WO2005098099A1 - Controle base sur une emulsion de morphologie de fibres electrofilees - Google Patents

Controle base sur une emulsion de morphologie de fibres electrofilees Download PDF

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Publication number
WO2005098099A1
WO2005098099A1 PCT/US2005/009048 US2005009048W WO2005098099A1 WO 2005098099 A1 WO2005098099 A1 WO 2005098099A1 US 2005009048 W US2005009048 W US 2005009048W WO 2005098099 A1 WO2005098099 A1 WO 2005098099A1
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WIPO (PCT)
Prior art keywords
poly
component
fiber
emulsion
evaporation rate
Prior art date
Application number
PCT/US2005/009048
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English (en)
Inventor
Venkatram P. Shastri
Jay C. Sy
I-Wei Chen
Original Assignee
The Children's Hospital Of Philadelphia
The Trustees Of The University Of Pennsylvania
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Application filed by The Children's Hospital Of Philadelphia, The Trustees Of The University Of Pennsylvania filed Critical The Children's Hospital Of Philadelphia
Priority to US10/594,094 priority Critical patent/US20070141333A1/en
Publication of WO2005098099A1 publication Critical patent/WO2005098099A1/fr

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Classifications

    • 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
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry 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
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

  • Electrospinning is an atomization process of a conducting fluid which exploits the interactions between an electrostatic field and the conducting fluid. During electrospinning, fibers with micron or sub-micron sized diameters are extruded by means of an electrostatic potential from apolymer solution (see U.S. Patent No.1,975,504 to Formhals).
  • a conducting fluid e.g., a semi-dilute polymer solution or a polymer melt
  • a conducting fluid e.g., a semi-dilute polymer solution or a polymer melt
  • Electrostatic atomization occurs when the electrostatic field is strong enough to overcome the surface tension of the liquid.
  • the liquid droplet then becomes unstable and a tiny jet is ejected from the surface of the droplet.
  • the material can be collected as an interconnected web containing relatively fine, i.e. small diameter, fibers.
  • the resulting films (or membranes) from these small diameter fibers have very large surface area to volume ratios and small pore sizes.
  • Electrospun materials possess a high aspect ratio to allow for cell attachment and spreading, which is a desired property for tissue engineering (TE) applications.
  • the longest axis of a spread cell is typically around 5-10 micrometers.
  • ES process is not amenable to significant modifications. Parameters that can be varied in the ES process are the electric field, the distance between the "Taylor Cone” and the target, and polymer solution viscosity (Fridrikh et al., G.C. PhysRevLett. 2003, 90(14), 144502). Due to the complexity of the fiber forming process, very few attempts have been made to alter geometry of electrospun fibers.
  • the process involves introducing the liquid into an electric field through a nozzle, under conditions to produce fibers from a fiber-forming material, which tends to be drawn to a charged collector, and collecting the fibers on a charged tubular collector, which rotates about its longitudinal axis to form a fiberous tubular product.
  • a fiber-forming material which tends to be drawn to a charged collector
  • a charged tubular collector which rotates about its longitudinal axis to form a fiberous tubular product.
  • the spinning process of the '525 patent is used to fabricate tubular products having a homogenous fiber matrix across the wall thickness.
  • U.S. Patent No. 4,689,186 to Bornat is directed to a process for making polyurethane tubular products by electrostatically spinning a fiber-forming solution containing polyurethane.
  • the electrospinning process of the '186 patent is used to fabricate tubular products having a homogenous fiber matrix.
  • Sanders et al. describe entrapment of water droplets in polyvinyl acetate fibers spun from a suspension containing a polymer in methylene chloride and protein (BSA) in a phosphate buffer.
  • the fiber-forming composition was a cloudy suspension and not an emulsion.
  • the ratio of organic solvent to water is 40:1 or about 2.4 vol%.
  • There was no emulsifying agent used in the fiber-forming composition see Macromolecules 2003, 36, 3803-3805).
  • Patent No.6,520,425 to Reneker describes forming nanofibers by using a pressurized gas stream to overcome problems associated with liquids having higher viscosities and inability to create higher forces than electric fields can supply.
  • a pressurized gas stream to overcome problems associated with liquids having higher viscosities and inability to create higher forces than electric fields can supply.
  • All references cited herein are incorporated herein by reference in their entireties.
  • BRIEF SUMMARY OF THE INVENTION Inventors have discovered that fiber morphology can be controlled by using multiphasic compositions, such as, for example, a water/oil emulsion or a double emulsion as a fiber-forming medium.
  • the present invention provides a method of making a fiber comprising providing a first component including water, wherein the first component has a first evaporation rate, providing a second component including a polymer dissolved in a solvent, wherein the second component has a second evaporation rate, provided that the second evaporation rate is higher than the first evaporation rate, combining the first component and the second component to make an emulsion, applying a force to the emulsion, and extruding the emulsion to make the fiber, wherein the fiber has an outer surface, an internal cavity and an outer diameter of at most 10 micrometers. Also provided is a fiber manufactured by the method of the invention.
  • a fiber made from the emulsion comprising water, poly(lactic acid), and optionally a nanoparticle comprising silicone oxide and a biomolecule.
  • the diameter of the fiber is from about 3 nm to 10 micrometers.
  • the invention provides an improvement to the known methods of making a fiber by electrospinning, wherein a fiber is formed by extruding a fiber-forming medium, such as a polymeric composition, from a vessel through an orifice under the influence of a force.
  • the fiber-forming medium comprises an emulsion comprising (1) a first component comprising water, said first component is provided in an amount of at most 20 vol.
  • Fig. 1 is a graph illustrating poly(lactic acid) (PLA) fiber diameter and mo ⁇ hology as a function of volume fraction of aqueous phase in a water/oil (W/O) emulsion.
  • Fig. 1 is a graph illustrating poly(lactic acid) (PLA) fiber diameter and mo ⁇ hology as a function of volume fraction of aqueous phase in a water/oil (W/O) emulsion.
  • Fig. 2 is an electronic microscope image of PLA fibers obtained by spinning from a single-phase system composed of PLA, chloroform and l-methyl-2-pyrrolidinone (NMP).
  • Fig. 3 is an electronic microscope image of PLA fibers obtained by spinning from a W/O emulsion composed of 2.5 v/v % aqueous phase; the porous nature of the fibers is shown in the inset on the bottom left.
  • Fig.4 is an electronic microscope image of PLA fibers obtained by spinning from a W/O emulsion composed of 14 v/v % aqueous phase.
  • Fig. 5 is an electronic microscope image of PLA fibers obtained by spinning from a W/O emulsion composed of 885 ⁇ l PLA, 27 ⁇ l NMP, 0 ⁇ l PVA(10%) and 100 ⁇ l colloid (sample E4).
  • Fig. 6 is an electronic microscope image of PLA fibers obtained by spinning from a W/O emulsion composed of 835 ⁇ l PLA, 25 ⁇ l NMP, 50 ⁇ l PVA, and 100 ⁇ l Colloid/Water (sample E2).
  • Fig.7 is an electronic microscope image of PLA fibers obtained by spinning from a W/O emulsion composed of 835 ⁇ l PLA, 25 ⁇ l NMP, 50 ⁇ l PVA, and 100 ⁇ l Colloid/Water (sample E2).
  • Fig. 8 is an electronic microscope image of PLA fibers obtained by spinning from a W/O emulsion composed of 980 ⁇ l PLA, 80 ⁇ l NMP, 2.5 ⁇ l PVA and 2.5 ⁇ l Colloid/Water (sample WC4).
  • Fig. 9 is an electronic microscope image of PLA fibers obtained by spinning from a W/O emulsion composed of 1 g of Alginate Beads suspended in about 2 ml E4 sample and 125 ⁇ l Colloid/Water (sample AB8).
  • FIG. 10 is an electronic microscope image of PLA fibers obtained by spinning from a W/O emulsion composed of 1 g of Alginate Beads suspended in about 2 ml E4 sample and 125 ⁇ l Colloid/Water (sample AB8).
  • a W/O emulsion composed of 1 g of Alginate Beads suspended in about 2 ml E4 sample and 125 ⁇ l Colloid/Water (sample AB8).
  • DETAILED DESCRIPTION OF THE INVENTION Inventors have discovered that that fiber mo ⁇ hology can be varied by spinning from a multiphasic fiber-forming medium such as, for example, an emulsion, rather than from a solution or a dispersion.
  • mo ⁇ hology of the resulting fiber can be controlled, wherein a preferential evaporation of the more volatile solvent causes the formation of outer surfaces or skins similar to those produced in, for example, a sausage casing process, where the less volatile liquid phase is entrapped and surrounded by a solidified polymer skin.
  • the invention provides a method for making fibers of different morphologies, including, for example, flattened and porous forms.
  • the ability to control morphology of the fiber is useful in various medical application such as, for example, tissue engineering, drug delivery, as well as non-medical application such as, for example, electronics.
  • the present invention provides a method of making a fiber from an emulsion comprising a first component including water, and a second component including a polymer dissolved in a solvent, hi the method, a force is applied to the emulsion to extrude and separate the emulsion into a fiber, wherein the fiber has an outer surface, an internal cavity and an outer diameter of at most 10 micrometers.
  • the force is preferably created by an electrostatic field, i.e., an electric force.
  • the emulsion is preferably electrically conductive or includes electrically conductive materials.
  • Other examples of the force include a magnetic force and an electromagnetic force.
  • Another non-limiting example of the force is a force of pressurized gas.
  • Apparatuses useful in this invention for creation of the electrostatic field are known in the art such as, for example, electrospinners described by Fridrikh et al. and Bornat supra. The technique of spinning liquids has been described in the art, for example, in U.S. Patent No. 4,044,404. These apparatuses employ the electric force for spinning the multiphasic fiber- forming medium of the invention.
  • Another type of apparatuses employs a compressed gas as described by U. S. Patent No. 6,520,425 by Reneker.
  • the multiphasic fiber-forming medium of the invention is an emulsion, such as, for example, a water/oil emulsion, a double emulsion or an emulsion in which particles are dispersed.
  • a emulsion such as, for example, a water/oil emulsion, a double emulsion or an emulsion in which particles are dispersed.
  • the first component an aqueous phase or a hydrophilic component
  • the second component an oil phase or a lipophilic component
  • desired mo ⁇ hology can be achieved as described below.
  • the fist component and the second component are provided at a ratio, wherein the ratio is adapted to change morphology of the fiber and its diameter.
  • fibers with various morphologies include flat fiber, round fiber, porous fiber and combinations thereof (see Figs.2-9). It was observed for an exemplary PLA emulsion, the transition from round to porous fibers occurs in the range of 2-5% volume fraction of aqueous phase in the emulsion. Above 5% volume fraction of aqueous phase, fibers with a flat-ribbon morphology are obtained.
  • the first component comprises water and optionally, glycerol and poly(vinyl alcohol). In certain embodiments, the first component comprises at most 20 vol.
  • the first component comprises from about 5 to about 20 vol. %. In certain embodiments, the first component comprises from about 2 to 5 vol.%. In certain embodiments, the second component comprises at least 80% of the emulsion.
  • the second component comprises polymer, preferably dissolved in an organic solvent.
  • suitable polymers include poly(styrene), poly(urethane), poly(lactic acid), poly(glycolic acid), poly(ester), poly(alpha-hydroxy acid), poly( ⁇ -ca ⁇ rolactone), poly(dioxanone), poly(orthoester), poly(ether-ester), poly(lactone), poly(carbonate), poly(phosphazene), poly(phosphanate), poly(ether), poly(anhydride), mixtures thereof and copolymers thereof.
  • the organic solvent is a member selected from the group consisting of methylene chloride, chloroform, ether, hexane, pentane, petroleum ether, cresol, dichloroethane, ethyl acetate, methyl ethyl ketone, dioxane, propylene carbonate, and butyl acetate.
  • Various additives can be added to the emulsion, such as, for example, a surfactant, an emulsifier, and a stabilizer for impacting properties of emulsion such as stability, consistency, etc.
  • the emulsion can be a microemulsion.
  • the emulsion comprises a third component such as, for example, a biomolecule, a cell, a particle, and a gel.
  • the third component can be dissolved in either or both of the phases or it can be dispersed. Depending on the choice of the phase, the third component can be located inside or outside of the fiber. For example, if the third component is dissolved in the aqueous phase, upon forming of the fiber, it will be trapped inside, upon evaporation of the solvent of the second phase. Also, if the third component is dissolved in the second phase, upon forming of the fiber, it will be trapped in the outer skin of the fiber.
  • Non-limiting examples of suitable biomolecules include a bioactive polypeptide, a polynucleotide coding for the bioactive polypeptide, a cell regulatory small molecule, a peptide, a protein, an oligonucleotide, a nucleic acid, a poly(saccharide), an adenoviral vector, a gene transfection vector, a drug, and a drug delivering agent.
  • Non-limiting examples of suitable cells include chondroblast, chondrocyte, fibroblast, an endothelial cell, osteoblast, osteocyte, an epithelial cell, an epidermal cell, amesenchymal cell, a hemopoietic cell, an embryoid body, a stem cell, and dorsal root ganglia.
  • the particle is a colloidal particle or a solid particle. Patterning the surfaces of fibers with particles has practical applications, for example, in tissue engineering where presentation of chemical and physical cues on degradable scaffolds allows a more precise control over cell-scaffold interactions.
  • the colloidal particle has a diameter of from about 3nm to about
  • the solid particle has a diameter of about 3nm to about 10 micrometers and said solid nanoparticle is a member selected from the group consisting of a polymer, an oxide, a nitride, a carbide, calcium silicate, calcium phosphate, calcium carbonate, a carbonaceous material, a metal, and a semiconductor.
  • SNP encapsulation silica nanoparticles
  • Non-limiting examples of surfactants include non-ionic surfactants such as, for example,
  • PLURONIC polyvinyl alcohol, poly(sorbate) (such as, for example, TWEEN-80 and SPAN-20), oleyl alcohol, glycerol ester, sorbitol, and carboxy methoxy cellulose or an ionic surfactant such as, for example, sodum dodecyl sulfonate, sodum dodecyl benzene sulfonate, oleic acid, albumin, ova-albumin, lecithin, natural lipids, and synthetic lipids.
  • the emulsion comprises water mixed with poly(vinyl alcohol) as the first components and poly(lactic acid) dissolved in organic solvent as the second component, and optionally, silicone oxide nanoparticle having a biomolecule attached to the nanopatricle's surface as the third component.
  • the invention also provides a fiber manufactured by the method of the invention as described above, wherein the morphology of the fiber is controlled by varying a ratio of the first component to the second component.
  • a non-limiting example of the desired fiber is a fiber made from the emulsion comprising water, poly(lactic acid), and optionally a nanoparticle comprising silicone oxide and a biomolecule.
  • the diameter of the fiber is from about 3 nm to 10 micrometers.
  • the invention provides an improvement to the known methods of making a fiber by electrospinning, wherein a fiber is formed by extruding a fiber-forming medium, such as a polymeric composition, from a vessel through an orifice under the influence of a force.
  • the fiber-forming medium comprises an emulsion comprising (1) a first component comprising water, said first component is provided in an amount of at most 20 vol. %, and (2) a second component comprising a polymer, said second component is provided in an amount of at least 80 vol. %, on a condition that the first component has a first evaporation rate and the second component has a second evaporation rate and wherein the second evaporation rate is higher than the first evaporation rate.
  • EXAMPLE As a non-limiting example, the invention will be described based on the effect of a water/oil emulsion on the morphology of poly(L-lactic acid) (PLA) fibers obtained by ES.
  • Poly(vinyl alcohol) (MW 10,000, 85% hydrolyzed) (PVA) and 1-methyl-
  • NMP NMP is added to the mixture to serve as a phase compatibilizer (NMP is soluble in both water and chloroform) and to retard the evaporation of chloroform (oil phase).
  • Formulations containing varying amounts of aqueous phase and PVA and PLA were studied and are shown in Table 1.
  • silica colloids ⁇ 1% v/v were added to some of the formulations. All components were metered using an Eppendorf pipette, mixed by vortexing and sonicated for 45 seconds (20 KHz, Vibra Cell, Sonic Systems) to ensure full emulsification. Table 1 Description of Composition of Samples
  • the polymer solution typically volume 1 ml
  • the syringe was mounted on a ring stand at a 45° angle below horizontal.
  • the needle was connected to a high voltage power supply (Gamma High Voltage Research, Ormond Beach, FL).
  • the counter electrode was connected to an aluminum foil (collecting target) placed at a distance of 15 cm away from the tip of the needle. The bias between each plate was then slowly increased until the eruption of the "Taylor Cone" and was then set at 25 kV. Fibers were collected on the aluminum foil until the solution was fully dispensed.
  • Electrospun fibers were imaged using a JEOL 6300FV field emission scanning electron microscope at an acceleration voltage of 10 KeV (see Figs. 2-9). Samples were mounted onto aluminum stubs using conductive carbon tape and then sputter coated with Pd-C to minimize charging. TIFF files of the images were then imported into Scion Image (NTH, Bethesda, MD) for analysis. W/O emulsions of PLA dissolved in a chloroform/NMP mixture and water, stabilized by PVA, were used as a model two-phase system to study its effect on fiber mo ⁇ hology in the ES process.
  • the polymer fraction which constitutes the vast majority undergoes solidification due to the evaporation of the volatile organic phase (chloroform) and the resulting fiber stretches as it approaches the target, while the aqueous phase remains entrapped within the rapidly solidifying polymer (oil) phase.
  • the aqueous droplets become regions of instability toward the later stage of solidification as it constitutes a larger portion of the liquid phase, and a surface tension driven phase segregation process can result yielding porous fibers upon the evaporation of the aqueous component.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

L'invention concerne une fibre présentant une morphologie différente ainsi qu'un procédé de fabrication de ladite fibre de manière prévisible. Le procédé consiste à utiliser un premier composant contenant de l'eau, le premier composant présentant un premier taux d'évaporation, à utiliser un second composant comprenant un polymère, le second composant présentant un second taux d'évaporation, à condition que le second taux d'évaporation soit supérieur au premier taux d'évaporation, à combiner le premier composant et le second composant afin d'obtenir une émulsion, à appliquer une force sur l'émulsion et à extruder l'émulsion afin de fabriquer la fibre, la fibre présentant une surface extérieure, une cavité intérieure et un diamètre inférieur ou égal à 10 micromètres.
PCT/US2005/009048 2004-03-25 2005-03-17 Controle base sur une emulsion de morphologie de fibres electrofilees WO2005098099A1 (fr)

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US10/594,094 US20070141333A1 (en) 2004-03-25 2005-03-17 Emulsion-based control of electrospun fiber morphology

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US55663704P 2004-03-25 2004-03-25
US60/556,637 2004-03-25

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WO2008030457A2 (fr) * 2006-09-06 2008-03-13 Corning Incorporated Nanofibres, nanofilms et procédés de fabrication/utilisation correspondants
WO2008093342A2 (fr) 2007-02-01 2008-08-07 Technion Research & Development Foundation Ltd. Fibres et tissus d'albumine et leurs procédés de génération et d'utilisation
EP2129517A1 (fr) * 2007-03-26 2009-12-09 The University of Connecticut Charpentes nanocomposites de polymères d'apatite électrofilées
WO2010014158A2 (fr) * 2008-07-31 2010-02-04 Corning Incorporated Nanofibres et procedes de fabrication associes

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US7901611B2 (en) * 2007-11-28 2011-03-08 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method for predicting and optimizing system parameters for electrospinning system
TR201810406T4 (tr) * 2014-04-07 2018-08-27 Trevira Gmbh Gelişmiş dağılabilirliğe sahip polimer lif.
US10124310B2 (en) 2014-10-27 2018-11-13 University Of Massachusetts Micro- and nano-particles with variable surface morphologies and methods of making same

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008030457A2 (fr) * 2006-09-06 2008-03-13 Corning Incorporated Nanofibres, nanofilms et procédés de fabrication/utilisation correspondants
WO2008030457A3 (fr) * 2006-09-06 2008-07-24 Corning Inc Nanofibres, nanofilms et procédés de fabrication/utilisation correspondants
JP2010502855A (ja) * 2006-09-06 2010-01-28 コーニング インコーポレイテッド ナノファイバー、ナノフィルムおよびそれらの製造／使用方法
WO2008093342A2 (fr) 2007-02-01 2008-08-07 Technion Research & Development Foundation Ltd. Fibres et tissus d'albumine et leurs procédés de génération et d'utilisation
EP2478924A1 (fr) 2007-02-01 2012-07-25 Technion Research & Development Foundation Fibres et tissus d'albumine et leurs procédés de génération et d'utilisation
EP2129517A1 (fr) * 2007-03-26 2009-12-09 The University of Connecticut Charpentes nanocomposites de polymères d'apatite électrofilées
EP2129517A4 (fr) * 2007-03-26 2012-11-21 Univ Connecticut Charpentes nanocomposites de polymères d'apatite électrofilées
WO2010014158A2 (fr) * 2008-07-31 2010-02-04 Corning Incorporated Nanofibres et procedes de fabrication associes
WO2010014158A3 (fr) * 2008-07-31 2010-04-08 Corning Incorporated Nanofibres et procedes de fabrication associes

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