited radial strength when manufactured via existing electrospinning methods, as described above.
  • the electric field magnitude in the vicinity of precipitation electrode 16 may exceed the air electric strength (about 30 kV/cm), and a corona discharge may develop in the area of precipitation electrode 16 .
  • the effect of corona discharge decreases the coating efficiency of the process as described hereinbelow, and may even resultant in a total inability of fibers to be collected upon precipitation electrode 16 .
  • Corona discharge initiation is accompanied by the generation of a considerable amount of air ions having opposite charge sign with respect to the charged fibers. Since an electric force is directed with respect to the polarity of charges on which it acts, theses ions start to move at the opposite direction to fibers motion i.e., from precipitation electrode 16 towards dispenser 12 . Consequently, a portion of these ions generate a volume charge (ion cloud), non-uniformly distributed in the inter-electrode space, thereby causing electric field lines to partially close on the volume charge rather than on precipitation electrode 16 .
  • a third electrode within an electrospinning apparatus enables to control the electric field generated between the dispenser and precipitation electrode.
  • a third electrode may either substantially decreases non-uniformities in the electric field or provides for controlled fiber orientation upon deposition.
  • apparatus 20 for manufacturing a polymer fiber shell from a liquefied polymer.
  • apparatus 20 includes a precipitation electrode 22 which serves for generating the polymer fiber shell thereupon.
  • Precipitation electrode 22 can be, for example, a mandrel of uniform or varying radius, which may include some structural elements such as, but not limited to, protrusions, orifices and grooves.
  • the surface of precipitation electrode 22 may also contain grinds.
  • the diameter of the mandrel may vary from about 0.1 millimeter up to about 20 millimeters depending on the diameter of the polymer fiber shell to be spun thereupon.
  • Apparatus 20 further includes a dispenser 24 , which is at a first potential relative to precipitation electrode 22 .
  • a dispenser 24 which is at a first potential relative to precipitation electrode 22 .
  • Such a potential can be generated by grounding dispenser 24 , and connecting a source of high voltage with negative polarity to precipitation electrode 22 .
  • precipitation electrode 22 can be grounded while dispenser 24 is connected to a source of high voltage with positive polarity.
  • an absolute value for the potential difference between dispenser 24 and precipitation electrode 22 may range between about 10 kV and about 100 kV.
  • dispenser 24 and precipitation electrode 22 ensures that an electric field is maintained therebetween, which electric field is important for the electrospinning process as described hereinabove.
  • Dispenser 24 serves for charging the liquefied polymer, thereby providing a charged liquefied polymer and dispensing the charged liquefied polymer in a direction of precipitation electrode 22 .
  • Dispenser 24 may also include a mechanism for moving it along a longitudinal axis of precipitation electrode 22 , thus enabling dispensing of the charged liquefied polymer at various points along the longitudinal axis of precipitation electrode 22 .
  • the charged liquefied polymer may be, for example polyurethane, polyester, polyolefin, polymethyl methacrylate, polyvinyl aromatic, polyvinyl ester, polyamide, polyimide, polyether, polycarbonate, polyacrilonitrile, polyvinyl pyrrolidone, polyethylene oxide, poly (L-lactic acid), poly (lactide-CD-glycoside), polycaprolactone, polyphosphate ester, poly (glycolic acid), poly (DL-lactic acid), and some copolymers.
  • Biolmolecules such as DNA, silk, chitozan and cellulose may also be used. Improved charging of the polymer may also be required.
  • Improved charging is effected according to the present invention by mixing the liquefied polymer with a charge control agent (e.g., a dipolar additive) to form, for example, a polymer-dipolar additive complex which apparently better interacts with ionized air molecules formed under the influence of the electric field.
  • a charge control agent e.g., a dipolar additive
  • the charge control agent is typically added in the grams equivalent per liter range, say, in the range of from about 0.001 N to about 0.1 N, depending on the respective molecular weights of the polymer and the charge control agent used.
  • U.S. Pat. Nos. 5,726,107; 5,554,722; and 5,558,809 teach the use of charge control agents in combination with polycondensation processes in the production of electret fibers, which are fibers characterized in a permanent electric charge, using melt spinning and other processes devoid of the use of an precipitation electrode.
  • a charge control agent is added in such a way that it is incorporated into the melted or partially melted fibers and remains incorporated therein to provide the fibers with electrostatic charge which is not dissipating for prolonged time periods, say months.
  • the charge control agent transiently binds to the outer surface of the fibers and therefore the charge dissipates shortly thereafter (within minutes). This is because polycondensation is not exercised at all such the chemical intereaction between the agent and the polymer is absent, and further due to the low concentration of charge control agent employed. The resulting shell is therefore substantially charge free.
  • Suitable charge control agents include, but are not limited to, monoand poly-cyclic radicals that can bind to the polymer molecule via, for example, —C ⁇ C—, ⁇ C—SH— or —CO—NH— groups, including biscationic amides, phenol and uryl sulfide derivatives, metal complex compounds, triphenylmethanes, dimethylmidazole and ethoxytrimethylsians.
  • dispenser 24 typically includes a bath for holding the liquefied polymer and a mechanism for forming a jet, which mechanism may be, for example, a dispensing electrode.
  • Apparatus 20 further includes at least one subsidiary electrode 26 which is at a second potential relative to precipitation electrode 22 .
  • Subsidiary electrode 26 serves for controlling the direction and magnitude of the electric field between precipitation electrode 22 and dispenser 24 and as such, subsidiary electrode 26 can be used to control the orientation of polymer fibers deposited on precipitation electrode 22 .
  • subsidiary electrode 26 serves as a supplementary screening electrode. Broadly stated, use of screening results in decreasing the coating precipitation factor, which is particularly important upon mandrels having at least a section of small radii of curvature.
  • the size, shape, position and number of subsidiary electrode 26 is selected so as to maximize the coating precipitation factor, while minimizing the effect of corona discharge in the area of precipitation electrode 22 and/or so as to provide for controlled fiber orientation upon deposition.
  • subsidiary electrode 26 is positioned 5-70 mm away from precipitation electrode 22 .
  • such a distance is selected according to the following:
  • ⁇ is a dimensionless constant named a fiber-charge accounting factor, which ranges between about 0.7 and about 0.9
  • R is the curvature-radius of precipitation electrode 22
  • V 1 is the potential difference between dispenser 24 and precipitation electrode 22
  • V 2 is the potential difference between subsidiary electrode 26 and precipitation electrode 22 .
  • Subsidiary electrode 26 may include a mechanism for moving it along a longitudinal axis of precipitation electrode 22 . Such a mechanism may be in use when enhanced control over fiber orientation is required.
  • Subsidiary electrode 26 may also be tilted through an angle of 45-90 degrees with respect to the longitudinal axis of precipitation electrode 22 . Such tilting may be used to provide for controlled fiber orientation upon deposition, hence to control the radial strength of the manufactured shell; specifically, large angles result in higher radial strength.
  • electrode 26 may also determine the quality of the shell formed by apparatus 20 .
  • electrode 26 may be fabricated in a variety of shapes each serving a specific purpose. Electrode shapes which can be used with apparatus 20 of the present invention include, but are not limited to, a plane, a cylinder, a torus a rod, a knife, an arc or a ring.
  • An apparatus 20 which includes a subsidiary electrode 26 of a cylindrical (FIG. 4) or a flat shape (FIG. 3) enables manufacturing intricate-profile products being at least partially with small radius of curvature, which radius may range between 0.025 millimeters and 5 millimeters.
  • the coating of such structures is characterized by random-oriented (FIG. 8) or even polar-oriented (FIG. 9) fibers, as opposed to an axial coating which is typical for small curvature products manufactured via existing electrospinning methods as demonstrated in FIG. 7 (further described in the Examples section).
  • the distance between subsidiary electrode 26 and precipitation electrode 22 can be determined as ⁇ /x where x is a factor ranging between 1.8 and 2, and where ⁇ is as defined by Equation 1 above.
  • positioning and/or shape of electrode 26 determines fiber orientation in the polymer fiber shell formed.
  • Control over fiber orientation is also advantageous when fabricating composite polymer fiber shells which are manufactured by sequential deposition of several different fiber materials.
  • FIG. 5 illustrates an apparatus 20 which utilizes a linear (e.g., a rod, a knife, an arc or a ring) subsidiary electrode 26 .
  • a linear e.g., a rod, a knife, an arc or a ring
  • the present invention provides an electrospinning apparatus in which the electric field is under substantial control, thereby providing either random or predetermined fibers orientation.
  • precipitation electrode 34 of apparatus 30 having a dispenser 32 can be designed and configured so as to reduce non-uniformities in the electric field.
  • precipitation electrode 34 is fabricated from at least two layers of materials, an inner layer 36 made of electroconductive material and an outer layer 38 made of a material having high dielectric properties. Such a fabrication design results in a considerable increase of corona discharge threshold thus considerably reducing corona discharge from precipitation electrode 34 .
  • Materials suitable for use with outer layer 38 of precipitation electrode 34 can be ceramic materials e.g., Titanium Nitride, Aluminum Oxide and the like, or polymer materials e.g., polyamide, polyacrylonitrile, polytetrafluoroethylene and the like.
  • the thickness of outer layer 38 depends on the dielectric properties of the material from which it is made and can vary from less than one micron, in the case of, for example, a Titanium Nitride layer, or tens of microns, in the case of, for example, polytetrafluoroethylene, polyamide or polyacrylonitrile layer.
  • this precipitation electrode configuration enables easier separation of formed structures therefrom.
  • outer layer 38 of precipitation electrode 34 can also be configured for facilitating the removal of the final product from the mandrel.
  • a polycarbonate resin grade Caliper 2071 was purchased from Daw Chemical Co. This Polymer is characterized as having good fiber forming abilities and is convenient for electrospinning. Chloroform was used as solvent in all of the examples described hereinbelow.
  • FIG. 7 is an example of non-randomized covering of thin mandrels via conventional electrospinning.
  • a 3-mm cylindrical mandrel was covered by polycarbonate fiber using prior art electrospinning approaches.
  • FIG. 7 is an electron microscope image of the final product, in which axial fiber orientation is well evident. Due to non-uniformities in the electric field, the fibers, while still in motion in the inter-electrode space, are oriented in conformity with the field configuration, and the obtained tubular structure exhibits axial orientation of fibers, and as such is characterized by axial, as opposed to radial strength.
  • FIG. 10 illustrates result obtained from an apparatus configuration which may be employed in order to obtain a predefined oriented structural fiber covering.
  • An apparatus which includes an elliptical subsidiary electrode and a dispenser both moving along the longitudinal axis of the mandrel in a reciprocating synchronous movement was used to coat a 3-mm cylindrical mandrel with polycarbonate fiber.
  • the subsidiary electrode had a large diameter of 120 mm, a small diameter of 117.6 mm and a thickness of 1.2 mm.
  • the subsidiary electrode was positioned 15 mm from the mandrel, at an 80° tilt with respect to the mandrel symmetry axis.

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Priority Applications (54)

Application Number Priority Date Filing Date Title
US09/982,017 US20020084178A1 (en) 2000-12-19 2001-10-19 Method and apparatus for manufacturing polymer fiber shells via electrospinning
JP2002551015A JP2005507464A (ja) 2000-12-19 2001-12-17 電界紡糸法によりポリマー繊維シェルを製造する方法および装置
MXPA03005551A MXPA03005551A (es) 2000-12-19 2001-12-17 Metodo y aparato para la manufactura de peliculas galvanicas de fibras de polimero via electrohilado.
CNA018227031A CN1635861A (zh) 2000-12-19 2001-12-17 含有药物的聚合物包覆的支架组件
CNA018226612A CN1489513A (zh) 2000-12-19 2001-12-17 通过电纺丝制造聚合物纤维壳的方法和设备
IL15651201A IL156512A0 (en) 2000-12-19 2001-12-17 Medicated polymer-coated stent assembly
AU2002222494A AU2002222494A1 (en) 2000-12-19 2001-12-17 Medicated polymer-coated stent assembly
AT01271232T ATE460903T1 (de) 2000-12-19 2001-12-17 Verfahren und gerät zur herstellung von polymerfaserhüllen durch elektrospinnen
CA2432164A CA2432164C (fr) 2000-12-19 2001-12-17 Prothese vasculaire et procede de production de celle-ci
EP01271185A EP1353606B1 (fr) 2000-12-19 2001-12-17 Prothese vasculaire et procede de production de celle-ci
AU2002216342A AU2002216342A1 (en) 2000-12-19 2001-12-17 Improved vascular prosthesis and method for production thereof
US10/433,620 US20040030377A1 (en) 2001-10-19 2001-12-17 Medicated polymer-coated stent assembly
US10/433,621 US7112293B2 (en) 2000-12-19 2001-12-17 Method and apparatus for manufacturing polymer fiber shells via electrospinning
CA002432156A CA2432156A1 (fr) 2000-12-19 2001-12-17 Procede et appareil de fabrication de gaines de fibres polymeres par electrobobinage
AU2002222494A AU2002222494A8 (en) 2000-12-19 2001-12-17 Medicated polymer-coated stent assembly
EP01271184A EP1578306A2 (fr) 2000-12-19 2001-12-17 Ensemble stent revetu de polymere
CA002432159A CA2432159A1 (fr) 2000-12-19 2001-12-17 Ensemble stent revetu de polymere
EP01271232A EP1355677B1 (fr) 2000-12-19 2001-12-17 Procede et appareil de fabrication de gaines de fibres polymeres par electrobobinage
AT01271185T ATE462371T1 (de) 2000-12-19 2001-12-17 Verbesserte vaskularprothese und verfahren zu ihrer herstellung
DE60141710T DE60141710D1 (de) 2000-12-19 2001-12-17 Verbesserte vaskularprothese und verfahren zu ihrer herstellung
AU2002216340A AU2002216340A1 (en) 2000-12-19 2001-12-17 Method and apparatus for manufacturing polymer fiber shells via electrospinning
IL15651401A IL156514A0 (en) 2000-12-19 2001-12-17 Improved vascular prosthesis and method for production thereof
IL15651301A IL156513A0 (en) 2000-12-19 2001-12-17 Method and apparatus for manufacturing polymer fiber shells via electrospinning
PCT/IL2001/001171 WO2002049535A2 (fr) 2000-12-19 2001-12-17 Ensemble stent revetu de polymere
JP2002550881A JP2004532665A (ja) 2000-12-19 2001-12-17 医用ポリマー被覆ステント組立体
DE60141607T DE60141607D1 (de) 2000-12-19 2001-12-17 Verfahren und gerät zur herstellung von polymerfaserhüllen durch elektrospinnen
CNA018226671A CN1599582A (zh) 2000-12-19 2001-12-17 改进型脉管假体及其制造方法
PCT/IL2001/001172 WO2002049536A2 (fr) 2000-12-19 2001-12-17 Prothese vasculaire et procede de production de celle-ci
MXPA03005552A MXPA03005552A (es) 2000-12-19 2001-12-17 Ensamble de espiral recubierto de polimero medicado.
PCT/IL2001/001168 WO2002049678A2 (fr) 2000-12-19 2001-12-17 Procede et appareil de fabrication de gaines de fibres polymeres par electrobobinage
JP2002550882A JP4145143B2 (ja) 2000-12-19 2001-12-17 改良型脈管プロテーゼおよびその製造方法
MXPA03005553A MXPA03005553A (es) 2000-12-19 2001-12-17 Protesis vascular mejorada y metodo para produccion de la misma.
US10/433,622 US7115220B2 (en) 2000-12-19 2001-12-17 Vascular prosthesis and method for production thereof
US10/471,277 US7244116B2 (en) 2000-12-19 2002-03-19 Apparatus for improving mechanical characteristics of nonwoven materials
US10/471,276 US7276271B2 (en) 2000-12-19 2002-03-19 Polymer fiber tubular structure having kinking resistance
JP2002572903A JP2004530054A (ja) 2001-03-20 2002-03-19 不織材料の機械的特性を改良する方法及び装置
JP2002572904A JP2004531652A (ja) 2001-03-20 2002-03-19 耐キンク形成性が改良された重合体繊維管形構造体
JP2002572905A JP4130364B2 (ja) 2001-03-20 2002-03-19 携帯式電気紡糸装置
AU2002241221A AU2002241221A1 (en) 2001-03-20 2002-03-19 Electrospinning nonwoven materials with rotating electrode
EP02707069A EP1377419A4 (fr) 2001-03-20 2002-03-19 Procede et appareil destines a ameliorer les caracteristiques mecaniques de nontisses
PCT/IL2002/000220 WO2002074191A2 (fr) 2001-03-20 2002-03-19 Appareil d'electrofilage portatif
DE60236919T DE60236919D1 (de) 2001-03-20 2002-03-19 Tragbare elektrospinnvorrichtung
PCT/IL2002/000219 WO2002074190A2 (fr) 2001-03-20 2002-03-19 Structure tubulaire en fibre polymere presentant une resistance a la deformation accrue
AT02707070T ATE473082T1 (de) 2001-03-20 2002-03-19 Tragbare elektrospinnvorrichtung
AU2002242929A AU2002242929A1 (en) 2001-03-20 2002-03-19 Polymer fiber tubular structure having improved kinking resistance
EP02708603A EP1377421A4 (fr) 2001-03-20 2002-03-19 Structure tubulaire en fibre polymere presentant une resistance a la deformation accrue
US10/471,278 US7794219B2 (en) 2001-03-20 2002-03-19 Portable electrospinning device
PCT/IL2002/000218 WO2002074189A2 (fr) 2001-03-20 2002-03-19 Procede et appareil destines a ameliorer les caracteristiques mecaniques de nontisses
AU2002241222A AU2002241222A1 (en) 2001-03-20 2002-03-19 Portable electrospinning device
EP02707070A EP1377420B1 (fr) 2001-03-20 2002-03-19 Appareil d'electrofilage portatif
IL156514A IL156514A (en) 2000-12-19 2003-06-18 Vascular prosthesis and method for production thereof
IL156513A IL156513A (en) 2000-12-19 2003-06-18 Method and apparatus for manufacturing polymer fiber shells via electrospinning
HK06100173.3A HK1080347A1 (zh) 2000-12-19 2006-01-04 含有藥物的聚合物包覆的支架組件
US11/398,573 US20070031607A1 (en) 2000-12-19 2006-04-06 Method and apparatus for coating medical implants

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US09/982,017 US20020084178A1 (en) 2000-12-19 2001-10-19 Method and apparatus for manufacturing polymer fiber shells via electrospinning

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US10/433,620 Continuation US20040030377A1 (en) 2000-12-19 2001-12-17 Medicated polymer-coated stent assembly
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